**Abstract**

Biochar is a carbon-rich material produced from the pyrolysis of organic biomasses in the absence of oxygen or under low-oxygen conditions. Biochar has received a great interest during the last few decades due to its beneficial roles for carbon dioxide capturing and soil fertility improvement. However, applications of biochar in arid soils are very limited, and there is a lack of knowledge on practical aspects of adding biochar to arid soils. In this chapter, we will focus on biochar applications in the Kingdom of Saudi Arabia soils as an example of arid soils. These soils are characterized by several marks, i.e., high soil pH, sand structures, high CaCO3 contents, and low soil fertility. In addition, the unsuccessful recycling practices of agricultural and food wastes in the Kingdom of Saudi Arabia are also discussed. This chapter provides an overview of current biochar knowledge pertinent to its application to arid soils, summarizes what is known so far about biochar and its applications in arid regions, and demonstrates the possible strategies that can be used for enhancing the practices of biochar addition to these soils.

**Keywords:** biochar, carbon sequestration, soil fertility, applications, limitations

### **1. Introduction**

Soil formation is a complex process resulting from long-term interactions among several environmental factors, i.e., climate, soil-forming processes, and land uses [1]. Such processes influence soil's physical, chemical, and biological characteristics and hence affect soil productivity [2]. In arid and semiarid regions, many challenges may face soil productivity; for example, many arid soils are of light texture with low organic matter and nutrient contents [3–5]. These soils exhibit low soil aggregation and can, therefore, be subjected easily to wind erosion [6]. Moreover, secondary minerals may dominate in such soils like calcite and gypsum [1], and these minerals can significantly diminish soil fertility [7, 8]. Another important threat that faces agricultural sustainability in arid sand semiarid soils is soil salinity [9]. Generally, the term arid or semiarid refers to the regions of limited rainfall and high evapotranspiration [10]. Areas with mean annual precipitation (MAP) ranging from 100 to 250 mm yr−1 are called arid climatic zones, while areas with MAP ranging between 250 and 600 mm yr−1 are called semiarid zones [11]. These two climatic regions cover approximately 30% or more of the total earth's surface [12]. To improve the productivity of low-fertility soils, organic applications should

therefore be incorporated within the top soil [13, 14] to raise soil contents of both C and nutrients [14]. However, the negative implications of using easily decomposed organic amendments on the environment should be taken into account, e.g., emissions of greenhouse that possesses global warming [15]. Accordingly, biochar might be the appropriate organic amendments to improve the characteristics of such soils but decrease the emissions of greenhouse gases on the other hand. In the following section, we will discuss the distribution of arid and semiarid soil and the potentialities of using biochar to improve soil properties and attain sustainability in crop production


3. Efficacy of biorational insecticides on Liriomyza sativae Blanchard without totally inhibiting the presence of the parasitoids

The leaf miner species present in the chickpea is Liriomyza sativae Blanchard. The aedeagus presents a barely conspicuous constriction (Figure 1A), where the edges of the distifalo have only a slight undulation. The ejaculatory pump apodema has a thin base that is wider at the distal end than the diameter of the bulb (Figure 1C).

Biorational Insecticides and Diatomaceous Earth for Control Sustainability of Pest in Chickpea and Mexican… http://dx.doi.org/10.5772/intechopen.71534 5

While in the entomology laboratory of the same, faculty research was done to determine the efficacy of diatomaceous earth doses, where the colony of beans weevil (Zabrotes subfasciatus Boheman) was purified in glass bottles with a capacity of 5 kg, which were kept under a temperature that fluctuated between 30 and 35�C, with a purpose of having a homogeneous

To establish the tests; polystyrene beakers with capacity of 500 g, and 2 kg of bean per treatment were used; the application of the diatomaceous earth was homogenized on the grain, then 20 adults of bean weevil were deposited in each repetition and covered with organza cloth. The investigation was carried out in two phases: (a) the first one was done in a completely random design with seven treatments and four repetitions. The treatments were diatomaceous earth at doses of 1.0, 2.0, 3.0, 4.0, and 5.0 g kg�1 of seed, a chemical control (deltamethrin) at a dose of 1.0 mL kg�1 of seed, plus an absolute control (without application of substances); (b) the second phase consisted of another completely random experimental design with the same amount of treatments and repetitions, but with the doses of 0.2, 0.4, 0.6, 0.8, and 1.0 g kg�1 of diatomaceous earth, a chemical control (deltamethrin) at a dose of 0.1 mL kg�1 of seed plus the absolute

In the both phases of the experiment, the response variables were the percentage of dead adults and the germination of bean seeds. In the first phase, mortality was determined with the number of live and dead insects in each experimental unit, at 15, 30, 45, and 60 days after application (daa), while in the second phase, it was done at 10, 20 30, and 40 daa. With the averages of mortality in each experimental unit, the percentage of effectiveness was obtained

Corrected mortality ¼ mortality of the treatment–mortality of the absolute control � 100

Germination was evaluated with 100 bean seeds planted in polystyrene trays filled with peat moss and determined at 10, 20 and 30 daa of the diatomaceous earth and deltamethrin doses, counting the seedlings emerged in each of the experimental units and comparison of averages with respect at average of the absolute control, while percentages were also determined with the equation of Abbott [24]. All data were subjected to an analysis of variance and multiple

comparison of means of Tukey test (α = 0.05) of the statistical package SAS 9.1 [23].

without totally inhibiting the presence of the parasitoids

distal end than the diameter of the bulb (Figure 1C).

3. Efficacy of biorational insecticides on Liriomyza sativae Blanchard

The leaf miner species present in the chickpea is Liriomyza sativae Blanchard. The aedeagus presents a barely conspicuous constriction (Figure 1A), where the edges of the distifalo have only a slight undulation. The ejaculatory pump apodema has a thin base that is wider at the

100 � mortality of the absolute control

colony for the test.

4 Insecticides - Agriculture and Toxicology

control.

by the following Eq. [24]:

Figure 1. Liriomyza Sativae: (A) aedeagus ventral view, (B) aedeagus side view, and (C) sperm pump.

Based on the final averages of the two experiments (Table 1), it could be interpreted that after applying the biorational insecticides, chlorantraniliprole, cyromazine, and spinosad, twice as well as the conventional insecticide, chlorpyrifos, there was no statistical difference between the efficacy of the biorationals and that of the conventional one, and live larval populations of L. sativae were reduced to 43, 33, 22, and 39%, respectively, compared to the 100% presence of larvae in the foliage on average in the absolute control in the cycle 2013, while in 2014, the respective decreases were 55, 47, 45, and 46%. The tendency of the population of L. sativae to stay below the economic threshold in the two experiments, from the second application, was perhaps due to the physiological maturity of the chickpea approaching the senescence of the foliage and, consequently, to the harvest grain.

According to the final averages of Table 2, in 2013, the percentage of empty mines was reduced to 29, 37, 11, and 29% with chlorantraniliprole, cyromazine, spinosad, and chlorpyrifos, respectively, compared with 100% represented by the average of the control. In 2014, the respective decreases were 19, 3, 16, and 22% with the same treatments. In addition, the time of action of biorationals was very similar to that of chlorpyrifos. The results allowed to corroborate that the biorationals are products that can be used for the control of L. sativae with the same effectiveness of the conventional insecticide chlorpyrifos.

 Average adult leaf miner Liriomyza sativae Blanchard in 40 chickpea leaves in Culiacan, Sinaloa, Mexico.

Treatments February 2013 March 2013 Final

Chlorantraniliprole 20.1 9.7b 9.9b 5.1b 2.8b 20.4 8.4b 4.5b 8.7b Cyromazine 20.2 9.1b 5.9bc 6.6b 5.0b 20.1 7.5b 8.1b 8.9b Spinosad 20.1 12.2b 4.9c 8.6b 4.6b 22.1 8.0b 8.6b 9.9b Chlorpyrifos 21.2 9.3b 4.2c 6.2b 3.2b 22.0 8.9b 9.5b 9.0b Absolute control 20.9 22.7a 22.1a 22.6a 31.2a 25.8 21.8a 23.9a 24.3a

73 14 212 28 7 14 22 28

Table 4. Percentage of damage by leaf miner Liriomyza sativae Blanchard in leaf chickpea plants. Culiacan, Sinaloa, Mexico.

Chlorantraniliprole 11.2ab 9.8bc 20.2 13.9 9.7 8.9 9.4b 7.9d 11.4d Cyromazine 16.4ab 14.8ab 21.0 19.7 7.6 11.1 9.3b 10.9cd 13.8bc Spinosad 18.5a 13.8ab 21.3 16.8 6.7 14.9 12.4ab 15.4b 15.0b Chlorpyrifos 11.1b 8.0c 20.4 16.0 8.6 12.3 10.5ab 14.3bc 12.7c Absolute control 20.3ab 20.2a 20.4 20.1 20.2 20.2 20.9a 22.2a 20.5a

February 2014 March 2014

71 14 21 28 7 142 22 28 Average

February 2014 March 2014

\*Means with the same letter in each column are statistically the same (Duncan α ≤0.05).

\*Means with the same letter in each column are statistically the same (Duncan α ≤0.05).

1

2

3

1

2

3

Two days before the first application.

Five days after the first application.

Two days before the second application.

Two days before the first application.

Five days after the first application.

Two days before the second application.

71 14 21 28 7 142 22 28 Average

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7

Biorational Insecticides and Diatomaceous Earth for Control Sustainability of Pest in Chickpea and Mexican…

\* Means with the same letter in each column are statistically the same (Duncan α ≤0.05).

1 Two days before the first application.

2 Two days before the second application.

3 Five days after the first application.

Table 1. Average live larvae of leaf miner Liriomyza sativae Blanchard in 40 chickpea leaves in Culiacan, Sinaloa, Mexico.

\*Means with the same letter in each column are statistically the same (Duncan α ≤0.05).

1 Two days before the first application.

2 Two days before the second application.

3 Five days after the first application.

Table 2. Average empty mines of leaf miner Liriomyza sativae Blanchard in 40 chickpea leaves in Culiacan, Sinaloa, Mexico.

Biorational Insecticides and Diatomaceous Earth for Control Sustainability of Pest in Chickpea and Mexican… http://dx.doi.org/10.5772/intechopen.71534 7

\*Means with the same letter in each column are statistically the same (Duncan α ≤0.05).

1 Two days before the first application.

Treatments February 2013 March 2013 Final Average

71 14 21 28 7 142 22 28

73 14 212 28 7 14 22 28

Table 1. Average live larvae of leaf miner Liriomyza sativae Blanchard in 40 chickpea leaves in Culiacan, Sinaloa, Mexico.

Treatments February 2013 March 2013 Final average

71 14 21 28 7 142 22 28

73 14 212 28 7 14 22 28

Table 2. Average empty mines of leaf miner Liriomyza sativae Blanchard in 40 chickpea leaves in Culiacan, Sinaloa, Mexico.

Chlorantraniliprole 2.58b 0.28b 1.08 1.68 1.10 3.20ab 3.05 2.43ab 1.92b Cyromazine 2.20b 0.98ab 1.45 1.38 0.83 3.93a 3.88 3.68a 2.29ab Spinosad 3.53a 1.33a 1.23 1.63 0.83 2.08b 2.55 2.70ab 1.98ab Chlorpyrifos 1.35c 0.85ab 1.50 1.13 1.10 3.75a 2.85 2.25b 1.84b Absolute control 2.78ab 1.93a 1.45 1.48 1.28 3.40ab 3.28 3.43ab 2.37a

Chlorantraniliprole 1.58 1.73 1.03a\* 0.38ab 0.83 0.65 1.33 0.98bc 0.99bc Cyromazine 1.30 1.30 0.68ab 0.60a 0.78 1.00 1.15 0.70c 0.88c Spinosad 1.38 1.58 0.80ab 0.85a 1.18 1.13 1.68 1.50a 1.24ab Chlorpyrifos 1.28 1.70 0.38b 0.08b 1.30 1.33 1.23 0.95bc 0.99bc Absolute control 1.38 1.78 1.38a 0.85a 1.33 1.38 1.95 1.15ab 1.40a

February 2014 March 2014

Chlorantraniliprole 0.70ab 1.60 2.65b 0.83b 1.58 1.20 1.00 1.05b 1.32b Cyromazine 0.78ab 1.80 2.70b 0.73b 1.85 1.20 1.88 1.68b 1.57b Spinosad 1.58ab 1.83 2.75b 0.85b 1.35 1.98 1.40 1.25b 1.62b Chlorpyrifos 0.75b 1.85 3.85a 1.00ab 1.88 1.25 1.03 1.05b 1.58b Absolute control 3.90a 3.83 3.68a 2.03a 2.68 2.30 2.13 3.10a 2.95a

Chlorantraniliprole 2.30 1.65 0.20bc\* 0.35b 1.65 3.95 0.40b 0.05b 1.17b Cyromazine 2.20 1.85 0.30b 0.55b 1.75 3.80 0.70ab 0.75ab 1.38b Spinosad 2.00 1.85 0.75a 0.80ab 1.90 4.15 0.40b 1.30a 1.59ab Chlorpyrifos 2.30 1.15 0.10c 0.35b 1.65 3.70 0.20b 1.60a 1.25b Absolute control 2.35 2.30 0.75a 1.55a 1.90 3.95 2.00a 1.90a 2.05a

February 2014 March 2014

Means with the same letter in each column are statistically the same (Duncan α ≤0.05).

\*Means with the same letter in each column are statistically the same (Duncan α ≤0.05).

\*

1

2

3

1

2

3

Two days before the first application.

Five days after the first application.

Two days before the second application.

Two days before the first application.

Five days after the first application.

Two days before the second application.

6 Insecticides - Agriculture and Toxicology

2 Two days before the second application.

3 Five days after the first application.

Table 3. Average adult leaf miner Liriomyza sativae Blanchard in 40 chickpea leaves in Culiacan, Sinaloa, Mexico.

\*Means with the same letter in each column are statistically the same (Duncan α ≤0.05).

1 Two days before the first application.

2 Two days before the second application.

3 Five days after the first application.

Table 4. Percentage of damage by leaf miner Liriomyza sativae Blanchard in leaf chickpea plants. Culiacan, Sinaloa, Mexico.

It was observed in 2013 that the number of adults of the leaf miner emerged from leafs decreased to 39, 39, 12, and 26%, with chlorantraniliprole, cyromazine, spinosad, and chlorpyrifos, with respect to 100% of the absolute control (Table 3). In 2014, it was decreased to 45, 66, 10, and 25%. The above was to be expected, since the same effect had been observed in the number of live larvae and empty mines. In this way, the results of this research can help

Biorational Insecticides and Diatomaceous Earth for Control Sustainability of Pest in Chickpea and Mexican…

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9

The percentage of folioles damaged after application of insecticides in 2013 indicates that, with chlorantraniliprole, cyromazine, and spinosad, the damage decreased to 64, 63, and 59, respectively (Table 4), while chlorpyrifos was 63%. In 2014, the damages decreased to 44, 33, 27, and

The parasitoids obtained from the leaf miner of the chickpea were Opius spp. (Braconidae), Diglyphus spp., Neochrysocharis spp., and Closterocerus spp. (Eulophidae) (Table 5). In 2013, the leaf miner parasitism was 1% where spinosad was applied, 4% in plots treated with chlorpyrifos, 8% with cyromazine, and 14% in plots managed with chlorantraniliprole, compared to the average of 19% of observed parasitism in the control plot. In 2014, the parasitism was 2, 3, 2, and 11%, respectively, and in the control 12%. Three types of parasitoids found and the percentage of parasitism in the chickpea, with respect to what was observed in the absolute control, coincide with the results [26]; since 2006 and 2007, they found parasitoids Opius monilicornis,

The estimate of net utility was determined by considering the value of production minus the cost of the crop, minus the value of the insecticides. The value of the ton of chickpea taken into account for operations was MX\$ 12,700. In 2013, the highest production of chickpea was obtained where chlorantraniliprole was applied, with a net utility of MX\$ 21,011, surpassing it to control with 71%, since its net utility was MX\$ 12,305. With chlorpyrifos, spinosad, and cyromazine, a production was obtained that surpassed to control in 53, 48, and 37%, respec-

In 2014, the highest production of chickpea was also obtained from the plots applied with chlorantraniliprole, from where a net utility of MX\$ 16,036 was obtained, surpassing the control with 45%, whose net utility was MX\$ 11,083. With chlorpyrifos, spinosad, and cyromazine, the respective increases were 39, 34, and 21%. Utility differences from 1 year to other may be due to

4. Efficiency of diatomaceous earth for control of Mexican bean weevil

The results show that all doses of diatomaceous earth (DE) exerted an excellent control, such that in the evaluations registered at 15 days after application; 100% mortality was recorded in

The doses of 2.0 and 3.0 g kg1 of DE caused 95 and 96% mortality, in adults of Zabrotes subfasciatus. The dose of 1.0 g of DE caused 93% mortality, without statistical differences

, similar to those observed with the chemical control (deltamethrin).

the higher incidence and damage of Liriomyza sativae Blanchard in 2014.

increase local awareness to reduce the use of broad-spectrum insecticides [25].

38%, respectively, in relation to 100% of the absolute control.

Diglyphus crassinervis and Neochrysocharis ambitiosa.

(Zabrotes subfasciatus Boheman)

doses 4.0 and 5.0 g kg1

tively.

LLs = Larvae of L. sativae, Ptoid = Parasitoid, and Ptism = Parasitism.

Table 5. Parasitoid species and parasitism (%) of larvae of Liriomyza sativae Blanchard in 400 chickpea leaves. Culiacan, Sinaloa, Mexico.

It was observed in 2013 that the number of adults of the leaf miner emerged from leafs decreased to 39, 39, 12, and 26%, with chlorantraniliprole, cyromazine, spinosad, and chlorpyrifos, with respect to 100% of the absolute control (Table 3). In 2014, it was decreased to 45, 66, 10, and 25%. The above was to be expected, since the same effect had been observed in the number of live larvae and empty mines. In this way, the results of this research can help increase local awareness to reduce the use of broad-spectrum insecticides [25].

Treatments Parasitoid species Total

LLs 74

Ptism 0 9.45 2.70 1.35 14 LLs 37

Ptism 0 2.70 2.70 2.70 8 LLs 75

Ptism 0 1.33 0 0 1 LLs 184

Ptism 0 3.26 0 0.54 4 LLs 116

Ptism 12.9 0 6.03 0 19

LLs 325

Ptism 3.08 0.31 0 7.69 11 LLs 242

Ptism 2.07 0.41 0 0 2 LLs 318

Ptism 0.63 0.63 0 0.63 2 LLs 392

Ptism 2.55 0 0 0.51 3 LLs 240

Ptism 4.1 0 0 8.3 12

2013 Neochrysocharis spp. Opius spp. Closterocerus spp. Diglyphus spp.

Chlorantraniliprole Ptoid 0 7 2 1 10

Cyromazine Ptoid 0 1 1 1 3

Spinosad Ptoid 0 1 0 0 1

Chlorpyrifos Ptoid 0 6 0 1 7

Absolute control Ptoid 15 0 7 0 22

Chlorantraniliprole Ptoid 10 1 0 25 36

Cyromazine Ptoid 5 1 0 0 6

Spinosad Ptoid 2 2 0 2 6

Chlorpyrifos Ptoid 10 0 0 2 12

Absolute control Ptoid 10 0 0 20 30

Table 5. Parasitoid species and parasitism (%) of larvae of Liriomyza sativae Blanchard in 400 chickpea leaves. Culiacan,

LLs = Larvae of L. sativae, Ptoid = Parasitoid, and Ptism = Parasitism.

2014

8 Insecticides - Agriculture and Toxicology

Sinaloa, Mexico.

The percentage of folioles damaged after application of insecticides in 2013 indicates that, with chlorantraniliprole, cyromazine, and spinosad, the damage decreased to 64, 63, and 59, respectively (Table 4), while chlorpyrifos was 63%. In 2014, the damages decreased to 44, 33, 27, and 38%, respectively, in relation to 100% of the absolute control.

The parasitoids obtained from the leaf miner of the chickpea were Opius spp. (Braconidae), Diglyphus spp., Neochrysocharis spp., and Closterocerus spp. (Eulophidae) (Table 5). In 2013, the leaf miner parasitism was 1% where spinosad was applied, 4% in plots treated with chlorpyrifos, 8% with cyromazine, and 14% in plots managed with chlorantraniliprole, compared to the average of 19% of observed parasitism in the control plot. In 2014, the parasitism was 2, 3, 2, and 11%, respectively, and in the control 12%. Three types of parasitoids found and the percentage of parasitism in the chickpea, with respect to what was observed in the absolute control, coincide with the results [26]; since 2006 and 2007, they found parasitoids Opius monilicornis, Diglyphus crassinervis and Neochrysocharis ambitiosa.

The estimate of net utility was determined by considering the value of production minus the cost of the crop, minus the value of the insecticides. The value of the ton of chickpea taken into account for operations was MX\$ 12,700. In 2013, the highest production of chickpea was obtained where chlorantraniliprole was applied, with a net utility of MX\$ 21,011, surpassing it to control with 71%, since its net utility was MX\$ 12,305. With chlorpyrifos, spinosad, and cyromazine, a production was obtained that surpassed to control in 53, 48, and 37%, respectively.

In 2014, the highest production of chickpea was also obtained from the plots applied with chlorantraniliprole, from where a net utility of MX\$ 16,036 was obtained, surpassing the control with 45%, whose net utility was MX\$ 11,083. With chlorpyrifos, spinosad, and cyromazine, the respective increases were 39, 34, and 21%. Utility differences from 1 year to other may be due to the higher incidence and damage of Liriomyza sativae Blanchard in 2014.


*2.3.3 Biochemical features and diagnostic biomarkers*

The key biochemical features of HP2 are elevated plasma and urinary levels of proline (about 10–15 folds higher in plasma) and P5C. A combination of both biomarkers is diagnostic of HP2 and distinguishes it from hyperprolinemia type 1 [119, 120]. Walker and Mills [121] identified a new metabolite,

#### **Figure 7.**

*L-Proline metabolic pathway. In HP2, inactivation of P5CD causes accumulation of the upstream metabolite P5C (red arrows). P5C spontaneously condenses with the enzymatic cofactor PLP leading to the formation of inactive adducts and depletion of the cofactor. GSA: glutamic-gamma-semialdehyde, ORN: ornithine, NAD(P): nicotinamide adenine dinucleotide (phosphate), POX: proline oxidase, P5CR: P5C reductase, P5C: pyrroline 5-carboxylate, OAT: ornithine aminotransferase, P5CD: P5C dehydrogenase, P5CS: P5C synthase. (Based on [63, 113]).*

N-(pyrrole-2-carboxyl) glycine, that accumulated in urine of HP2 subject. They subsequently confirmed the presence of this compound in another 4 patients and suggested its use as a diagnostic biomarker for HP2. Other metabolic alterations reported in HP2 patients include increased plasma concentrations of lactate [116, 119], glycine [115, 120], ornithine [120], and alanine [119] and urinary xanthurenic acid; probably secondary to PLP deficiency [59]. VitB6 was previously analyzed in 5 HP2 patients [59, 116, 119] and found to be decreased in 3 patients and at low normal levels in the other two.

#### *2.3.4 Treatment and its outcome*

VitB6 supplementation has been used to treat HP2 associated seizures with variable response. Most of the case studies reported effective control of seizures with vitB6, either alone or in conjugation with anti-seizure medications [59, 114, 116], while few described irresponsiveness to vitB6 therapy [119]. Van de Ven et al. [119] assessed the long-term clinical outcome in 4 HP2 patients treated with vitB6 and/or anti-seizure medications. Seizures resolved spontaneously in 3 patients by the age of 12–18 years, however, neurobehavioral problems were persistent in most patients despite therapy. The clinical course was non-progressive and did not correlate with the vitB6 dose and vitB6 therapy [119].

#### **2.4 Hypophosphatasia**

#### *2.4.1 Disease mechanism*

Hypophosphatasia (HPP) results from autosomal recessive or dominant mutations affecting *ALPL*, the gene encoding tissue nonspecific alkaline phosphatase (TNSALP). TNSALP is an ecto-enzyme that is highly expressed in bone, liver, kidney and developing teeth [122, 123]. The enzyme catalyzes extracellular dephosphorylation of multiple substrates including inorganic pyrophosphate (PPi), phosphoethanolamine (PEA), and PLP (**Figure 3**) [122, 124]. On the osteoblast membrane, TNSALP hydrolyzes PPi into inorganic phosphate (Pi). Together with calcium ions (Ca2+), Pi is required for the synthesis of hydroxyapatite (HA) which is the major inorganic constituent of bones and teeth. In HPP, TNSALP deficiency leads to extracellular accumulation of PPi which impairs the formation of HA and proper bone mineralization leading to an array of skeletal abnormalities [122, 123]. TNSALP is also required for the extracellular hydrolysis of PLP to PL to facilitate its entry into the cell which explains the occurrence of intracellular PLP deficiency and vitB6-dependent seizures in some forms of HPP [123, 124].

#### *2.4.2 Clinical features*

There is a remarkable heterogeneity in the clinical presentation of HPP and 5 principal clinical types have been recognized based on skeletal disease features and age of onset. In order of escalating severity, these types are "odonto", "adult", "childhood", "infantile", and "perinatal" HPP [124, 125]. The severe forms (infantile and perinatal) show autosomal recessive inheritance, while in the milder forms both autosomal dominant or recessive inheritance has been described [124, 126]. Defective mentalization of bone and/or teeth is the clinical hallmark feature of HPP in all of these types [127]. Seizures are the most well described extra-skeletal feature of HPP and are exclusively observed in the infantile and perinatal types [128]. According to a recent metanalysis [128], seizures occurred in about 20% of patients with pediatric-onset HPP.

#### *Vitamin B6 and Related Inborn Errors of Metabolism DOI: http://dx.doi.org/10.5772/intechopen.99751*

Odonto-HPP is the mildest form and can manifest at any age. It involves minor dental problems like premature shedding of deciduous teeth without any other symptoms [123, 124]. Adult HPP typically manifest during middle age or later and can cause debilitating symptoms like osteomalacia leading to bone fractures, chondrocalcinosis, musculoskeletal pain and loss of dentition. Some patients also suffer from pseudogout due to increased extracellular concentrations of PPi [123, 126]. Childhood HPP presents after the age of 6 months and common features include rickets and premature loss of deciduous teeth. Severe forms are also associated with muscle weakness causing delay in walking and abnormal gait [125]. Infantile HPP is a severe type and can lead to death in about 50% of affected infants [123]. It is diagnosed before 6 months of age and features delayed postnatal development, failure to thrive, hypotonia along with rachitic deformities [125]. Hypercalcemia and hypercalciuria are frequently seen and may lead to renal failure [126]. In rapidly progressive cases, rickets causes thoracic deformity and death may ensue due to respiratory insufficiency [125, 129]. VitB6-dependent seizures may develop, sometimes preceding the skeletal features, and usually predict a fatal outcome [123, 125]. Perinatal HPP is the most severe type in which the symptoms start *in utero* or at birth and almost always lead to lethal outcome. Skeletal hypomineralization is profound and causes deformities such as caput membranaceum, wide fontanels and short limb dwarfism [123, 125, 130]. Chest malformation followed by pulmonary compromise is also a common fatal consequence of the rachitic disease [126]. Additional features described in this extreme form of HPP comprise vitB6 dependent seizures, apnea, irritability, myelophthisic anemia and intracranial hemorrhage [123].

## *2.4.3 Biochemical features and diagnostic biomarkers*

HPP can be diagnosed by the presence of pathognomonic skeletal radiographic changes along with characteristic biochemical features. The most commonly used biochemical marker for HPP is low serum alkaline phosphatase activity which consistently observed in all forms of HPP [126]. Other reported biochemical findings in HPP include increased levels of TNSALP substrates PPi and PEA in urine, elevated Pi in plasma, hypercalciuria and/or hypercalcemia and high urinary levels of phosphoserine [6, 123, 124, 126]. These features can only be used to support the diagnosis of HPP because they may not be present in all HPP forms and are sometimes observed in other skeletal diseases. A more sensitive and specific biomarker for HPP is elevated serum levels of PLP, which has been detected even in the mildest form of HPP (odonto-HPP) and the degree of PLP elevation seems to correlate with disease severity [123, 131].

## *2.4.4 Treatment and its outcome*

HPP-related seizures are usually responsive to PN supplementation [56, 129]. Effective treatment against the skeletal manifestations was lacking until the advent of Asfotase alfa, an enzyme-replacement therapy that was approved in 2015 [124, 126]. Asfotase alfa is recombinant, fusion protein consisting of the catalytic ectodomain of human TNSALP, the Fc fragment of human immunoglobulin G1 (IgG1) and a deca-aspartate motif for bone targeting [123, 131, 132]. Clinical trials have demonstrated the long-term safety and efficacy of Asfotase alfa in preventing life-threatening complications of HPP [123, 132, 133]. HPP patients, including those with severe forms, treated with Asfotase alfa showed marked improvements in all clinical aspects (radiography, pulmonary, neurodevelopmental and motor functions) along with resolution of pain and disability

[123, 126, 133]. At the biochemical level, Asfotase alfa therapy was associated with normalization of plasma levels of PPi and PLP [133].

### **2.5 PLPHP deficiency**

#### *2.5.1 Disease mechanism*

PLPHP deficiency is the latest addition to B6EEs that is caused by recessive mutations in *PLPBP*, a gene previosly known as proline synthetase co-transcribed homolog (*PROSC*) [7]. The product of this gene, known as PLP homeostasis protein (PLPHP), belongs to a highly conserved family of proteins known to bind PLP. The function of these PLP-binding proteins in humans as well as other species is poorly understood. Their structures have remarkable similarity with a bacterial enzyme known as alanine racemase [134]. An insight into the function of this protein came from ananlysis of samples from PLPHP-deficient pateints which showed a widely deranged vitB6 vitamer profile. It has therefore been suggeseted that this protein plays an imprtant role in vitB6 homeostasis [7, 68]. However, the exact mechanism of how PLPHP dysfunction disrupts PLP homeostasis and leads to the observed epileptic encephalopathy is still unknown. Darin et al. [7] hypothesized that PLPHP is a PLP-carrier that protects the reactive cofactor from binding to other cellular molecules, shields it from degradative enzymes like phosphatases and securely delivers it to PLP-dependent enzymes.

#### *2.5.2 Clinical features*

The general clinical picture of PLPHP deficiency remarkably overlaps with that of ALDH7A1 deficiency and PNPO deficiency which is dominated by pharmacoresistant seizures that respond to vitB6 treatment. Seizures typically manifest during the first week of life [7, 67, 68, 135] with possible prenatal onset in some cases [68] and a recent report of late onset at 14 months of age [136]. Johnstone et al. [68] reported two patients who presented with fatal mitochondrial encephalopathy and a patient with unique movement disorder who lacked epileptic seizures. Developmental delay, intellectual disability, acquired microcephaly and structural brain abnormalities are common co-morbidities observed in this form of B6EEs [7, 67, 68, 137–139]. Systemic features like metabolic acidosis, anemia and gastrointestinal problems have been also described in PLPHP-deficient pateints [7, 67].

### *2.5.3 Biochemical features and diagnostic biomarkers*

Biochemical investigations performed in patient samples revealed amino acid and neurotransmitter abnormalities, reflecting the pleiotropic metabolic effects associated with altered PLP homeostasis. Among amino acids, elevated glycine in plasma and/or CSF was the most frequent alteration identified [7, 67, 68]. The enzyme that breaks down glycine, glycine cleavage system, requires PLP as a cofactor [140]. Abnormal monoamine neurotransmitter profile was detected in some patients, possibly due to suboptimal activity of the PLP-dependent enzyme AADC. Reported changes included low CSF levels of HVA (marker of low dopamine) and raised concentrations of 3-OMD, L-dopa, 5-HTP (CSF) and VLA (urine) indicating accumulation of AADC substrates [7, 67, 86]. Low PLP levels were detected in pretreatment plasma [68] and CSF [7] samples from two patients. Johnstone et al. [68] described accumulation of high levels of PNP in patient fibroblasts and PLPHPdeficient HEK293 cells. There is currently no established biomarker for this disease.


**3. Results**

Below we describe three new species previously recognized as candidate species [2,3]. However, as candidate species without a formal description they probably will not get legal protection. Legal protection is afforded for taxa with scientific names in a formal species description. Once candidate species have names, they will be available and can be incorporated into local protected and international conservation lists. For this reason, we describe three new species of *Liolaemus* lizards and we hope in the near future they will be evaluated and be part of a conservation program if needed.


**Mauricio Roche \*, Mikko Helle and Henrik Saxén**

Thermal and Flow Engineering Lab, Åbo Akademi University, 20500 Turku, Finland **\*** Correspondence<EMAIL_ADDRESS>
Received: 4 July 2019; Accepted: 5 August 2019; Published: 7 August 2019

**Abstract:** Monitoring and control of the blast furnace hearth is critical to achieve the required production levels and adequate process operation, as well as to extend the campaign length. Because of the complexity of the draining, the outflows of iron and slag may progress in different ways during tapping in large blast furnaces. To categorize the hearth draining behavior, principal component analysis (PCA) was applied to two extensive sets of process data from an operating blast furnace with three tapholes in order to develop an interpretation of the outflow patterns. Representing the complex outflow patterns in low dimensions made it possible to study and illustrate the time evolution of the drainage, as well as to detect similarities and differences in the performance of the tapholes. The model was used to explain the observations of other variables and factors that are known to be affected by, or affect, the state of the hearth, such as stoppages, liquid levels, and tap duration.

**Keywords:** hearth; drainage; PCA; analysis tool; pattern; tapholes


**2. Material and method**

The methodology is based on the study of patent citation and is divided into two stages. In the first stage, patent documents were retrieved with bibliometric analysis carried out through the PatSeer® commercial patent database. It uses keywords such as: alcohol, bioalcohol, ethanol, bioethanol, saccharum, sugarcane, "sugar cane," bagasse, cellulose, biomass, lignocellulose and molasses. In the title and summary fields, it used the extend family filter. The study made use of Boolean operators "OR," "AND" and words truncated with asterisk (\*). We covered the period between 2000 and 2018, according to the priority date. All the retrieved documents were classified according to the keywords in the title, summary and claim fields, which resulted in the following categories: (i) pretreatment with acid and enzymatic hydrolysis, (ii) fermentation with yeast, bacteria or non-yeast fungus, (iii) distillation and (iv) sugarcane.

The second step was the data analysis per se, composed by:

**15**

**Figure 1.**

*Technological Trajectories Studies of Sugarcane Ethanol Production Using Patent Citation*

(4) Analysis of the profile of main authors of "breakthrough inventions";

(6) Analysis of citations of the downstream of breakthrough inventions.

As highlighted in the methodology section, the technology focus of the study

It is worth highlighting again that, on industrial levels, ethanol is considered to be a very relevant biofuel for producer countries, and which can be obtained from various primary and secondary (lignocellulosic biomass types) sources, such as:

i.through the hydrolysis of starch of cereal grains (corn, sorghum, wheat,

*Distribution over time of patent documents related to the production of sugarcane ethanol, highlighting 301 highly cited documents. Period: 2000–2018. N = 2023. Source: Compiled by the authors, PatSeer® database.*

is the production of ethanol from sugarcane in its various first-generation (ethanol) and second-generation (bioethanol) modalities. The search strategy used retrieved 223 patent documents in the 2000–2018 period according to the year of priority. Out of those 301 have more than five forward citations by patent family. An expressive range of data on first-generation (ethanol) and secondgeneration (bioethanol) production were observed positively that when stimulated and directed, there is a growing interest in the patent protection of the intellectual assets (in the form of patent depositories) coming from research and industrial

(5) Analysis of the interrelation of the technologies in the most cited "breakthrough documents" and the calculation of the technical impact index (TII) of the breakthrough inventions—the percent of patents in a period analyzed, which are in the most highly cited of all the breakthrough inventions. The expected value of the TII has been normalized to equal 1. "A TII below 1 indicates that patents are not especially highly cited" ([3], p. 272).

*DOI: http://dx.doi.org/10.5772/intechopen.88428*

**3. Results and discussion**

developments (**Figure 1**).

triticale, rye, malted barley, rice);

**3.1 Overview**

A ratio of >1 is good, a ratio of <1 is relatively low.

*Technological Trajectories Studies of Sugarcane Ethanol Production Using Patent Citation DOI: http://dx.doi.org/10.5772/intechopen.88428*

A ratio of >1 is good, a ratio of <1 is relatively low.


New Discoveries in the Ripening Processes

*Edited by Romina Alina Marc and Crina Carmen Mureșan*

Published in London, United Kingdom

#### New Discoveries in the Ripening Processes http://dx.doi.org/10.5772/intechopen.111017 Edited by Romina Alina Marc and Crina Carmen Mureșan

#### Contributors

Stefan Toepfl, Oleksii Parniakov, Sam David Hopper, Alamu Emmanuel Oladeji, Ekpereka Oluchukwu Anajekwu, Wasiu Awoyale, Delphine Amah, Rahman Akinoso, Busie Maziya-Dixon, Zulfiya Mukhidova Shabzalovna, Salakhutdin Zakirov Khashimovich, Martín-Ernesto Tiznado-Hernández, Eduardo-Antonio Trillo-Hernández, Miguel-Angel Hernández-Oñate, Jamal Ayour, Mohamed Benichou, Hassnâa Harrak, Maged E. A. Mohammed, Nashi Alqahtani, Muhammad Munir, Romina Alina Marc, Crina Carmen Mureșan, Anamaria Pop, Georgiana Smaranda Marțiș, Andruța Elena Mureșan, Alina Narcisa Postolache, Florina Stoica, Ioana Cristina Crivei, Ionuț-Dumitru Veleșcu, Roxana Nicoleta Rațu

#### © The Editor(s) and the Author(s) 2024

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#### Notice

Statements and opinions expressed in the chapters are these of the individual contributors and not necessarily those of the editors or publisher. No responsibility is accepted for the accuracy of information contained in the published chapters. The publisher assumes no responsibility for any damage or injury to persons or property arising out of the use of any materials, instructions, methods or ideas contained in the book.

First published in London, United Kingdom, 2024 by IntechOpen IntechOpen is the global imprint of INTECHOPEN LIMITED, registered in England and Wales, registration number: 11086078, 5 Princes Gate Court, London, SW7 2QJ, United Kingdom Printed in Croatia

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New Discoveries in the Ripening Processes Edited by Romina Alina Marc and Crina Carmen Mureșan p. cm.

This title is part of the Food Science and Nutrition Book Series, Volume 3 Topic: Food Chemistry Series Editor: Maria Rosário Bronze Topic Editor: Thuan-Chew Tan

Print ISBN 978-0-85014-126-9 Online ISBN 978-0-85014-127-6 eBook (PDF) ISBN 978-0-85014-128-3 ISSN 2977-8174


**5. Relationship between exocrine disease and prognosis in cystic fibrosis**

Pancreatic insufficiency is an extremely common complication of CF and affects over 85% of patients at some point during the course of their disease [27]. Loss of pancreatic exocrine function leads to malabsorption of fat, protein, and micronutrients, which in turn causes failure to thrive, steatorrhoea symptoms, and fat-soluble vitamin deficiencies. This arises as a consequence of obstruction of proximal intralobular ducts in the pancreas due to inspissated mucus plugs and tends to arise early in the disease. Chronic pancreatitis is another less common manifestation generally associated with milder (IV-VI) CF genotypes [28, 29], as residual pancreatic acinar tissue is a prerequisite for pancreatitis to develop. Pancreatitis affects over 10% of CF patients and tends to occur in a chronic relapsing and remitting fashion. It is thought to be due to a combination of obstructive tubulopathy and acidification of the acinar lumen due to reduced ductal bicarbonate secretion. Those with symptomatic pancreatitis can often become pancreatic insufficient as their disease progresses. A recent review of the European Cystic Fibrosis registry demonstrated that pancreatic insufficiency was associated with a statistically significant decreases in FEV1%, with pancreatic insufficient patients twice as likely as sufficient patients to experience severe lung disease, defined as FEV < 40% predicted [30]. This indicates that lack of pancreatic exocrine function is associated with worsening prognosis.


**2. Method of analysis**

To explain the effects of earthquakes on buildings using the same analysis criteria, we will use as reference the 1998 European Macroseismic Scale (EMS-98) [8], based on the MSK scale, consisting of twelve incremental levels of intensity in Roman numerals (I-XII) and six vulnerability classes identified by the first letters of the alphabet (A, B, C, D, E and F). The scale also distinguishes and describes four types of structures (masonry, reinforced concrete, steel and timber) of which we will focus on those of masonry and reinforced concrete (hereinafter, RC) without earthquake-resistant design (ERD), the most common in the Ibero-Maghrebian region. Both types of construction, masonry (non-engineered) and reinforced concrete (engineered), present a vulnerability class A, B or C; classes D, E or F, require the implementation of moderate or high ERD measures or the use of steel or timber as the main construction material, unusual within the study area. Here, as we will see later, the buildings share similar construction patterns and offer up the same level of resistance: vulnerability class A or B for masonry buildings, with the exception of those made of massive stone or ashlars (class C), and vulnerability class C for RC buildings. We will prove, for example, how a building of class A located in the Algarve (Portugal) is very similar in terms of construction pattern to another of equal vulnerability in Ait Kamra (Morocco); or how a building of class C in Lorca (Spain) can be damaged in the same way as a similar one in Al Hoceima.

With respect to the classification of damage, which is carried out by direct observation in the field, the EMS-98 scale considers five levels: grade 1, negligible to slight damage; grade 2, moderate damage; grade 3, substantial to heavy damage; grade 4, very heavy damage or partial collapse; and grade 5, destruction or total collapse. Buildings with a grade of damage 1 to 3 do not result in structural or significant structural damage, being easy to repair and recover, while those of grade 4 or 5 have severe or complete structural damage and are difficult or impossible to recover. In this scientific contribution we will explain these effects in detail based on three of the most destructive and best documented earthquakes recorded in the study area: southwest Cape St. Vincent, 1969; Al Hoceima, 2004; and Lorca, 2011.


**5.5 Ineffective civil society**

Mozambique's civil society has so far been very ineffective in protecting communities like Cubo from losing their land to private interests. Civil society faces the challenge of balancing the different expectations of the government and the local communities, especially as the functions of government agencies in implementing and enforcing the land law are constrained by weak processes of accountable governance, limited financial resources, and scarce capacity. The national civil society needs capacity building so that it should be able to encourage the government to prioritize implementation of existing laws and policies that already promote devolved natural resources management and work on harmonizing cross-sectoral policy and legislation that improve the management effectiveness of land and natural resources. This process should be reinforced by strong civil society's advocacy for CBNRM models that strengthen locally accountable institutions for natural resource management and use, enabling local communities to protect their land and resources against foreign acquisitions. Civil society should also focus more on improving transparency and effectiveness in enforcing the land law, to ensure that all its statutes are adequately implemented and enforced.

The civil society should also strongly advocate for Mozambique to implement various international conventions, such as Convention on Biodiversity (CBD) and the United Nations Convention on Combating Desertification (UNCCD), among many others. While national sovereignty is paramount for any country, these Conventions have been widely embraced by many countries in the world in promoting and implementing biodiversity conservation programs, and Mozambique is a party to these conventions. The CBD, for example, specifically recognizes the potential role of local communities in biodiversity conservation through Articles 8 (j), 10 (c), 10 (d), and 11 [23].

Additionally, UNCCD also recognizes the importance of secure land and resource tenure and forms of decentralization. The UNCCD places considerable emphasis on promoting the sustainable use of natural resources [Article 3 (b)], alternative livelihoods [Article 10. 4], and capacity building of local communities for sustainable land and resource management [Article 19]. The strong convergence between the key principles of the CBD, UNCCD, and the generic approach to CBNRM in southern Africa should provide sufficient impetus for the civil society in Mozambique to encourage the government to improve its effort in implementing policies and legislative mechanisms that safeguard community's land rights, prevents alienation of their land without their collective consent, and guarantees their participation in conservationbased enterprises as a means of diversifying community livelihood strategies, and contribution to sustainable rural development.


**3. Methodology**

#### **3.1 Field observations and basic data**

Sedimentological data is collected from 26 localities measuring 5–10 meter vertical sections mostly along the river and small tributaries in all the four areas. Once all outcrops were located, multiple measurements were collected including set-thickness, average grain sizes, and total thickness. Cross-bed sets thickness were measured in the z-plane with 30 cm scale and the minimum distance between measured vertical sections was roughly 0.50 km. The cross bedding sets in the study area are interpreted to be mostly dunes for the following reasons:

(1) cross bedding sets are truncated, (2) Paleocurrent directions were much less variable than one would expect in bars, (3) even if there are some bars within the data, they are usually made up of many layers of truncated dunes, and (4) all ripples observed on the outcrops were flowing in the same direction as the cross bedding sets rather than in a separate direction as see on a bar [12, 13].

#### *3.1.1 Cross-sets*

Cross-set heights were measured as these data can be used to reconstruct original bedform heights and formative flow depths. Trough- and planar cross bedding, which are genetically indicative of bed load transport, were present at nearly all studied field sites. They occurred predominantly in sand grade deposits, but omnipresent in pebble grade deposits of southern coalfields. To establish mean cross-set heights, the sampling strategy of [7] was followed.

#### *3.1.2 Grain size*

Grain sizes were measured at each outcrop. These measurements are taken using a standard 10 hand lens and a grain size card. Grains were identified in each set according to Udden-Wentword grain size scale. Grains within each set tended to be unimodal or at least largely represented by one size; this made finding the average size within cross bedding sets and was substituted for D50 which represents the median of the grain size distribution used in this study.

Sedimentological data so acquired from the Barakar exposures include grain size, cross bedding height, and bar-form height. These data were then used to determine multiple channel geometry, paleohydraulic parameters and paleo dynamics including: mean bed form height, channel depth and width, channel belt width, paleoslope, boundary shear stress, Darcy-Weisbach friction factor, paleoflow velocity, paleodrainage, and overall drainage area by the methods outlined below.


*2.4. Phenolic Compounds*

As mentioned in the Materials and Methods section, at an initial stage of analysis, samples underwent two different preparation procedures, based on the use of PBS and methanol, respectively. Once the method was optimized, the first procedure was preferred, due to better analytical performance in terms of speed and efficiency. The UV spectrophotometric analysis determined the total phenolic content in dried bells and oral arms of male and female organisms in terms of μg of gallic acid

equivalents (GAE) g- on a dw basis (Figure 4). According to the two-way ANOVA test, the interaction of specimen's sex and anatomical part was statistically significant (*p* < 0.05, Table S4). In general, phenolic compounds were more abundant in oral arms rather than in bells (1892–2126 μg GAE g−1 vs. 914–1303 μg GAE g−1, respectively, *p* < 0.05). Considering the same anatomical part (bell or arms), a statistically significant difference (*p* < 0.05) was also determined between the phenolic contents of male and female specimens: 1303.32 μg GAE g−1 vs. 914.22 μg GAE g−1; and 2126.56 μg GAE g−1 vs. 1892.69 μg GAE g−1, in males and females, respectively.

**Figure 4.** Total phenolic content (μg GAE g−1) determined in male and female jellyfishes' bell and oral arms. Data are expressed as mean ± standard deviation (*n* = 3), on a dw basis. Samples marked by different letter differ significantly (*p* < 0.05 by post hoc Tukey's HSD test).


**4. CNSL as petrochemical feedstock**

As a substituted phenol which can take part in a variety of reactions, naturally occurring cashew nut shell liquid (CNSL), a renewable product, offers advantages over synthetics. Its innumerable application stems from the phenolic nature of its constituents, with enshrined features for transformation into high value specialty chemicals [26].

The industrial applications of CNSL-based products are numerous and include fungicide, pesticide, insecticide, brake linings, paints and primers, foundry chemicals, lacquers, cements, specialty coatings and resin. The application of CNSL component in bacteriostatic antibiotics is recently gaining attention. Their effect on plant growth, acid activity, wood preservative and pressure treatment activity are being explored. From the literature [27 - 29], much of the biological activity of CNSL has been attributed to anacardic acid: a major constituent of CNS. Conversely, technical CNSL, as obtained by roasting or oil bath method contained mainly cardols and cardanols [27].

**Components**

14 Advances in Petrochemicals

**Table 4.** Composition of the extracted CNSL

pH obtained for the extracts.

heating temperature of 140°C for 1 h.

**4. CNSL as petrochemical feedstock**

**CNSL (pyrolysis)**

does not require further processing like Trans esterification.

respectively. This gave credence to the report of [25].

Cardol (%) 27 30 31 Cardanol (%) 54 20 65 Anacardic acid (%) 5 43 2 Others (%) 14 7 2

Decarboxylation of raw CNSL involves loss of a carbon dioxide molecule from anacardic acid. The anacardic acid in the oil was converted to cardanol. This is reflected in the composition variation of the components reported in table 4. It is also significant that the pyrolysis of the CNS results in loss of the carboxylic acid content of the cashew nut shell to the process. The decarboxylated anacardic acid is termed CNSL biodiesel. The biodiesel obtained from CNSL

CNSL biodiesel is considered as offering many advantages, including sustainability, decrease of HC, CO, NOx gas emissions and many harmful pollutants [23]. Reference [24] explains the pyrolysis procedure of CNSL. The decarboxylation of CNSL is responsible for the trend in the

Most of the characteristics evaluated gave similar results as those already reported in the literature. In the present findings, the highest occurrence of cardanol was in the decarboxylated CNSL while anacardic acid and cardol occur most in the hexane-extracted and pyrolysis CNSL,

Heating CNSL decomposed the anacardic acid into cardanol and CO2. Decarboxylation of CNSL to convert anacardic acid into cardanol could be done by heating, with an optimum

As a substituted phenol which can take part in a variety of reactions, naturally occurring cashew nut shell liquid (CNSL), a renewable product, offers advantages over synthetics. Its innumerable application stems from the phenolic nature of its constituents, with enshrined

The industrial applications of CNSL-based products are numerous and include fungicide, pesticide, insecticide, brake linings, paints and primers, foundry chemicals, lacquers, cements, specialty coatings and resin. The application of CNSL component in bacteriostatic antibiotics is recently gaining attention. Their effect on plant growth, acid activity, wood preservative and pressure treatment activity are being explored. From the literature [27 - 29], much of the biological activity of CNSL has been attributed to anacardic acid: a major constituent of CNS.

features for transformation into high value specialty chemicals [26].

**CNSL (hexane extracted)**

**CNSL (decarboxylated)**

> CNSL reduces the extent of the electrochemical processes taking place on carbon steel surface undergoing corrosion. The inhibition tendency is excellent for both static and dynamic conditions. CNSL and its derivatives have antioxidative characteristics [28 - 30]. This antioxi‐ dative tendency is related to the electron-donating nature and steric effect of the substituents. The electron-donating effect usually enhances the electron density at the phenolic oxygen of the cashew nut oil, resulting in the trapping of the radicals which normally propagates oxidation reaction. CNSL is a mixture of hindered phenols with long alkyl substitution at the *meta* position. The unsaturation on the long side chain substituents is an important factor enhancing higher anti-oxidant activity of CNSL. CNSL films are thermally stable. This stability increases in the presence of thiophosphate ester additives.

> Olefin metathesis (OM) reaction on cardanol is an important class of reactions that allows for the synthesis of new olefins that are sometimes impossible to prepare via other methods [31]. Cardanol- a renewable, low cost, main constituent (about 85%) of CNSL possesses character‐ istic long alkyl chains in *meta* position of its phenol ring [12] that promotes this OM reaction, and also influences several chemical transformations leading to novel functionalities [31].

> Cardanol based polyhydrins improve the photo-catalytic activity of bare TiO2. The porphyrins are brown-red sticky solids, very soluble in CHCl3 or CH2Cl2 [32]. This substituted cardanolbased porphyrin and their metallic complexes have been used extensively in photo degrada‐ tion of toxic, bio-refractory 4-nitro phenol in water, which is dangerous for the ecosystem and for human health [32]. CNSL is also useful in fuel blends and fuel mixtures [33] and for producing diesel oil [34]. Cracking of CNSL with a molecular sieve at 500° C for 2 h generates brown coloured liquid product. This is diesel fuel.

> Cashew Nut Shell Liquid (CNSL) was used as an alternative fuel for diesel engine. The viscosity of CNSL is 30 - 35 times higher than diesel; hence different blends of CNSL would have different properties and application. Also, modification of the oil and its application condition such as, injection pressure, injection timing and preheating the oil also optimizes the perform‐ ance of the engine. There were indications that preheating of CNSL25 blends at 200 kg/cm2 injection pressure and 28° injection timing gives encouraging results suitable for commercial purposes [35]. CNSL as a bioadditive in engines increases the durability of the equipment. Hence, the application of CNSL as a bioadditive will reduce the dependency on petroleum products besides preserving the environment by lowering pollutant residues from fuel combustion products. Some of the properties of diesel, biofuel and ethanol are presented against CNSL in Table 5.

> CNSL has higher density than diesel. It can be reduced by degumming and trans esterification. Cetane for CNSL is expected to be poor due to the presence of aromatic compounds. The usual C:H:O ratio for vegetable oils is 78:12:10 whereas for CNSL it is 80:12:8; hence, it justifies the higher calorific value of CNSL (47 MJ/kg), whereas for diesel it is 42 MJ/kg. Also, ash content is well within the limits for CNSL. The water content of CNSL is quite high. The sulphur content does not exceed 0.006% for any vegetable oil. Thus it is anticipated that CNSL has no sulphur

content. The flash point for CNSL is 164°C; this is higher than the flash point for diesel and represents the higher starting ignition temperatures and compression of CNSL [35].

**Table 5.** Fuel properties

The physicochemical properties of cashew nut shell liquid (CNSL) make it potentially useful for improved adhesion between bitumen and aggregates. Thus, the asphalt resulting from bitumen modified with CNSL has better stripping resistance and satisfactory mechanical properties compared with conventional asphalts. The CNSL, as an additive, prevents stripping in the asphalts, thereby contributing to its moisture damage resistance [36].

CNSL has also been used in production of asbestos with free friction composition for brake linings [37]. In combination with cardanol, it is used extensively in automotive break-lining applications [38]. CNSL/cardol-based surface coatings possess excellent gloss and surface finish with a high level of toughness and elasticity.

Valuable chemicals result from the pyrolysis of CNSL at high temperatures (450°C to 750°C) and at short residence times [39]. The products of pyrolysis include tar, phenols, hydrocarbons and gases with high petrochemical values.

On the other hand, cardanol which is highly resistant to softening action of mineral oil, acids, alkalis, microbes, termites and insects is widely used in the coating and resin industry. Reference [40] reported that technical CNSL may also contain phytosterol, such as stigma sterol and β-sitosterol, which have cholesterol-lowering properties.

Cardanol polysulfide (CPS) has been used as a vulcanizing agent for natural rubber as reported by [41]. Coordination bond linkage in cardanol-aldehyde condensation polymers improved its physicomechanical properties. This positively influences the anticorrosive properties and stability of the polymeric compound at high temperature [42]. The blend of cardanol-based novolac-type phenolic resins, with commercial epoxy or isocynate monomers produces thermoset polymers [43]. Also, in [44], the conversion of CNSL-based cardols (6-alkenylresor‐ cinols) into lasiodiplodin, a naturally occurring 12-membered orsellinic acid type macrolide, exhibits plant growth-regulating and antileukemic properties.

Immature CNSL (iCNSL) has excellent protective activities in strains of *S. cerevisiae* against oxidative damage induced by hydrogen peroxide and inhibits acetyl cholinesterase activity [45]. The high in vitro antibacterial activity of cashew nut shell liquid (CNSL) has been attributed to its anacardic acid content [46]. Both anacardic acid and cardol were reported to have antitumor [47-49], antimicrobial [48], urease inhibitory [50] and lipoxygenase activities [51]. Gram positive bacteria, which cause tooth decay, acne, tuberculosis, *Streptococcus pneumonia, Francisella tularensis,* and leprosy are killed by anacardic chemicals [52].

content. The flash point for CNSL is 164°C; this is higher than the flash point for diesel and

The physicochemical properties of cashew nut shell liquid (CNSL) make it potentially useful for improved adhesion between bitumen and aggregates. Thus, the asphalt resulting from bitumen modified with CNSL has better stripping resistance and satisfactory mechanical properties compared with conventional asphalts. The CNSL, as an additive, prevents stripping

CNSL has also been used in production of asbestos with free friction composition for brake linings [37]. In combination with cardanol, it is used extensively in automotive break-lining applications [38]. CNSL/cardol-based surface coatings possess excellent gloss and surface

Valuable chemicals result from the pyrolysis of CNSL at high temperatures (450°C to 750°C) and at short residence times [39]. The products of pyrolysis include tar, phenols, hydrocarbons

On the other hand, cardanol which is highly resistant to softening action of mineral oil, acids, alkalis, microbes, termites and insects is widely used in the coating and resin industry. Reference [40] reported that technical CNSL may also contain phytosterol, such as stigma sterol

Cardanol polysulfide (CPS) has been used as a vulcanizing agent for natural rubber as reported by [41]. Coordination bond linkage in cardanol-aldehyde condensation polymers improved its physicomechanical properties. This positively influences the anticorrosive properties and stability of the polymeric compound at high temperature [42]. The blend of cardanol-based novolac-type phenolic resins, with commercial epoxy or isocynate monomers produces thermoset polymers [43]. Also, in [44], the conversion of CNSL-based cardols (6-alkenylresor‐ cinols) into lasiodiplodin, a naturally occurring 12-membered orsellinic acid type macrolide,

Immature CNSL (iCNSL) has excellent protective activities in strains of *S. cerevisiae* against oxidative damage induced by hydrogen peroxide and inhibits acetyl cholinesterase activity [45]. The high in vitro antibacterial activity of cashew nut shell liquid (CNSL) has been

represents the higher starting ignition temperatures and compression of CNSL [35].

) 0.84 0.789 0.9326

**Properties Diesel\* Ethanol\* CNSL**

Kinematic viscosity (cost) 2-5 1.19 17.2 Calorific value (kJ/kg) 42000 30000 47600 Flash point (°C) 62 16 193 Auto-ignition temperature (°C) 210 362 206

in the asphalts, thereby contributing to its moisture damage resistance [36].

finish with a high level of toughness and elasticity.

and β-sitosterol, which have cholesterol-lowering properties.

exhibits plant growth-regulating and antileukemic properties.

and gases with high petrochemical values.

Density (kg/m3

16 Advances in Petrochemicals

\*Source: [28]

**Table 5.** Fuel properties

Anacardic acid has also been found to reduce the expression of survivin and X-linked inhibitor of apoptosis protein, anti apoptotic proteins associated with cellular survival and radio resistance, and radio-sensitized pituitary adenoma cells [53]. Also, these acids have been used effectively against tooth abscesses due to their lethality to bacteria.

The monophenolics of CNSL have been found to form stable quaternary nitrogen compounds which are soluble in water, odourless and act as surface-active agents [54]. These properties including their high bacterial activity, have made them significantly useful as germicides, disinfectants and sanitizing agents in food and dairy industries. Also, sodium salts of anacardic acid, for example disodium anarcadates, are anionic surfactant and could be used as bacteri‐ cidal surfactant while sodium anarcadate is useful for the control of vector mosquitoes which are responsible for causing dengue fever [55].

Energy studies established that cashew nut by-products CNSL, its isolates and spent CN Shell compare quite favourably with conventional fuels in terms of energy content. CNSL, cardanol and cardol, which are liquid by-products, were superior to conventional liquid and solid fuels while spent CN shell was more superior to a number of liquid fuels, e.g. ethanol and methanol, as well as fire wood in terms of energy content. This material is advocated for use by cashew nut processors and other industries as fuel to reduce environmental pollution. This material is not only a cleaner fuel but also has low ash and is renewable [56].

Substitution of phenol with CNSL in both resol and novolacs decreased the tensile strength, but improved the impact strength of wood flour-based laminate of these resins. Thermal properties of phenol-cardanol-based resin depletes with increasing cardanol content in the resin [57, 58].

The synthesis of polymers from renewable resources has attracted considerable attention worldwide due to its potential attribute as a substitute for petrochemical feedstock. CNSL may act as a potential raw material for the manufacture of polymers in the 21st century [58] due to its components and depletion in petroleum production which increasingly faces exhaustion. Long-chain, *m*-substituted phenol in CNSL is highly reactive. Thus a wide variety of resins are synthesized from CNSL, such as polyesters, phenolic resins, epoxy resins, polyurethanes, acrylics, vinyls and alkyds to mention a few [59].

CNSL contains four major components: 3-pentadecenyl phenol (cardanol), 5-pentadecenyl resorcinol (cardol), 6-pentadecenyl salicylic acid (anacardic acid) and 2-methyl 5-pentadecenyl resorcinol (2-methyl cardol), which can be good replacement for synthetic resins, owing to the current climate of diminishing petroleum reserves. Cardanol, which is a phenol derivative, has a meta substitute of a C15 unsaturated hydrocarbon chain with one to three double bonds [31, 32, 60, 61]. Being a major component of CNSL, its abundant production promised renew‐ able feedstock for the petrochemical industry with a total production of CNS approaching 2.6 million tons annually [1].

Resoles and novolacs resins are the major products of reaction of CNSL with formaldehyde. While novolac results from acid-catalyzed reactions, resoles are a product of base-catalyzed reactions.

CNSL can be polymerized by different methods. This includes addition polymerization through the side-chain double-bonds using cationic initiators such as diethylsulphate, condensation polymerization through the phenolic rings with aldehydic compound, e.g. formaldehyde, oxidative polymerization, polymerization after chemical modification to produce specialty properties, etc. The most common method is condensation reaction with formaldehyde. The CNSL-based polymers offer advantages such as improved flexibility and reduced brittleness, solubility in organic solvents, improved process ability, compatibility with other polymers, high performance and resistance to microbes, insects and termites.

CNSL were successfully applied as a thermosetting wood adhesive for wood panels to reduce formaldehyde emission. These renewable phenolic compounds give excellent adhesive performance, good moisture resistance and tend to give a lower formaldehyde emission than UF resin [62, 63].


*Article* **Smartphones as a Platform for Tourism Management Dynamics during Pandemics: A Case Study of the Shiraz Metropolis, Iran**

**Hadigheh Morabi Jouybari 1 , Amir Ghorbani 2 , Hossein Mousazadeh 3,\* , Azadeh Golafshan 4 , Farahnaz Akbarzadeh Almani 5 , Dávid Lóránt Dénes 6,7,\* and Ritter Krisztián 6**

**Abstract:** During the past three years and with the spread of the pandemic, smartphones were the most important communication bridge between tourists and organizations; now more than ever, they are intertwined with the lives of tourists and destination management organizations. Although much research has been conducted in this field, the investigation of the effects of the pandemic on the technology and functionality of smartphones is one of the topics that has been less discussed. Therefore, the current research was conducted to determine the role of smartphones in tourism management dynamics during the pandemic. The research method was qualitative (content analysis, theme analysis), and 32 people participated in the interview process as a statistical sample. Then, the oral interviews were transcribed, and a thematic analysis was performed. For the analysis of the interviews, MAXQDA 2020 software was used. The results of the research indicate that smartphones were one of the most important platforms for tourism management dynamics during the pandemic, and in the event of a pandemic in the future, they can help contain the destruction to a great extent in their current position.

**Keywords:** destination management organizations; tourism technology; content analysis; thematic analysis