*Removal efficiency of polycyclic aromatic hydrocarbons in relation to the molecular compounds present in the five photobioreactors with different gradients concentrations of water produced diluted in saline water.*

**121**

**Figure 3.**

sorbent), S

in natura.

pre-treated fibers.

*Mangrove Ecosystem Restoration after Oil Spill: Bioremediation, Phytoremediation, Biofibers…*

and treatment with Protic Ionic Liquids (PIL). In acetylation, mercerized fibers were immersed in a solution of acetic anhydride and glacial acetic acid (1.5:1.0 by mass) with 12 drops of sulfuric acid at 80°C for 3 hours. For the treatment with PIL, a sample of coconut fiber was added in 2-hydroxyidoethylammonium acetate [2-HEA] [Ac] at 80°C for 2 hours [44]. These fibers (in natura, pretreated by mercerization followed by acetylation and with PIL) were characterized from the

After the pre-treatment procedures, the fibers were weighed (0.5 g) and conditioned in mini barriers made from TNT (non-woven fabric) to continue the sorption and kinetics tests. The tests were performed in a thermostatic bath, with reciprocal movements of approximately 126 cycles/minute and temperature of 25°C (average temperature of the marine environment). The kinetic experiment was conducted in beakers with 95 mL of saline water and 5 mL of oil from the Campos Basin with the mini-barriers in contact with the oil slick for 120 minutes, in which samples were taken, in triplicate, in the time intervals of 5, 20, 40, 60, 90 and 120 min [7]. In the sorption equilibrium experiment, the oil concentration was varied for the construction of the isotherms [45]. After testing, the samples were cold dried in the lyophilize and weighed. The sorption capacity of the fibers was determined through Eq. (3), where S is the adsorption capacity (sorbate g/g of

after adsorption [6, 7]. The tests were performed by the barriers with in natura and

Through SEM analysis, it was possible to observe a large irregularity and pores on the surface of fibers in natura (**Figure 3a**). After the treatments, the mercer

ized/acetylated fiber increased the rough area of the cross section, in comparison with the fiber in natura (**Figure 3b**). The fiber with PIL, on the other hand, had a higher number of pores (**Figure 3c**), resulting from the cleaning by treatment with this organic solvent. Thus, chemically treated fibers have more space available for adsorption through the pores and the roughened surface compared to fibers

The kinetic results of the adsorption of the barriers with coconut fibers are shown in **Figure 4**. In all fibers studied (in natura, mercerized/acetylated and with PIL) the kinetic behavior was very similar. There was a marked sorption up to 5 minutes and then the sorption remained practically constant. This happens because the initial number of pores and available surface in the fibers are occupied over time, reducing the availability and consequently the sorption capacity [6, 7, 42, 45–47]. From these results, it can be concluded that the time of 5 minutes has more significant efficiency in adsorption, requiring a minimum contact time between the

*SEM coconut fiber (a) in natura (b) treated with mercerization/acetylation (c) treated with PIL.*

f (g) is the final mass of the fiber


*SSSS* = − ( *fo o* )/ (3)

*DOI: http://dx.doi.org/10.5772/intechopen.95342*

morphology by the Scanning Electron Microscope (SEM).

0 (g) is the initial mass of the fiber and S

*Mangrove Ecosystem Restoration after Oil Spill: Bioremediation, Phytoremediation, Biofibers… DOI: http://dx.doi.org/10.5772/intechopen.95342*

and treatment with Protic Ionic Liquids (PIL). In acetylation, mercerized fibers were immersed in a solution of acetic anhydride and glacial acetic acid (1.5:1.0 by mass) with 12 drops of sulfuric acid at 80°C for 3 hours. For the treatment with PIL, a sample of coconut fiber was added in 2-hydroxyidoethylammonium acetate [2-HEA] [Ac] at 80°C for 2 hours [44]. These fibers (in natura, pretreated by mercerization followed by acetylation and with PIL) were characterized from the morphology by the Scanning Electron Microscope (SEM).

After the pre-treatment procedures, the fibers were weighed (0.5 g) and conditioned in mini barriers made from TNT (non-woven fabric) to continue the sorption and kinetics tests. The tests were performed in a thermostatic bath, with reciprocal movements of approximately 126 cycles/minute and temperature of 25°C (average temperature of the marine environment). The kinetic experiment was conducted in beakers with 95 mL of saline water and 5 mL of oil from the Campos Basin with the mini-barriers in contact with the oil slick for 120 minutes, in which samples were taken, in triplicate, in the time intervals of 5, 20, 40, 60, 90 and 120 min [7]. In the sorption equilibrium experiment, the oil concentration was varied for the construction of the isotherms [45]. After testing, the samples were cold dried in the lyophilize and weighed. The sorption capacity of the fibers was determined through Eq. (3), where S is the adsorption capacity (sorbate g/g of sorbent), S0 (g) is the initial mass of the fiber and Sf (g) is the final mass of the fiber after adsorption [6, 7]. The tests were performed by the barriers with in natura and pre-treated fibers.

$$\mathcal{S} = \left(\mathcal{S}\_f - \mathcal{S}\_o\right) / \mathcal{S}\_o \tag{3}$$

Through SEM analysis, it was possible to observe a large irregularity and pores on the surface of fibers in natura (**Figure 3a**). After the treatments, the mercerized/acetylated fiber increased the rough area of the cross section, in comparison with the fiber in natura (**Figure 3b**). The fiber with PIL, on the other hand, had a higher number of pores (**Figure 3c**), resulting from the cleaning by treatment with this organic solvent. Thus, chemically treated fibers have more space available for adsorption through the pores and the roughened surface compared to fibers in natura.

The kinetic results of the adsorption of the barriers with coconut fibers are shown in **Figure 4**. In all fibers studied (in natura, mercerized/acetylated and with PIL) the kinetic behavior was very similar. There was a marked sorption up to 5 minutes and then the sorption remained practically constant. This happens because the initial number of pores and available surface in the fibers are occupied over time, reducing the availability and consequently the sorption capacity [6, 7, 42, 45–47]. From these results, it can be concluded that the time of 5 minutes has more significant efficiency in adsorption, requiring a minimum contact time between the

**Figure 3.** *SEM coconut fiber (a) in natura (b) treated with mercerization/acetylation (c) treated with PIL.*

*Mangrove Ecosystem Restoration*

**120**

**Concentration of polycyclic aromatic hydrocarbons (**μ**g L −1)**

Initial concentration

**LMW**

**IMW** 

**HMW** 

**LMW**

**IMW** 

**LMW**

**Initial**

**Final**

**Removal** 

**efficiency**

**(5 - 6 rings**

**(4 rings)**

**(2 - 4 rings)**

**(5 - 6 rings**

**(4 rings)**

**(2 - 4 rings)**

102.8 ±4.92

8.26± 0.35

5.84± 0.31

94± 4.91

9.99± 0.77

1.34± 0.02

116.9±4.78

105.33±

10%

2.98

Conway medium

25% produced water

50% produced water

75% produced water

100% produced

3016.43± 93.75

13.59± 0.89

7.38± 0.49 *Low Molecular Weight (LMW), Intermediate Molecular Weight (IMW) and Hight Molecular Weight (HMW). Data shown as the mean ± SD, n = 3.*

*Removal efficiency of polycyclic aromatic hydrocarbons in relation to the molecular compounds present in the five photobioreactors with different gradients concentrations of water produced* 

152.22± 1.91

35.73± 4.05

6.89± 0.02

3037.4± 2.40

194.84±

94%

4.56

water

**Table 6.**

*diluted in saline water.*

1823.72±166.45

13.29± 0.57

5.02± 0.12

131.79± 8.74

14.56± 0.91

5.43± 0.01

1842.03±

151.78±

92%

1.05

4.86

1537.25± 41.48

13.52± 0.47

5.38± 0.71

127.38±

9.08± 0.71

1.87± 0.01

1556.15± 4.61

138.33±

91%

2.06

13.84

687.84 ±19.23

14.09± 1.13

8.3± 0.98

92.44± 4.90

13.84± 1.02

2.32± 0.13

710.23± 4.88

108.6± 2.57

85%

Final concentration

Total composition of PAHs

**Figure 4.** *Comparison of the kinetic behavior of sorption among all coconut fibers.*

adsorbent material and the adsorbate to removal of crude oil in the marine environment, in addition to the contact technology operator time with toxic oil.

The equilibrium sorption was 4.00 g / g for fresh coconut fiber, 4.27 g / g for mercerized / acetylated fiber and 5.37 g/g for PIL fiber. Therefore, the fiber with PIL adsorbed 20.5% more than the mercerized/acetylated coconut fiber and 25.5% more than the fresh fiber. (b).

The result of the higher sorption of the treated coconut fibers can be explained by the chemical, structural and morphological modification presented in relation to the natural fibers through the characterizations. The greater quantity and density of pores resulting from the removal of chemical constituents, such as lignin and hemicellulose, waxes and impurities, made the pores of coconut fibers clear and consequently increased the surface area for interaction with oil.

#### **3. Conclusions**

Our study with phytoremediation in mangroves, showed that it is possible to accelerate the process of removing oil hydrocarbons in sediments when using the mechanisms of plants, their rhizosphere and the associated microorganisms. Phytoremediation is the most suitable technique for mangrove areas, since sediments have low oxygen solubility and have granulometric characteristics that increase the residence time of persistent organic pollutants such as PAHs. Based on the results found, it can be said that the barriers with chemically treated fibers are more efficient than in natura to be used in the containment and cleaning of oil spilled in marine environments so that it does not affect sensitive areas such as mangroves. The barrier composed of the fiber treated with PIL obtained greater oil sorption, followed by the fiber treated by mercerization-acetylation and finally the fiber in natura. These fiber barriers that were produced by our group can be used during emergency combat of oil stains in estuarine waters, preventing oil from reaching the sediment. They can also be used as sponges to clean oil already adhered to the surface of plants and mangrove sediments, preventing the infiltration of hydrocarbons. In this study it was identified that the *Nannochloropsis oculata* marine microalgae used for the removal of polycyclic aromatic hydrocarbons in produced water showed greater efficiency in the produced water with 94% removal, demonstrating that this marine microalgae is able to contribute to the degradation of

**123**

*Mangrove Ecosystem Restoration after Oil Spill: Bioremediation, Phytoremediation, Biofibers…*

organic pollutants and to prevent PAHs from reaching sensitive ecosystems such as mangroves. Microalgae photobioreactors can be used in the treatment of effluents from the oil industry that are released into the mangrove. In addition, the use of microalgae biorefineries has already been used to remedy river waters, and may be an option during the emergency combat of oil spills in mangrove estuarine waters. A sequential application of bioremediation and adequacy contributed positively to the biodegradation of petroleum hydrocarbons. There were improvements in the quality of the sediment, due to the variation of the physical–chemical characteristics provided by the action of rhizosmic microorganisms, stimulated by enzymes released by the plants, during the oil hydrocarbon metabolism. This process was also noticeable in the growth curve of microorganisms and in the variation in the speed of consumption of petroleum hydrocarbons. The studies that our group has been carrying out for more than 10 years show that there is not a single biotechnology that can restore oil-impacted mangroves. Each biotechnology presented here has its particular contribution in removing pollutants in the various environmental matrices of the ecosystem. Recently our group has advanced in the studies of advanced molecular biology (studies of genomics, transcriptome, proteomics and metabolomics) for the improvement of bioprocesses in a faster restoration and with

We thank CAPES and FAPESB for providing scholarships to the graduate students involved, we also thank CNPQ for providing scholarships to researchers

We want to honor with this pubication our eternal advisor Professor Ph.D. Jorge Alberto Trigüis (in memoriam) for all the teachings passed to the area of geochemistry in Brazil and in the world. We also want to thank our family members for supporting us in the career we have followed, especially in this pandemic moment where we have to organize ourselves with the different demands (professional and private). For this reason, our tribute to the future great professionals Yasmin M. P.

involved in the studies in addition to financing the DEMBPETRO project.

Andrade Moreira and Rafaella M. P. Andrade Moreira.

*DOI: http://dx.doi.org/10.5772/intechopen.95342*

economic viability (bioeconomy).

**Acknowledgements**

**Note**

*Mangrove Ecosystem Restoration after Oil Spill: Bioremediation, Phytoremediation, Biofibers… DOI: http://dx.doi.org/10.5772/intechopen.95342*

organic pollutants and to prevent PAHs from reaching sensitive ecosystems such as mangroves. Microalgae photobioreactors can be used in the treatment of effluents from the oil industry that are released into the mangrove. In addition, the use of microalgae biorefineries has already been used to remedy river waters, and may be an option during the emergency combat of oil spills in mangrove estuarine waters. A sequential application of bioremediation and adequacy contributed positively to the biodegradation of petroleum hydrocarbons. There were improvements in the quality of the sediment, due to the variation of the physical–chemical characteristics provided by the action of rhizosmic microorganisms, stimulated by enzymes released by the plants, during the oil hydrocarbon metabolism. This process was also noticeable in the growth curve of microorganisms and in the variation in the speed of consumption of petroleum hydrocarbons. The studies that our group has been carrying out for more than 10 years show that there is not a single biotechnology that can restore oil-impacted mangroves. Each biotechnology presented here has its particular contribution in removing pollutants in the various environmental matrices of the ecosystem. Recently our group has advanced in the studies of advanced molecular biology (studies of genomics, transcriptome, proteomics and metabolomics) for the improvement of bioprocesses in a faster restoration and with economic viability (bioeconomy).

#### **Acknowledgements**

We thank CAPES and FAPESB for providing scholarships to the graduate students involved, we also thank CNPQ for providing scholarships to researchers involved in the studies in addition to financing the DEMBPETRO project.

#### **Note**

*Mangrove Ecosystem Restoration*

than the fresh fiber. (b).

**Figure 4.**

**3. Conclusions**

adsorbent material and the adsorbate to removal of crude oil in the marine environ-

The equilibrium sorption was 4.00 g / g for fresh coconut fiber, 4.27 g / g for mercerized / acetylated fiber and 5.37 g/g for PIL fiber. Therefore, the fiber with PIL adsorbed 20.5% more than the mercerized/acetylated coconut fiber and 25.5% more

The result of the higher sorption of the treated coconut fibers can be explained by the chemical, structural and morphological modification presented in relation to the natural fibers through the characterizations. The greater quantity and density of pores resulting from the removal of chemical constituents, such as lignin and hemicellulose, waxes and impurities, made the pores of coconut fibers clear and

Our study with phytoremediation in mangroves, showed that it is possible to accelerate the process of removing oil hydrocarbons in sediments when using the mechanisms of plants, their rhizosphere and the associated microorganisms. Phytoremediation is the most suitable technique for mangrove areas, since sediments have low oxygen solubility and have granulometric characteristics that increase the residence time of persistent organic pollutants such as PAHs. Based on the results found, it can be said that the barriers with chemically treated fibers are more efficient than in natura to be used in the containment and cleaning of oil spilled in marine environments so that it does not affect sensitive areas such as mangroves. The barrier composed of the fiber treated with PIL obtained greater oil sorption, followed by the fiber treated by mercerization-acetylation and finally the fiber in natura. These fiber barriers that were produced by our group can be used during emergency combat of oil stains in estuarine waters, preventing oil from reaching the sediment. They can also be used as sponges to clean oil already adhered to the surface of plants and mangrove sediments, preventing the infiltration of hydrocarbons. In this study it was identified that the *Nannochloropsis oculata* marine microalgae used for the removal of polycyclic aromatic hydrocarbons in produced water showed greater efficiency in the produced water with 94% removal, demonstrating that this marine microalgae is able to contribute to the degradation of

ment, in addition to the contact technology operator time with toxic oil.

*Comparison of the kinetic behavior of sorption among all coconut fibers.*

consequently increased the surface area for interaction with oil.

**122**

We want to honor with this pubication our eternal advisor Professor Ph.D. Jorge Alberto Trigüis (in memoriam) for all the teachings passed to the area of geochemistry in Brazil and in the world. We also want to thank our family members for supporting us in the career we have followed, especially in this pandemic moment where we have to organize ourselves with the different demands (professional and private). For this reason, our tribute to the future great professionals Yasmin M. P. Andrade Moreira and Rafaella M. P. Andrade Moreira.

## **Author details**

Ícaro Thiago Andrade Moreira1 \*, Célia Karina Maia Cardoso1 , Evelin Daiane Serafim Santos Franco2 , Isadora Machado Marques3 , Gisele Mara Hadlich4 , Antônio Fernando de Souza Queiroz<sup>5</sup> , Ana Katerine de Carvalho Lima Lobato6 and Olívia Maria Cordeiro de Oliveira7

1 Program in Chemical Engineering (PPEQ-UFBA), Federal University of Bahia, Salvador, Bahia, Brazil

2 Geochemistry: Petroleum and Environment (POSPETRO-UFBA), Federal University of Bahia, Salvador, Bahia, Brazil

3 Industrial Engineering (PEI-UFBA), Federal University of Bahia, Salvador, Bahia, Brazil

4 Department of Geography, Federal University of Bahia (UFBA), Salvador, Bahia, Brazil

5 Department of Oceanography, Federal University of Bahia (UFBA), Salvador, Bahia, Brazil

6 Program in Chemical Engineering (PPEQ ), Salvador University (UNIFACS), Brazil

7 Department of Geophysics, Geosciences Institute, Federal University of Bahia (UFBA), Salvador, Bahia, Brazil

\*Address all correspondence to: icarotam@ufba.br

© 2021 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

**125**

*Mangrove Ecosystem Restoration after Oil Spill: Bioremediation, Phytoremediation, Biofibers…*

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[9] Silva C.C. et al. Influence of plasma treatment on the physical and chemical properties of sisal fibers and environmental application in adsorption of methylene blue. Journals & Books.

[10] Lopes F. C. S. M. R. Ag/ TiO2 photocatalyst immobilized onto modified natural fibers for photodegradation of anthracene. Chemical Engineering Science. 2020:

[11] Streltsova E., Linton J. D. Biotechnology patents in BRICS countries: strategy and dynamics. Trends in Biotechnology. 2018: 36:

[12] Santos J. J., Maranho L. T. Rhizospheric microorganisms as a solution for the recovery of soils contaminated by petroleum: A review. Journal of Environmental Management.

[13] Straathof A. J. J. et al. Major research challenges in sustainable industrial biotechnology .Biotechnology trends.

[14] Arbib Z. et al. Capability of different microalgae species for phytoremediation

processes: Wastewater tertiary treatment, CO2 bio-fixation and low cost biofuels production. Water

[15] Duke N. C. Oil spill impacts on mangroves: Recommendations for operational planning and action based on a global review. Marine Pollution

Research. 2014: 465-474.

Bulletin. 2016: 109: 700-715.

Actabra1120179.

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227: 115939.

642-645.

2018:20:104-113.

2019: 37: 1042-1050.

*DOI: http://dx.doi.org/10.5772/intechopen.95342*

[1] Almeida A. G., Vinnem J. E. Major accident prevention illustrated by hydrocarbon leak case studies: A comparison between Brazilian and Norwegian offshore functional

petroleum safety regulatory approaches. Journals & Books. 2020: 121: 652-665.

[3] Oliveira O. M.C. et al. Environmental

[2] Yanting Z., Liyun X. Research on Risk Management of Petroleum Operations. Energy Procedia. 2011:5:2330-2334. DOI: https://doi. org/10.1016/j.egypro.2011.03.400.

disaster in the northeast coast of Brazil: Forensic geochemistry in the identification of the source of the oily material. Marine Pollution Bulletin.

[4] Zeng C., Hu. 2018 petroleum & chemical industry development report.

Chemical Engineering. 2019: 27:

[5] Aghaalikhani A. et al. Poplar from phytoremediation as a renewable energy source: gasification properties and pollution analysis. Energy Procedia.

[6] Cardoso, C. K. M., Santana, R. S. G. de, Silva, V. L. da, Meirelles, A. C. L. E., Mattedi, S., Moreira, Ícaro T. A., & Lobato, A. K. de C. L. (2020). Kinetic and equilibrium study of petroleum adsorption using pre-treated coconut fibers. Research, Society and Development, 9(7), e523974413. DOI: https://doi.org/10.33448/rsd-v9i7.4413

[7] Annunciado, TR, Sydenstricker, THD, Amico, SC. Experimental

Pollution Bulletin. 2005;50:1340- 1346. DOI: https://doi.org/10.1016/j.

marpolbul.2005.04.043

investigation of various vegetable fibers as sorbent materials for oil spills. Marine

2020: 160: 1-7.

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2606-2614.

Chinese Journal of

2017: 142: 924-931.

*Mangrove Ecosystem Restoration after Oil Spill: Bioremediation, Phytoremediation, Biofibers… DOI: http://dx.doi.org/10.5772/intechopen.95342*

#### **References**

*Mangrove Ecosystem Restoration*

**Author details**

Gisele Mara Hadlich4

Salvador, Bahia, Brazil

Salvador, Bahia, Brazil

(UFBA), Salvador, Bahia, Brazil

\*Address all correspondence to: icarotam@ufba.br

provided the original work is properly cited.

Brazil

Brazil

Brazil

Ícaro Thiago Andrade Moreira1

Evelin Daiane Serafim Santos Franco2

Ana Katerine de Carvalho Lima Lobato6

University of Bahia, Salvador, Bahia, Brazil

\*, Célia Karina Maia Cardoso1

, Antônio Fernando de Souza Queiroz<sup>5</sup>

1 Program in Chemical Engineering (PPEQ-UFBA), Federal University of Bahia,

3 Industrial Engineering (PEI-UFBA), Federal University of Bahia, Salvador, Bahia,

4 Department of Geography, Federal University of Bahia (UFBA), Salvador, Bahia,

6 Program in Chemical Engineering (PPEQ ), Salvador University (UNIFACS),

7 Department of Geophysics, Geosciences Institute, Federal University of Bahia

© 2021 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,

2 Geochemistry: Petroleum and Environment (POSPETRO-UFBA), Federal

5 Department of Oceanography, Federal University of Bahia (UFBA),

, Isadora Machado Marques3

,

,

and Olívia Maria Cordeiro de Oliveira7

,

**124**

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[3] Oliveira O. M.C. et al. Environmental disaster in the northeast coast of Brazil: Forensic geochemistry in the identification of the source of the oily material. Marine Pollution Bulletin. 2020: 160: 1-7.

[4] Zeng C., Hu. 2018 petroleum & chemical industry development report. Chinese Journal of Chemical Engineering. 2019: 27: 2606-2614.

[5] Aghaalikhani A. et al. Poplar from phytoremediation as a renewable energy source: gasification properties and pollution analysis. Energy Procedia. 2017: 142: 924-931.

[6] Cardoso, C. K. M., Santana, R. S. G. de, Silva, V. L. da, Meirelles, A. C. L. E., Mattedi, S., Moreira, Ícaro T. A., & Lobato, A. K. de C. L. (2020). Kinetic and equilibrium study of petroleum adsorption using pre-treated coconut fibers. Research, Society and Development, 9(7), e523974413. DOI: https://doi.org/10.33448/rsd-v9i7.4413

[7] Annunciado, TR, Sydenstricker, THD, Amico, SC. Experimental investigation of various vegetable fibers as sorbent materials for oil spills. Marine Pollution Bulletin. 2005;50:1340- 1346. DOI: https://doi.org/10.1016/j. marpolbul.2005.04.043

[8] CALDAS, A. S.; VIANA, Z. C. V.; SANTOS, V. L. C. S. Fibers of *Cocos nucifera* L. as sorbent of petroleum in marine environment. Acta Brasiliensis, [S.l.], v. 1, n. 1, p. 13-18, jan. 2017. DOI: https://doi.org/10.22571/ Actabra1120179.

[9] Silva C.C. et al. Influence of plasma treatment on the physical and chemical properties of sisal fibers and environmental application in adsorption of methylene blue. Journals & Books. 2020: 23: 1-9.

[10] Lopes F. C. S. M. R. Ag/ TiO2 photocatalyst immobilized onto modified natural fibers for photodegradation of anthracene. Chemical Engineering Science. 2020: 227: 115939.

[11] Streltsova E., Linton J. D. Biotechnology patents in BRICS countries: strategy and dynamics. Trends in Biotechnology. 2018: 36: 642-645.

[12] Santos J. J., Maranho L. T. Rhizospheric microorganisms as a solution for the recovery of soils contaminated by petroleum: A review. Journal of Environmental Management. 2018:20:104-113.

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Section 3

Conservation and

Management

Section 3
