Remotion of the 17α-Ethinylestradiol Hormone (EE2) by Biosorbent (Arachis hypogaea) in Aqueous Solutions: Validation of Analytical Methodology and Adsorption Study

Alley Michael da Silva Procópio, Thayná Aparecida Cais, Waleska Freitas Da Silva, Márcia Matiko Kondo, Flávio Soares Silva, Sandro José de Andrade

Abstract


This study describes the application of peanut shells, a biodegradable agroindustrial residue as a biosorbent, in the 17α-ethinylestradiol (EE2) removal in water matrices. An analytical method was developed and validated from the high-performance liquid chromatographic technique with fluorescence detection (HPLC-FLD) in a λEx= 230 nm and λEm= 310 nm in the determination of EE2. The evaluated parameters were: selectivity, linearity (R2 = 0.9984 and R = 0.9992), precision (Variation coefficient = 2.90% and 2.95% for the first and second analyst, respectively), accuracy (recovery rate = 100.2 – 110.4%), detection limit (3.4 – 5.0 μg L-1), quantification limit (10.0 – 11.3 μg L-1) and robustness (recovery rate = 98.7 – 115.5%). The chromatographic analysis conditions were: mobile phase (water 2:3 acetonitrile), mobile phase flow (0.5 mL min-1), injection volume (10 µL), column temperature (45ºC) and race time (10 min). An experiment planning (Box-Behnken Model) was carried out for the investigation and verification of the adsorptive capacity of the peanut shells, of which 3 parameters were evaluated (stirring rate, pH and adsorbent mass) on 3 levels. Optimum experimental condition (2 g of adsorbent, pH = 6 and stirring at 500 rpm) with a removal rate of 90% in 24 hours of the process.


Keywords


17α-ethinylestradiol. endocrine disruptors. emerging pollutants. validation of analytical methodology. Box-Behnken. Removal. Biosorbents. peanut shells

Full Text:

HTML

References


CHOINA J, KOSSLICK H, FISCHER CH, FLECHSING GU, FRUNZA L, SCHULZ, A. Photocatalytic decomposition of pharmaceutical ibuprofen pollutions in water over titania catalyst. Applied Catalysis B: Environmental. 2013;129:589-598.

CANDIDO JP, ANDRADE SJ, FONSECA AL, SILVA FS, SILVA MRA, KONDO MM. Ibuprofen removal by heterogeneous photocatalysis and ecotoxicological evaluation of the treated solutions. Environmental Science and Pollution Research. 2016; 23:19911-19920.

SILVA CGA, COLLINS CH. Aplicações de cromatografia líquida de alta eficiência para o estudo de poluentes orgânicos emergentes. Química Nova, 2011, 34, 665-676.

DEBLONDE T, COSSU-LEGUILLE C, HARTEMANN P. Emerging pollutants in wastewater: A review of the literature. International Journal of Hygiene and Environmental Health, 2011, 214, 442-448.

JURADO A, VÀZQUEZ-SUÑÉ E, CARRERA J, ALADA ML, PUJADES E, BARCELÓ D. Emerging organic contaminants in groundwater in Spain: A review of sources, recente occurrence and fate in a European context. Science of the Total Environmental, 2012, 440, 82-94.

LUO Y, GUO W, NGO HH, NGHIEM LD, HAI FI, ZHANG J, LIANG S, WANG XC. A review on the occurrence of micropollutants in the aquatic environment and their fate and removal during wastewater treatment. Science of the Total Environmental, 2014, 473-474, 619-641.

BRAZ FS, SILVA MRA, SILVA FS, ANDRADE SJ, FONSECA AL, KONDO MM. Photocatalytic Degradation of Ibuprofen Using TiO2 and Ecotoxicological Assessment of Degradation Intermediates against Daphnia similis. Journal of Environmental Protection, 2014, 5, 620-626.

BIRCH GF, DRAGE DS, THOMPSON K, EAGLESHAM G, MUELLER JF. Emerging contaminants (pharmaceutical, personal care products, a food additive and pesticides) in waters of Sidney estuary, Australia. Marine Pollution Bulletin, 2015, 97, 56-66.

Patiño, Y.; Díaz, E.; Ordóñez, S.; Gallegos-Suarez, E.; Guerrero-Ruiz, A.; Rodríguez-Ramos, I. Adsorption of emerging pollutants on functionalized multiwall carbon Nanotubes. Chemosphere, 2015, 136, 174-180.

Barreiros, L.; Queiroz, J.F.; Magalhães, L.M.; Silva, A.M.T.; Segundo, M.A. Analysis of 17-β-estradiol and 17-α-ethinylestradiol in biological and environmental matrices — A review. Microchemical Journal, 2016, 126, 243-262.

Mei, S.; Wub, D.; Jiang, M.; Lu, B.; Lim, J.; Zhou, Y.; Lee, Y. Determination of trace bisphenol A in complex samples using selective molecularly imprinted solid-phase extraction coupled with capillary electrophoresis. Microchemical Journal, 2011, 98, 150-155.

Giulivo, M.; Alda, M.L.; Capri, E.; Barceló, D. Human exposure to endocrine disrupting compounds: Their role in reproductive systems, metabolic syndrome and breast cancer. A review. Environmental Research, 2016, 151, 251-264.

Diamanti-Kandarakis, E.; Bourguignon, J.P.; Giudice, L.C.; Hauser, R.; Prins, G.S.; Soto, A.M.; Zoeller, R.T.; Gore, A.C. Endocrine-disrupting chemicals: an endocrine society scientific statement. Endocrine Reviews, 2009, 30, 293-342.

NOHYNEK, G. J.; BORGERT, C. J.; DIETRICH, D.; ROZMAN, K. K. Endocrine disruption: fact or urban legend?. Toxicology Letters, 2013, 223, 295-305.

Sodré, F.F.; Montagner, C.C.; Locatelli, M.A.F.; Jardim, W.F. Ocorrência de interferentes endócrinos e produtos farmacêuticos em águas superficiais da região de Campinas (SP, Brasil). Journal of the Brazilian Society of Ecotoxicology, 2007, 2, 187-196.

Choina, J.; Duwensee, H.; Flechsing, G.-U.; Kosslick, H.; Morawski, A.W.; Tuan, V.A.; Schulz, A. Removal of hazardous harmaceutical from water by photocatalytic treatment. Central European Journal of Chemistry, 2010, 8, 1288-1297.

Fernandes, A.N.; Giovanela, M.; Almeida, C.A.P.; Esteves, V.I.; Sierra, M.M.D.; Grassi, M.T. Remoção dos hormônios 17β-estradiol e 17α-etinilestradiol de soluções aquosas empregando Turfa Decomposta como material adsorvente. Química Nova, 2011, 34, 1516-1533.

Silva, C.P.; Otero, M.; Esteves, V. Processes for the elimination of estrogenic steroid hormones from water: a review. Environmental Pollution, 2012, 165, 38-58.

Han, J.; Qiu, W.; Cao, Z.; Hu, J.; Gao, W. Adsorption of ethinylestradiol (EE2) on polyamide 612: Molecular modeling and effects of water chemistry. Water Research, 2013, 47, 2273-2284.

Aris, A.Z.; Shamsuddin, A.S.; Praveena, S.M. Occurrence of 17 α-ethynylestradiol (EE2) in the environment and effect on exposed biota: a review. Environment International, 2014, 69, 104-119.

Leonard, J.A.; Cope, W.G.; Hammer, E.J.; Barnhart, M.C.; Bringolf, R.B. Extending the toxicity-testing paradigm for freshwater mussels: Assessing chronic reproductive effects of the synthetic estrogen 17α-ethinylestradiol on the unionid mussel Elliptio complanata. Comparative Biochemistry and Physiology C, 2017, 191, 14-25.

Ifelebuegu, A.O. Removal of Steriod Hormones by Activated Carbon Adsorption-Kinetic and Thermodynamic Studies. Journal of Environmental Protection, 2012, 3, 469-475.

Clouzot, L.; Doumenq, P.; Vanloot, P.; Roche, N.; Marrot, B. Membrane bioreactors for 17α-ethinylestradiol removal. Journal of Membrane Science, 2010, 362, 81-85.

Papaevangelou, V.A.; Gikas, G.D.; Tsihrintzis, V.A.; Antonopoulou, M.A.; Konstantinou, I.K. Removal of Endocrine Disrupting Chemicals in HSF and VF pilot-scale constructed wetlands. Chemical Engineering Journal, 2016, 294, 146-156.

Liu, Z.H.; Kanjo, Y.; Mizutani, S. Removal mechanisms for endocrine disrupting compounds (EDCs) in wastewater treatment – physical means, biodegradation, and chemical advanced oxidation: a review. Science of the Total Environmental, 2009, 407, 731-748.

Rosal, R.; Rodríguez, A.; Perdigón-Melón, J. A.; Petre, A.; García-Calvo, E.; Gómez, M.J. Occurrence of emerging pollutants in urban wastewater and their removal through biological treatment followed by ozonation. Water Research, 2010, 44, 578-588.

Aquino, S.F.; Brandt, E.M.F.; Chernicharo, C.A.L. Removal of pharmaceuticals and endocrine disrupters in sewage treatment plants: literature review. Engenharia Sanitária Ambiental, 2013, 18, 187-204.

Diagboya, P.N.E.; Dikio, E.D. Silica-based mesoporous materials; emerging designer adsorbents for aqueous pollutants removal and water treatment. Microporous and Mesoporous Materials, 2018, 266, 252-267.

Tapia-Orozco, N.; Ibarra-Cabrerab, R.; Tecantea, A.; Gimenoa, M.; Parrac, R.; Garcia-Arrazola, R. Removal strategies for endocrine disrupting chemicals using cellulose-based materials as adsorbents: A review. Journal of Environmental Chemical Engineering, 2016, 4, 3122-3142.

Saxena, S.; Garg, S.; Jana, A.K. Synthesis of cellulose based polymers for sorption of azo dyes from aqueous solution. Journal of Environmental Research and Development, 2012, 6, 424-431.

Gonçalves, A.C., Descontaminação e monitoramento de águas e solos na região amazônica utilizando materiais adsorventes alternativos, visando a remoção de metais pesados tóxicos e pesticidas. Inclusão Social, 2013, 6, 105-113.

Bharathi, K.S.; Ramesh, S.T. Removal of dyes using agricultural waste as low-cost adsorbents: a review. Applied Water Science, 2013, 3, 773-790.

Grassi, M.; Kaykioglu, G.; Belgiorno, V.; Lofrano, G. Removal of emerging contaminants from water and wastewater by adsorption process In: Emerging Compounds Removal from Wastewater. SpringerBriefs in Molecular Science; Springer Netherlands, Ed.; Springer, Dordrecht, 2012; pp. 15-37.

Tanyildizi, M.S. Modeling of adsorption isotherms and kinetics of reactive dye from aqueous solution by peanut hull. Chemical Engineering Journal, 2011, 168, 1234-1240.

Deniz, F.; Karaman, S. Removal of an azo-metal complex textile dye from colored aqueous solutions using an agro-residue. Microchemical Journal, 2011, 99, 296-302.

Sharma, R.K.; Kumar, A.; Joseph, P.E. Removal of Atrazine from Water by Low Cost Adsorbents Derived from Agricultural and Industrial Wastes. Bulletin of Environmental Contamination and Toxicology, 2008, 80, 461-464.

Seixas, F.L.; Gimenes, M.L.; Fernandes-Machado, N.R.C. Tratamento da vinhaça por adsorção em carvão de bagaço de cana-de-açúcar. Química Nova, 2016, 39, 172-179.

Ribani, M.; Bottoli, C.B.G.; Collins, C.H.; Jardim, I.C.S.F.; Melo, L.F.C. Validação em métodos cromatográficos e eletroforéticos. Química Nova, 2004, 27, 771-780.

INMETRO. Instituto Nacional de Metrologia, Normalização e Qualidade Industrial. Orientações sobre Validação de Métodos de Ensaios Químicos DOQ-CGCRE-008, http://www.inmetro.gov.br/Sidoq/Arquivos/CGCRE/DOQ/DOQ-CGCRE-8_01.pdf, 2010 (acessed 12.10.16).

ANVISA. Agência Nacional de Vigilância Sanitária. RE 899/2003, http://www.anvisa.gov.br/medicamentos/RE_899_validacao.pdf, 2003 (acessed 12.10.16)

Brito, N.M.; Amarente, O.P; Polese, L.; Ribeiro, M.L. Validação de métodos analíticos: Estratégia e discussão. Pesticidas: Revista de Ecotoxicologia e Meio Ambiente, 2003, 13, 129-146.

González, A.G.; Herrador, M.A.; Asuero, A.G. Intra-laboratory assessment of method accuracy (trueness and precision) by using validation standards. Talanta, 2010, 82, 1995-1998.

Liz, M.V.; Amaral, B.; Stets, S.; Nagata, N.; Peralta-Zamora, P. Sensitive Estrogens Determination in Wastewater Samples by HPLC and Fluorescence Detection. Journal of the Brazilian Chemical Society, 2017, 28, 1453-1460.

Clara, M.; Strenn, B.; Saracevic, E.; Kreuzinger, N. Adsorption of bisphenol-A, 17β-estradiole and 17α-ethinylestradiole to sewage sludge. Chemosphere, 2004, 56, 843-851.

Rudder, J.; Van De Wiele, T.; Dhooge, W.; Comhaire, F.; Verstraete, W. Advanced water treatment with manganese oxide for the removal of 17a-ethynylestradiol (EE2). Water Research, 2004, 38, 184-192.




DOI: http://dx.doi.org/10.5902/2179460X42691

Refbacks

  • There are currently no refbacks.


Copyright (c) 2020 Ciência e Natura

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.

Creative Commons License

This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.