Antibióticos na produção de etanol combustível: análise, dispersão no meio ambiente e efeitos na biodigestão da vinhaça
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Data
2021-05-14
Autores
Silva, Josiel José da [UNESP]
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Editor
Universidade Estadual Paulista (Unesp)
Resumo
A vinhaça é um resíduo líquido proveniente da produção de etanol combustível a partir da cana-de-açúcar. Este resíduo tem sido utilizado há mais de 4 décadas na fertirrigação dos solos dos canaviais, sendo um aporte de água e nutrientes. Apesar da importância agronômica e econômica desta prática, a fertirrigação pode ser uma fonte de contaminantes para o meio ambiente, especialmente com relação à antibióticos, os quais são utilizados no processo de produção do etanol. Desta forma, o objetivo deste trabalho é avaliar possíveis riscos associados à prática da fertirrigação, do ponto de vista da dispersão de contaminantes orgânicos no meio ambiente, com maior foco em antibióticos, e avaliar o impacto da presença de antibióticos na biodigestão anaeróbia da vinhaça. Para isso, três distintas abordagens foram adotadas, sendo: i) desenvolvimento de método LC-MS/MS para a análise de antibióticos (monensina, penicilina G, virginiamicina M1, virginiamicina S1, tetraciclina e eritromicina) em vinhaça, sendo avaliadas as técnicas SPE, SALLE e SPE on-line para o preparo de amostras. ii) Análise de amostras de vinhaça, solo e água subterrânea de áreas fertirrigadas com vinhaça, por dois métodos. O primeiro, baseado em LC-MS/MS para a determinação de 32 antibióticos de múltiplas classes, sendo avaliadas as técnicas de extração QuEChERS e ELP para as amostras de solo. O segundo, baseado em análise de investigação de compostos suspeitos (Suspect Screening) empregando estratégias avançadas com base LC-HRMS para avaliar a presença de 7811 contaminantes, incluindo pesticidas, produtos farmacêuticos e uma ampla gama de produtos químicos industriais, entre outras substâncias. iii) Avaliação da inibição da produção de metano na biodigestão anaeróbia da vinhaça contaminada com diferentes concentrações dos antibióticos monensina, penicilina G e tetraciclina empregando reator em batelada (500 mL). Como resultado, foi verificado que as técnicas SPE, SALLE e SPE on-line mostraram-se adequadas para a extração da maioria dos analitos na vinhaça. Além disso, com o método SPE on-line-LC-MS/MS desenvolvido, foi verificado que a monensina é capaz de resistir ao processo de produção de etanol e foi detectada em uma amostra de vinhaça na concentração de 14,3 ng mL-1. Nas análises LC-MS/MS para múltiplas classes de antibióticos não foram detectados contaminantes adicionais, sendo que as técnicas de extração QuEChERS e ELP alcançaram desempenho semelhante, com pontos positivos específicos para cada caso. As análises por LC-HRMS permitiram a identificação por tentativa de 19 contaminantes de preocupação ambiental na vinhaça, 12 no solo e 25 na água subterrânea de áreas fertirrigadas. Porém, nenhum destes compostos estão diretamente ligados à vinhaça, sendo que os resultados mostraram a existência de outras fontes potenciais de contaminação para as amostras analisadas, principalmente associadas à atividade agrícola moderna. Os estudos de biodigestão permitiram verificar que os antibióticos estudados são capazes de inibir parcialmente a produção de metano nas concentrações de 0,5 ppm para a monensina, 1,0 ppm para a tetraciclina e 0,01 ppm para a penicilina. Estes resultados indicam que a vinhaça contaminada com antibióticos pode comprometer a eficiência da produção de biogás por biodigestão anaeróbia.
Vinasse is a liquid residue from sugarcane ethanol fuel production. This residue has been used for more than 4 decades in the fertigation of the soil of the sugarcane fields, providing water and nutrients. Despite the agronomic and economic importance of this practice, fertigation can be a source of contaminants for the environment, especially in relation to antibiotics, which are used in the ethanol production process. Thus, the objective of this work is to evaluate possible risks associated with the practice of fertigation, from the point of view of the dispersion of organic contaminants in the environment, with a greater focus on antibiotics, and to evaluate the impact of the presence of antibiotics on anaerobic digestion of vinasse. For this, three different approaches were adopted, being: i) development of LC-MS/MS method for the analysis of antibiotics (monensin, penicillin G, virginiamycin M1, virginiamycin S1, tetracycline and erythromycin) in vinasse, being evaluated the techniques SPE, SALLE and on-line SPE for sample preparation. ii) Analysis of vinasse, soil and groundwater samples from fertigates areas with vinasse, using two methods. The first, based on LC-MS/MS for the determination of 32 antibiotics from multiple classes, being that QuEChERS and PLE extraction techniques were evaluated for soil samples preparation. The second, based on suspect screening analysis employing advanced strategies based on LC-HRMS to assess the presence of 7811 contaminants, including pesticides, pharmaceuticals and a wide range of industrial chemicals, among other substances. iii) Evaluation of the inhibition of methane production in anaerobic digestion of vinasse contaminated with different concentrations of the antibiotics monensin, penicillin G and tetracycline in a batch reactor (500 mL). As result, it was possible to verify that the SPE, SALLE and on-line SPE techniques were suitable for the extraction of most analytes in vinasse. In addition, with the developed on-line SPE-LC-MS/MS method, it was possible to verify that monensin can resist to the ethanol production process and was detected in a vinasse sample at a concentration of 14.3 ng mL-1. In the LC-MS/MS analyzes for multiple classes antibiotics, no additional contaminants were detected, and the QuEChERS and PLE extraction techniques achieved similar performance, with specific positive points for each case. The analysis by LC-HRMS allowed the identification by tentative of 19 contaminants of environmental concern in the vinasse, 12 in the soil and 25 in the groundwater from fertigated areas. However, none of these compounds are causally linked to vinasse, and the results showed the existence of other potential sources of contamination for the analyzed samples, mainly associated with modern agricultural activity. The digestion experiments showed that the studied antibiotics can partially inhibit the production of methane at concentrations of 0.5 ppm for monensin, 1.0 ppm for tetracycline and 0.01 ppm for penicillin G. These results indicate that vinasse contaminated with antibiotics can compromise the efficiency of biogas production by anaerobic digestion.
Vinasse is a liquid residue from sugarcane ethanol fuel production. This residue has been used for more than 4 decades in the fertigation of the soil of the sugarcane fields, providing water and nutrients. Despite the agronomic and economic importance of this practice, fertigation can be a source of contaminants for the environment, especially in relation to antibiotics, which are used in the ethanol production process. Thus, the objective of this work is to evaluate possible risks associated with the practice of fertigation, from the point of view of the dispersion of organic contaminants in the environment, with a greater focus on antibiotics, and to evaluate the impact of the presence of antibiotics on anaerobic digestion of vinasse. For this, three different approaches were adopted, being: i) development of LC-MS/MS method for the analysis of antibiotics (monensin, penicillin G, virginiamycin M1, virginiamycin S1, tetracycline and erythromycin) in vinasse, being evaluated the techniques SPE, SALLE and on-line SPE for sample preparation. ii) Analysis of vinasse, soil and groundwater samples from fertigates areas with vinasse, using two methods. The first, based on LC-MS/MS for the determination of 32 antibiotics from multiple classes, being that QuEChERS and PLE extraction techniques were evaluated for soil samples preparation. The second, based on suspect screening analysis employing advanced strategies based on LC-HRMS to assess the presence of 7811 contaminants, including pesticides, pharmaceuticals and a wide range of industrial chemicals, among other substances. iii) Evaluation of the inhibition of methane production in anaerobic digestion of vinasse contaminated with different concentrations of the antibiotics monensin, penicillin G and tetracycline in a batch reactor (500 mL). As result, it was possible to verify that the SPE, SALLE and on-line SPE techniques were suitable for the extraction of most analytes in vinasse. In addition, with the developed on-line SPE-LC-MS/MS method, it was possible to verify that monensin can resist to the ethanol production process and was detected in a vinasse sample at a concentration of 14.3 ng mL-1. In the LC-MS/MS analyzes for multiple classes antibiotics, no additional contaminants were detected, and the QuEChERS and PLE extraction techniques achieved similar performance, with specific positive points for each case. The analysis by LC-HRMS allowed the identification by tentative of 19 contaminants of environmental concern in the vinasse, 12 in the soil and 25 in the groundwater from fertigated areas. However, none of these compounds are causally linked to vinasse, and the results showed the existence of other potential sources of contamination for the analyzed samples, mainly associated with modern agricultural activity. The digestion experiments showed that the studied antibiotics can partially inhibit the production of methane at concentrations of 0.5 ppm for monensin, 1.0 ppm for tetracycline and 0.01 ppm for penicillin G. These results indicate that vinasse contaminated with antibiotics can compromise the efficiency of biogas production by anaerobic digestion.
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Palavras-chave
Vinhaça, Etanol Combustível, Antibióticos, LC-MS/MS, Biodigestão anaeróbia