Many parameters are usually used as gauges to describe water quality worldwide, such as the concentrations of phosphorus, forms of nitrogen, dissolved oxygen (DO), among others. Though legislative limits for the concentrations of these substances are in place, such is not the case for caffeine. Caffeine is a pharmacologically active alkaloid, from the xanthine group, which can be used as a chemical tracer for anthropic influence over water resources. The objective of this study was to analyze the pollution indicators over the Igua?u River, one of the main rivers in Southern Brazil, through the examination of nutrients, DO and their correlations to caffeine. The water samples were collected from 10 sampling sites along the river course, unevenly spaced to better represent the different environmental scenarios present in its basin, extracted from 2014 to 2017. Caffeine was detected and quantified through high-efficiency liquid state chromatography. Results show that both nutrient and caffeine concentrations increased in intensely urbanized areas, specially from IG2 to IG5 sampling sites. Downstream from IG6 the contaminant concentrations decreased mainly due to higher river flows and lower population density. Caffeine was detected in 82% of the samples, indicating that most of the sampling sites were under anthropic influence.
KeywordsWater ResourcesWater QualityCaffeineUrban Areas
Gao, H., Zhang, L., Lu, Z., He, C., Li, Q. and Na, G. (2018) Complex Migration of Antibiotic Resistance in Natural Aquatic Environments. Environmental Pollution, 232, 1-9. https://doi.org/10.1016/j.envpol.2017.08.078
Lomsadze, Z., Makharadze, K., Tsitskishvili, M. and Pirtskhalava, R. (2017) Water Resources of Kakheti and Ecological Problems. Annals of Agrarian Science, 15, 204-208. https://doi.org/10.1016/j.aasci.2017.03.002
Zhu, Y.-G., Reid, B.J., Merharg, A.A., Banwart, S.A. and Fu, B.-J. (2017) Optimizing Peri-URban Ecosystems (PURE) to Re-Couple Urban-Rural Symbiosis. Science of the Total Environment, 586, 1085-1090. https://doi.org/10.1016/j.scitotenv.2017.02.094 https://www.sciencedirect.com/science/article/pii/S004896971730342X
Souza, J.R., Moraes, M.E.B., Sonoda, S.L. and Santos, H.C.R.G. (2014) A Importancia da Qualidade da água e os seus Múltiplos Usos: Caso Rio Almada, Sul da Bahia, Brasil. Revista Eletronica do Prodema, 8, 26-45.
Ahmad, J., Naeem, S., Ahmad, M., Usman, A.R.A. and Al-Wabel, M.I. (2019) A Critical Review on Organic Micropollutants Contamination in Wastewater and Removal through Carbon Nanotubes. Journal of Environmental Management, 246, 214-228. https://www.sciencedirect.com/science/article/pii/S0301479719307807
Brasil Ministério da Saúde, Fundacao Nacional de Saúde (2014) Manual de controle da qualidade da água para técnicos que trabalham em ETAS/Ministério da Saúde, Fundacao Nacional de Saúde. Funasa, Brasília. https://doi.org/10.1016/j.jenvman.2019.05.152
CONAMA (Conselho Nacional do meio Ambiente) (2005) Dispoe sobre a classificacao dos corpos de água e diretrizes ambientais para o seu enquadramento, bem como estabelece as condicoes e padroes de lancamento de efluentes, e dá outras providências. Resolucao n. 357, de 17 de marco de 2005 Diário Oficial [da] República Federativa do Brasil, Brasília.
Sun, Y., Chen, Z., Wu, G., Wu, Q., Zhang, F., Niu, Z. and Hu, H-Y. (2016) Characteristics of Water Quality of Municipal Wastewater Treatment Plants in China: Implications for Resource Utilization and Management. Journal of Cleaner Production, 131, 1-9. https://doi.org/10.1016/j.jclepro.2016.05.068
Chaneama, S., Inpotab, P., Saisarai, S., Wilairatd, P., Ratanawimarnwong, N., Uraisin, K., Meesiri, W. and Nacapricha, D. (2018) Green Analytical Method for Simultaneous Determination of Salinity, Carbonate and Ammoniacal Nitrogen in Waters Using Flow Injection Coupled Dual-Channel C4D. Talanta, 189, 196-204. https://doi.org/10.1016/j.talanta.2018.06.082
Aguado, D., Barat, R., Soto, J. and Martínez-manez, R. (2016) Monitoring Dissolved Orthophosphate in a Struvite Precipitation Reactor with a Voltammetric Electronic Tongue. Talanta, 159, 80-86. https://doi.org/10.1016/j.talanta.2016.06.002
Padedda, B.M., Sechi, N., Lai, G.G., Mariani, M.A., Pulina, S., Sarria, M., Satta, C.T., Virdis, T., Buscarinu, P. and Lugliè, A. (2017) Consequences of Eutrophication in the Management of Water Resources in Mediterranean Reservoirs: A Case Study of Lake Cedrino (Sardinia, Italy). Global Ecology and Conservation, 12, 21-35. https://doi.org/10.1016/j.gecco.2017.08.004
Montagner, C.C., Umbuzeiro, G.A., Pasquini, C. and Jardim, W.F. (2014) Caffeine as an Indicator of Estrogenic Activity in Source Water. Environmental Science: Processes and Impacts, 16, 1866-1869. https://doi.org/10.1039/C4EM00058G
Mizukawa, A., Cristina Filippe, T., Otávio Miranda Peixoto, L., Scipioni, B., Leonardi, I.R. and de Azevedo, J.C.R. (2019) Caffeine as a Chemical Tracer for Contamination of Urban Rivers. Revista Brasileira de Recursos Hídricos, 24, Article No. e29. https://doi.org/10.1590/2318-0331.241920180184 http://www.scielo.br/scielo.php?script=sci_arttext&pid=S2318-03312019000100225
Marques, J.P. and Lopes, G.C. (2015) Alcaloides como agentes antitumorais: Consideracoes químicas e biológicas. Revista Uningá, Maringá, 24, 56-61.
De Moraes, P.C.V (2018) Avaliacao da Distribuicao de Esteróis e Hormonios Estrógenos no Sedimento como Marcador Pontencial de Contaminacao e Toxicidade-Rio Jaguaribe/CE. Tese ao Programa de Pós-Graduacao em Ciências Marinhas Tropicais do Instituto de Ciências do Mar, como requisito parcial para obtencao do título de Doutor, outorgada pela Universidade Federal do Ceará. Fortaleza, 2018. 139 f. http://www.repositorio.ufc.br/bitstream/riufc/43231/1/2018_tese_pcvmorais.pdf
INCTAA (Instituto Nacional de Ciências e Tecnologias Analíticas Avancadas) (2014) Cafeína em águas de abastecimento público no Brasil. Instituto Nacional de Ciências e Tecnologias Analíticas Avancadas, Sao Carlos.
Kramer, R.D., Mizukawa, A., Ide, A.H., Marcante, L.O., Santos, M.M. and Azevedo, J.C.R. (2015) Determinacao de anti-inflamatórios na água e sedimento e suas relacoes com a qualidade da água na bacia do Alto Iguacu, Curitiba-PR. Revista Brasileira de Recursos Hídricos, 20, 657-667. https://doi.org/10.21168/rbrh.v20n3.p657-667
Osawa, R.A., Ide, A.H., Sampaio, N.M.F.M. and Azevedo, J.C.R. (2015) Determinacao de fármacos anti-hipertensivos em águas superficiais na regiao metropolitana de Curitiba. Revista Brasileira de Recursos Hídricos, 20, 1039-1050. https://doi.org/10.21168/rbrh.v20n4.p1039-1050
Verlicchi, P. and Zambello, E. (2015) Pharmaceuticals, and Personal Care Products in Untreated and Treated Sewage Sludge: Occurrence and Environmental Risk in the Case of Application on Soil—A Critical Review. Sci. Total Environ, 538, 750-767. https://doi.org/10.1016/j.scitotenv.2015.08.108
Sui, Q., Cao, X., Lu, S., Zhao, W., Qiu, Z. and Yu, G. (2015) Occurrence, Sources and Fate of Pharmaceuticals and Personal Care Products in the Groundwater: A Review. Emerging Contaminants, 1, 14-24. https://doi.org/10.1016/j.emcon.2015.07.001
Santos, M.M., Brehm, F.A., Filippe, T.C., Knapik, H.G. and Azevedo, J.C.R. (2016) Occurrence and Risk Assessment of Parabens and Triclosan in Surface Waters of Southern Brazil: A Problem of Emerging Compounds in an Emerging Country. Revista Brasileira de Recursos Hídricos, 21, 603-617. https://doi.org/10.1590/2318-0331.011616018
Machado, K.S., Azevedo, J.C.R., Braga, M.C.B., Ferreira, P.A.L. and Figueira, R. (2017) Distribution and Characterization of Sex Hormones in Sediment and Removal Estimate by Sewage Treatment Plant in South Brazil. Environment Pollutions and Climate Change, 1, Article No. 115. https://doi.org/10.4172/2753-458X.1000115
Mizukawa, A., Delgado, D.M., Azevedo, J.C.R., Fernandes, C.V.S., Díaz-Cruz, S. and Barceló, D. (2017) Sediments as a Sink for UV filters And Benzotriazoles: The Case Study of Upper Iguacu Watershed, Curitiba (Brazil). Environmental Science and Pollution Research, 24, 18284-18294. https://doi.org/10.1007/s11356-017-9472-9
Tran, N.H., Reinhard, M. and Gin, K.Y.H. (2018) Occurrence and Fate of Emerging Contaminants in Municipal Wastewater Treatment Plants from Different Geographical Regions—A Review. Water Research, 133, 182-207. https://doi.org/10.1016/j.watres.2017.12.029
Bem, C.C., Knapik, H.G., Fernandes, C.V.S., Braga, M.C.B. and Azevedo, J.C.R. (2013) Características da Matéria Organica-Estudo Comparativo de Padroes de Espectrometria de Fluorescência e UV-Vis de Rio e Lago em Bacias Urbanizadas. Revista Brasileira de Recursos Hídricos, 18, 135-147. https://doi.org/10.21168/rbrh.v18n1.p135-147
Ide, A.H., Cardoso, F.D., Santos, M.M., Kramer, R.D., Azevedo, J.C.R. and Mizukawa, A. (2013) Utilizacao da Cafeína como Indicador de Contaminacao por Esgotos Domésticos na Bacia do Alto Iguacu. Revista Brasileira de Recursos Hídricos, 18, 201-211. https://doi.org/10.21168/rbrh.v18n2.p201-211
Osawa, R.A. (2013) Determinacao de fármacos anti-hipertensivos na bacia do Alto Iguacu. 85 f. Dissertacao (Mestrado em engenharia de recursos hídricos e Ambiental), Universidade Federal do Paraná, Setor de tecnologia, Curitiba.
Knapik, H.G., Fernandes, C.V.S. and Avevedo, J.C.R. (2014) Aplicabilidade de técnicas de espectroscopia e da concentracao de carbono organico dissolvido na caracterizacao da matéria organica em rios urbanos. Revista Brasileira de Recursos Hídricos, 19, 214-225. https://doi.org/10.21168/rbrh.v19n4.p214-225
Ide, A.H. (2014) Produtos farmacêuticos e de higiene pessoal no rio Iguacu e seus afluentes. 119f. Dissertacao (Mestrado em Ciências e Tecnologia Ambiental), Universidade Tecnológica Federal do Paraná, Curitiba.
Machado, K.S., Cardoso, F.D., Azevedo, J.C.R. and Braga, C.B. (2014) Occurrence of Female Sexual Hormones in the Iguazu River Basin, Curitiba, Paraná State, Brazil. Acta Scientiarum Technology, 36, 421-427. https://doi.org/10.4025/actascitechnol.v36i3.18477
Knapik, H.G., Fernandes, C.V.S., Azevedo, J.C.R., Santos, M.M., Dall’Agnol, P. and Fontane, D.G. (2015) Biodegradability of Anthropogenic Organic Matter in Polluted Rivers Using Fluorescence, UV, and BDOC Measurements. Environmental Monitoring Assessment, 187, Article No. 104. https://doi.org/10.1007/s10661-015-4266-3
Leithold, J. (2017) Variabilidade espacial e temporal da matéria organica no ecossistema aquático nas bacias hidrográficas do alto e médio Iguacu. 179 f. Dissertacao (Mestrado em Engenharia de Recursos Hídricos e Ambiental) Setor de Tecnologia, Universidade Federal do Paraná, Curitiba, Brazil.
Sanepar (2017) Companhia de Saneamento do Paraná. Da nascente à foz, Iguacu. https://www.extraguarapuava.com.br/ultimas-noticias/rio-iguacu-da-nascente-a-foz/
Mizukawa, A., Reichert, G., Filippe, T.C., Brehm, F.A. and Azevedo, J.C.R. (2018) Occurrence and Risk Assessment of Personal Care Products in Subtropical Urban Rivers. Environmental Engineering Science, 35, 1263-1272. https://doi.org/10.1089/ees.2018.0066
SEMA (Secretaria de Estado do Meio Ambiente) and ANA (Agência Nacional de águas) (2010) BACIAS HIDROGRáFICAS DO PARANá. Secretaria de Estado do Meio Ambiente, PARANá. Curitiba.
Fernandes, C.V.S., Azevedo, J.C.R. and Porto, M.F.A. (2014) Integra 2: Bases Técnicas para Integracao de Instrumentos de Gestao de Recursos Hídricos. Relatório Parcial n. 1, Detalhamento da bacia do Alto Iguacu. Edital MCTI/CNPq/CT-Hidro n. 35/2013. Processo: 404259/2013-08. Universidade Federal do Paraná, UFPR; Universidade Tecnológica Federal do Paraná, UTFPR; Universidade de Sao Paulo, USP; Agosto/Dezembro de 2014.
Sanepar (2015) Companhia de Saneamento do Paraná. Plano Diretor do Sistema de Esgotamento Sanitário Integrado de Curitiba e Regiao Metropolitana (SEIC). Plano Diretor de Esgotamento Sanitário dos Sistemas Isolados da Regiao Metropolitana de Curitiba. Plano Diretor dos Resíduos Sólidos Gerados nos Sistemas de Abastecimento de água e nos Sistemas de Esgotamento Sanitário. Sanepar, Curitiba, 225 p.
American Public Health Association (APHA), Water Environment Federation and American Water Works Association (2005) Standard Methods for the Examination of Water and Wastewater Part 4000 Inorganic Nonmetallic Constituents. American Public Health Association, Washington DC.
SIMEPAR (Sistema Meteorológico do Paraná) (2017) Acesso ao sistema de dados de estacoes pluviométricas. Curitiba, 14 set. 2017. http://www.simepar.br/
Gunda, T., Hess, D., Hornbergrc, G.M. and Worland, S. (2019) Water Security in Practice: The Quantity-Quality-Society Nexus. Water Security, 6, Article ID: 100022.
Li, D. and liu, S. (2019) Detection of River Water Quality. In: Water Quality Monitoring and Management: Basis, Technology and Case Studies, Academic Press, Cambridge, 211-220. https://doi.org/10.1016/B978-0-12-811330-1.00007-7
Karmakar, S., Haque, S.M.S., Hossain, M.M., Sen, M. and Hoque, M.E. (2019). Water Quality Parameter as a Predictor of Small Watershed Land Cover. Ecological Indicators, 106, Article ID: 105462. https://doi.org/10.1016/j.ecolind.2019.105462 https://doi.org/10.1016/j.ecolind.2019.105462
Adeel, M., Song, X., Wang, Y., Francis, D. and Yang, Y. (2017) Environmental Impact of Estrogens on Human, Animal and Plant Life: A Critical Review. Environment International, 99, 107-119. https://doi.org/10.1016/j.envint.2016.12.010 https://www.sciencedirect.com/science/article/pii/S0160412016304494
Liu, Y., Tam, N.F.Y., Guan, Y. and Gao, B. (2012) Influence of a Marine Diatom on the Embryonic Toxicity of 17α-Ethynylestradiol to the Abalone Haliotis diversicolor supertexta. Water, Air, & Soil Pollution, 223, 4383-4395. https://doi.org/10.1007/s11270-012-1202-9 https://link.springer.com/article/10.1007/s11270-012-1202-9
Gomes, J.P. (2018) Análise da ocorrência do hormonio estrogênico, 17α-etinilestradiol, no Lago Paranoá. Dissertacao (mestrado), Fundacao Oswaldo Cruz, Escola Nacional de Saúde Pública Sergio Arouca. Brasília. https://www.arca.fiocruz.br/bitstream/icict/34185/2/ve_Juliana_Pinheiro_ENSP_2018
Yang, T.-H., Lin, C.-W. and Kao, C.-H. (2019) Occurrence, and Distribution of Pharmaceutical Compounds in the Danshuei River Estuary and the Northern Taiwan Strait. Marine Pollution Bulletin, 146, 509-520. https://doi.org/10.1016/j.marpolbul.2019.06.069
Orn, S., Holbech, H., Madsen, T.H., Norrgren, L. and Petersen, G.I. (2003) Gonad Development and Vitellogenin Production in Zebrafish (Danio rerio) Exposed to Ethinylestradiol and Methyltestosterone. Aquatic Toxicology, 65, 397-411. https://doi.org/10.1016/S0166-445X(03)00177-2 https://www.sciencedirect.com/science/article/abs/pii/S0166445X03001772
Peters, R.E., Courtenay, S.C., Hewitt, L.M. and Maclatchy, D.L. (2010) Effects of 17α-Ethynylestradiol on Early-Life Development, Sex Differentiation and Vitellogenin Induction in Mummichog (Fundulus heteroclitus). Marine Environmental Research, 69, 178-186. https://doi.org/10.1016/j.marenvres.2009.10.002 https://www.sciencedirect.com/science/article/abs/pii/S0141113609001287
Zhang, H., Kong, F.X., Yu, Y., Shi, X.L., Zhang, M. and Tian, H.E. (2010) Assessing the Combination Effects of Environmental Estrogens in Fish. Ecotoxicology, 19, 1476-1486. https://doi.org/10.1007/s10646-010-0533-9 https://link.springer.com/article/10.1007%2Fs10646-010-0533-9
Aoki, J.Y., Hatsuyama, A., Hiramatsu, N. and Soyano, K. (2011) Effects of Ethynylestradiol on Vitellogenin Synthesis and Sex Differentiation in Juvenile Grey Mullet (Mugil cephalus) Persist after Long-Term Exposure to a Clean Environment. Comparative Biochemistry and Physiology Part C: Toxicology & Pharmacology, 154, 346-352. https://doi.org/10.1016/j.cbpc.2011.07.001 https://www.sciencedirect.com/science/article/abs/pii/S1532045611001268
Liu, S., Ying, G.G., Zhou, L.J., Zhang, R.Q., Chen, Z.F. and Lai, H.J. (2012) Steroids in Typical Swine Farm and Their Release into the Environment. Water Research, 46, 3754-3768. https://doi.org/10.1016/j.watres.2012.04.006 https://pubmed.ncbi.nlm.nih.gov/22591816/
Barel-Cohen, K., Shore, L.S., Shemesh, M., Wenzel, A., Mueller, J. and Kronfeld-Schor, N. (2006) Monitoring of Natural and Synthetic Hormones in a Polluted River. Journal of Environmental Management, 78, 16-23. https://doi.org/10.1016/j.jenvman.2005.04.006 https://www.sciencedirect.com/science/article/pii/S0301479705001507