In this article, we report the results of the work carried out on the Verde River, a predominantly urban river located in the city of Ponta Grossa, Paraná, Brazil. Developed in three stages, it aimed to evaluate the water quality through physical-chemical parameters, the presence of caffeine as a chemical tracer, and the compound Triclosan (TCS), considered a pollutant of emerging concern. An attempt was made to identify possible polluting sources along the river. Samples were collected at 4 points from the spring region, with sampling upstream and downstream of a Sewage Treatment Plant (STP). The physical-chemical parameters were determined in situ, through portable analysers, as well as in the laboratory, in this case, through analyses using molecular absorption spectroscopy. For the determination of TCS and Caffeine, high-performance liquid chromatography (HPLC) was used, preceded by a pre-concentration step in the solid phase (SPE), and the techniques were implemented after validation. The physicochemical evaluations of the surface samples showed a decline in water quality after the STP. Mean total phosphorus concentrations of 1.0 mg · L -1 (±0.4), as well as dissolved oxygen (DO) levels below 5.0 mg · L -1 were verified downstream of the STP. Caffeine concentrations for Verde River were between 49.0 to 299.0 μg · L -1 , verified upstream and downstream of the STP. The results demonstrated the relationship between the presence of caffeine and impaction, either by the input of raw sewage or by treated effluent. TCS was detected by chromatographic analysis, downstream of the STP, with an average concentration of 27.6 (±1.7) μg · L -1 , noting that its presence was associated with the reactor maintenance procedure, with the STP in the process called bypass. Obtaining quality data from Verde River is important for the protection of the environment and affects the health of the population.
KeywordsSurface WaterMicropollutantsTriclosan
Instituto Brasileiro de Geografia e Estatística (IBGE) (2020) Pesquisa nacional de saneamento básico 2017: Abastecimento de água e esgotamento sanitário. IBGE, Coordenacao de Populacao e Indicadores Sociais, Rio de Janeiro, 124 p.
Kasonga, T.K., Coetzee, M.A., Kamika, I., Ngole-Jeme, V.M. and Momba, M.N.B. (2021) Endocrine-Disruptive Chemicals as Contaminants of Emerging Concern in Wastewater and Surface Water: A Review. Journal of Environmental Management, 277, Article ID: 111485. https://doi.org/10.1016/j.jenvman.2020.111485
Canela, M.C., Jardim, W.F., Sodré, F.F. and Grassi, M.T. (2014) Cafeína em águas de abastecimento público no Brasil. Editora Cubo, Sao Carlos, 96 p.
Pastorino, P. and Ginebreda, A. (2021) Contaminants of Emerging Concern (CECs): Occurrence and Fate in Aquatic Ecosystems. International Journal of Environmental Research and Public Health, 18, Article No. 13401. https://doi.org/10.3390/ijerph182413401
Soares, A.F.S. and Souza e Souza, L.P. (2020) Contaminacao das águas de abastecimento público por poluentes emergentes e o direito à saúde. Revista De Direito Sanitário, 20, 100-133. https://doi.org/10.11606/issn.2316-9044.v20i2p100-133
Shihomatsu, H.M., Martins, E.A.J., Cotrim, M.E.B., Lebre, D.T., Ortiz, N. and Pires, M.A.F. (2017) Guarapiranga Reservoir—Pharmaceuticals and Historical Urban Occupation in a Water Source. Journal of Geoscience and Environment Protection, 5, 1-17. https://doi.org/10.4236/gep.2017.513001
Reis Filho, R.W., de Araújo, J.C. and Vieira, E.M. (2006) Sexual Estrogenic Hormones: Bioactive Contaminants. Química Nova, 29, 817-822. https://doi.org/10.1590/S0100-40422006000400032
Correia, J. (2008) Análise de Poluentes Emergentes. Instituto da água da Regiao Norte (IAREN). Revista dos Antigos Alunos da Universidade do Porto, 5, 20-21. https://issuu.com/uporto/docs/uporto_alumni_06_novembro_2008
Matamoros, V., Nguyen, L.X., Arias, C.A., Salvadó, V. and Brix, H. (2012) Evaluation of Aquatic Plants for Removing Polar Microcontaminants: A Microcosm Experimente. Chemosphere, 88, 1257-1264. https://doi.org/10.1016/j.chemosphere.2012.04.004
Podder, A., Anwar Sadmani, A.H.M., Reinhart, D. Chang, N.-B. and Goel, R. (2021) Per and Poly-Fluoroalkyl Substances (PFAS) as a Contaminant of Emerging Concern in Surface Water: A Transboundary Review of Their Occurrences and Toxicity Effects. Journal of Hazardous Materials, 419, Article ID: 126361. https://doi.org/10.1016/j.jhazmat.2021.126361
Yang, L.J., Zhang, C.R., Huang, F., Liu, J.J., Zhang, Y.M., Yang, C.H., Ren, C.H., Chu, L.P., Liu, B. and Liu, J.F. (2020) Triclosan-Based Supramolecular Hydrogels as Nanoantibiotics for Enhanced Antibacterial Activity. Journal of Controlled Release, 324, 354-365. https://doi.org/10.1016/j.jconrel.2020.05.034
Piccoli, A., Fiori, J., Andrisano, V. and Orioli, M. (2002) Determination of Triclosan in Personal Health Care Products by Liquid Chromatography (HPLC). IL Farmaco, 57, 369-372. https://doi.org/10.1016/S0014-827X(02)01225-9
Adolfsson-Erici, M., Pettersson, M., Parkkonen, J. and Sturve, J. (2002) Triclosan, a Commonly Used Bactericide Found in Human Milk and in the Aquatic Environment in Sweden. Chemosphere, 46, 1485-1489. https://doi.org/10.1016/S0045-6535(01)00255-7
Lumbreras-Gonzalo, R., Landaluze-Sanz, J. and Cámara, C. (2014) Analytical Performance of Two Miniaturised Extraction Methods for Triclosan and Methyltriclosan, in Fish Roe and Surimi Samples. Food Chemistry, 146, 141-148. https://doi.org/10.1016/j.foodchem.2013.09.055
Koerich, P., Gilson, I. K., Vieira, M.G., Barbosa, S.C., Silva, M.R.V., Prime, E.G., Radunz, A.L. and Cabrera, L.C. (2021) Determinacao de contaminantes emergentes no Rio Lontra (Salto do Lontra-Paraná). Biodiversidade, 20, 106-121.
Bila, D.M. and Dezotti, M. (2003) Pharmaceutical Drugs in the Environment. Química Nova, 26, 523-530. https://doi.org/10.1590/S0100-40422003000400015
Melo, S.A.S., Trovo, A.G., Bautitz, I.R. and Nogueira, R.F.P. (2009) Degradation of Residual Pharmaceuticals by Advanced Oxidation Processes. Química Nova, 32, 188-197. https://doi.org/10.1590/S0100-40422009000100034
Tiburtius, E.R.L. and Scheffer, E.W.O. (2014) Triclosan: Destino no Meio Ambiente e Perspectivas no Tratamento de águas de Abastecimento Público. Revista Virtual de Química, 6, 1144-1159. https://doi.org/10.5935/1984-6835.20140075
Goncalves, E.S. (2008) O uso da cafeína como indicador de contaminacao por esgoto doméstico em águas superficiais. Universidade Federal Fluminense, Niterói, RJ.
Seiler, L.R., Zaugg, S.D., Thomas, J.M. and Howcroft, D.L. (1999) Caffeine and Pharmaceuticals as Indicators of Wastewater Contamination in Wells. Groundwater, 37, 405-410. https://doi.org/10.1111/j.1745-6584.1999.tb01118.x
Seigener, R. and Chen, R.F. (2002) Caffeine in Boston Harbor Seawater. Marine Pollution Bulletin, 44, 383-387. https://doi.org/10.1016/S0025-326X(00)00176-4
Buerge, I.J., Poiger, T., Müller, M.D. and Buser, H.-R. (2003) Caffeine, an Anthropogenic Marker for Wastewater Contamination of Surface Waters. Environmental Science and Technology, 37, 691-700. https://doi.org/10.1021/es020125z
Mizukawa, A., Filippe, T.C., Peixoto, L.O.M., Scipioni, B., Leonardi, I.R. and de Azevedo, J.C.R. (2019) Caffeine as a Chemical Tracer for Contamination of Urban Rivers. Brazilian Journal of Water Resources, 24, 1-10. https://doi.org/10.1590/2318-0331.241920180184
Bega, J.M.M. Oliveira, J.N., Albertin, L.L. and Isique, W.D. (2021) Uso da cafeína como indicador de poluicao por esgoto doméstico em corpos d’água urbanos. Revista de Engenharia Sanitária Ambiental, 26, 381-388. https://doi.org/10.1590/s1413-415220190084
Higdon, J.V. and Frei, B. (2006) Coffee and Health: A Review of Recent Human Research. Critical Reviews in Food Science and Nutrition, 46, 101-123. https://doi.org/10.1080/10408390500400009
Gnoatto, S.C.B., Bassani, V.L., Coelho, G.C. and Schenkel, E.P. (2007) Influence of the Extraction Methodology on the Methylxanthines Content of Maté (Ilex paraguariensis a. St.-Hil., aquifoliaceae). Química Nova, 30, 304-307. https://doi.org/10.1590/S0100-40422007000200012
Silva, A.R.M. and Nogueira, J.M.F. (2008) New Approach on Trace Analysis of Triclosan in Personal Care Products, Biological and Environmental Matrices. Talanta, 74, 1948-1504. https://doi.org/10.1016/j.talanta.2007.09.040
Silva, A.R.M. (2010) Desenvolvimento de novas metodologias analíticas para monitorizacao de PPCPs em matrizes reais. Universidade de Lisboa, Lisboa, 183 p.
Silva, C.G.A. and Collins, C.H. (2011) Applications of High Performance Liquid Chromatography for the Study of Emerging Organic Pollutants. Química Nova, 34, 665-676. https://doi.org/10.1590/S0100-40422011000400020
Zheng, C., Zhao, J., Bao, P. and Gao, J. (2011) Dispersive Liquid-Liquid Microextraction Based on Solidification of Floating Organic Droplet Followed by High-Performance Liquid Chromatography with Ultraviolet Detection and Liquid Chromatography-Tandem Mass Spectrometry for the Determination of Triclosan and 2,4-Dichlorophenol in Water Samples. Journal of Chromatography A, 1218, 3830-3836. https://doi.org/10.1016/j.chroma.2011.04.050
Verma, K.S. and Xia, K. (2010) Analysis of Triclosan and Triclocarban in Soil and Biosolids Using Molecularly Imprinted Solid Phase Extraction Coupled with HPLC-UV. Journal of AOAC International, 93, 1313-1321. https://doi.org/10.1093/jaoac/93.4.1313
Feitosa, L., Henriques, D.M., Olivier, B.C. and Chiapetta, S. (2010) Desenvolvimento de metodologia para determinacao de Triclosan em cremes empregando-se Cromatografia Líquida de Ultra Eficiência. Sociedade Brasileira de Química (SBQ) Livro de Resumos. 33a Reuniao Anual da Sociedade Brasileira de Química, Sao Paulo.
Skoog, D.A., Holler, F.J. and Nieman, T.A. (2006) Princípios de Análise Instrumental. 5th Edition, Bookman, Porto Alegre, 999 p.
Silveira, E.L. (2020) Estrutura da ictiofauna de uma microbacia neotropical: diversidade funcional e ecologia trófica. Universidade Federal do Paraná, Curitiba, 226 p.
BRASIL (2005) Resolucao No. 357 de 17 de marco de 2005. Ministério do Meio Ambiente, CONAMA-Conselho Nacional do Meio Ambiente.
Ponta Grossa (2017) A Cidade: Características Gerais. Prefeitura Municipal de Ponta Grossa, Paraná. https://www.pontagrossa.pr.gov.br/acidade
CETESB-Companhia de Saneamento de Sao Paulo (2016) Relatório 2016. Apêndice E: Significado Ambiental e Sanitário das Variáveis de Qualidade. https://cetesb.sp.gov.br/aguas-interiores/wp-content/uploads/sites/12/2017/11/Ap%C3%AAndice-E-Significado-Ambiental-e-Sanit%C3%A1rio-das-Vari%C3%A1veis-de-Qualidade-2016.pdf
ANA-Agência Nacional de águas (2016) Portal da qualidade das águas: índice de qualidade das águas. http://portalpnqa.ana.gov.br/indicadores-indice-aguas.aspx
Silva, G.S. and Jardim, W.F. (2006) A New Water Quality Index for Protection of Aquatic Life Appllied to the Atibaia River, Region of Campinas/Paulínia Cities-Sao Paulo State. Química Nova, 29, 689-694. https://doi.org/10.1590/S0100-40422006000400012
Merten, G.H. and Minella, J.P. (2002) Qualidade da água em bacias hidrográficas rurais: Um desafio atual para a sobrevivência futura. Agroecologia e Desenvolvimento Rural Sustentável, 3, 32-37.
Elser, J.J., Bracken, M.E.S., Cleland, E.E., Gruner, D.S., Harpole, W.S., Hillebrand, H., Ngai, J.T., Seabloom, E.W., Shurin, J.B. and Smith, J.E. (2007) Global Analysis of Nitrogen and Phosphorus Limitation of Primary Producers in Freshwater, Marine and Terrestrial Ecosystems. Ecology Letters, 10, 1135-1142. https://doi.org/10.1111/j.1461-0248.2007.01113.x
Ribani, M., Bottoli, C.B.G., Collins, C.H., Jardim, I.C.S.F. and Melo, L.F.C. (2004) Validation for Chromatographic and Electrophoretic Methods. Química Nova, 27, 771-780. https://doi.org/10.1590/S0100-40422004000500017
Huber, L. (1998) Validation of Analytical Methods. LC GC Internacional, 11, 96-105.
Wang, Y., Suidan, M.T. and Rittman, B.E. (1986) Anaerobic Treatment of Phenol by an Expanded-Bed Reactor. Journal-Water Pollution Control Federation, 58, 227-233. http://www.jstor.org/stable/25042885
Gardner, D.A., Suidan, M.T. and Kobayashi, H.A. (1988) Role of GAC Activity and Particle Size during the Fluidized-Bed Anaerobic Treatment of Refinery Sour Water Stripper Bottoms. Journal-Water Pollution Control Federation, 60, 505-513. http://www.jstor.org/stable/25043526
Pfeffer, J.T. and Suidan, M.T. (1989) Continuous Processing of Toxic Organics in a Fluidized-Bed GAC Reactor Employing Carbon Replacement. Biotechnology and Bioengineering, 33, 139-148. https://doi.org/10.1002/bit.260330202
Suidan, M.T., Flora, J.R.V., Boyer, T.K., Wuellner, A.M. and Narayanan, B. (1996) Anaerobic Dechlorination Using a Fluidized-Bed GAC Reactor. Water Research, 30, 160-170. https://doi.org/10.1016/0043-1354(95)00098-6
Tsuno, H., Kawamura, M. and Somiya, I. (1996) Anaerobic Degradation of Pentachlorophenol (PCP) in Biological Expanded-Bed Reactor. Water Science and Technology, 34, 335-344. https://doi.org/10.2166/wst.1996.0568
Deere, J.R., Streets, S., Jankowski, M.D., Ferrey, M., Chenaux-Ibrahim, Y., Convertino, M., Isaac, E.J., Phelps, N.D., Primus, A., Servadio, J.L., Singer, R.S., Travis, D. A., Moore, S. and Wolf, T.M. (2021) A Chemical Prioritization Process: Applications to Contaminants of Emerging Concern in Freshwater Ecosystems. Science of the Total Environment, 772, Article ID: 146030. https://doi.org/10.1016/j.scitotenv.2021.146030
Freire, F.B., Pires, E.C. and Freire, J.T. (2008) Tratamento anaeróbio de pentaclorofenol em reator de leito fluidificado alimentado com água residuária sintética contendo glicose como fonte única de carbono. Revista de Engenharia Sanitária Ambiental, 13, 339-346. https://doi.org/10.1590/S1413-41522008000300014
Chen, X., Nielsen, J.L., Furgal, K., Liu, Y., Lolas, I.B. and Bester, K. (2011) Biodegradation of Triclosan and Formation of Methyl-Triclosan in Activated Sludge under Aerobic Conditions. Chemosphere, 84, 452-456. https://doi.org/10.1016/j.chemosphere.2011.03.042
Froehner, S., Souza, D.B., Machado, K.S. and Rosa, E.C. (2010) Tracking Anthropogenic Inputs in Barigui River, Brazil Using Biomarkers. Water Air and Soil Pollution, 210, 33-41. https://doi.org/10.1007/s11270-009-0220-8
Montagner, C.C. and Jardim, W.F. (2011) Spatial and Seasonal Variations of Pharmaceuticals and Endocrine Disruptors in the Atibaia River, Sao Paulo State (Brazil). Journal of Brazilian Chemical Society, 22, 1452-1462. https://doi.org/10.1590/S0103-50532011000800008
Ministério do Meio Ambiente (2005) Resolucao No. 430 de 13 de maio de 2011. CONAMA-Conselho Nacional do Meio Ambiente.