Agrochemical Residues in Fish and Bivalves from Sepetiba Bay and Parnaiba River Delta, Brazil
Abstract
:1. Introduction
2. Materials and Methods
2.1. Sampling Area
2.2. Reagents and Standards
2.3. Sample Preparation
2.4. Instrumental Analysis and Optimization of the Analytical Method
2.5. Analytical Method Validation
2.6. Determination of Analytes in Samples
3. Results and Discussion
3.1. Optimization of Extraction Method
3.2. Determination of Analytes in Samples
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
- IPCS, W. Global Assessment of the State-of-the-Science of Endocrine Disruptors; World Health Organization: Geneva, Switzerland, 2002; Available online: https://apps.who.int/iris/handle/10665/67357 (accessed on 25 November 2022).
- Bila, D.M.; Dezotti, M. Endocrine disruptors in the environment: Effects and consequences. New Chem. 2007, 30, 651–666. [Google Scholar]
- Cunha, D.L.; Silva, S.M.C.; Bila, D.M. Regulation of Synthetic Estrogen 17α-Ethinylestradiol in Aquatic Matrices in Europe, United States and Brazil. Public Health Notebooks 2016, 32, 1–13. Available online: https://www.scielo.br/j/csp/a/sMfbYgmKM9yMTFpNVzPFStf/?format=pdf&lang=en (accessed on 25 November 2022).
- Brasil, 2002. Decree No. 4074, 4 January 2002. Brasília: Federal Official Gazette. Available online: http://www.planalto.gov.br/ccivil_03/decreto/2002/d4074.htm (accessed on 25 November 2022).
- EFSA 2014. Conclusion on the peer review of the pesticide human health risk assessment of the active substance chlorpyrifos. EFSA J. 2014, 12, 3640. Available online: https://www.efsa.europa.eu/en/efsajournal/pub/3640 (accessed on 18 March 2022).
- Tornero, V.; Hanke, G. Chemical contaminants entering the marine environment from sea-based sources: A review with a focus on European seas. Mar. Pollut. Bull. 2016, 112, 17–38. [Google Scholar] [CrossRef] [PubMed]
- EC, European Comission 2020. European Commission Pesticide Residue Database. Available online: https://ec.europa.eu/food/plant/pesticides/eu-pesticides-db_en (accessed on 13 February 2022).
- Cunha, S.C.; Menezes-Sousa, D.; Mello, F.V.; Miranda. J., A.T.; Fogaça, F.H.; Alonso, M.B.; Torres, J.P.; Fernandes, J.O. Survey on endocrine-disrupting chemicals in seafood: Occurrence and distribution. Environ. Res. 2022, 210, 112886. [Google Scholar] [CrossRef] [PubMed]
- Govett, G.; Genuis, S.J.; Govett, H.E.; Beesoon, S. Chlorinated pesticides and cancer of the head and neck: A retrospective case series. Eur. J. Cancer Prev. 2011, 20, 320–325. [Google Scholar] [CrossRef] [PubMed]
- Burns, J.S.; Williams, P.L.; Korrick, S.A.; Hauser, R.; Sergeyev, O.; Revich, B.; Lam, T.; Lee, M.M. Association between chlorinated pesticides in the serum of prepubertal Russian boys and longitudinal biomarkers of metabolic function. Am. J. Epidemiol. 2014, 180, 909–919. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Maisano, M.; Cappello, T.; Oliva, S.; Natalotto, A.; Giannetto, A.; Parrino, V.; Battaglia, P.; Romeo, T.; Salvo, A.; Spanò, N.; et al. PCB and OCP accumulation and evidence of hepatic alteration in the Atlantic bluefin tuna, T. thynnus, from the Mediterranean Sea. Mar. Environ. Res. 2016, 121, 40–48. [Google Scholar] [CrossRef] [PubMed]
- Lam, T.; Williams, P.L.; Burns, J.S.; Sergeyev, O.; Korrick, S.A.; Lee, M.M.; Birnbaum, L.S.; Revich, B.; Altshul, L.M.; Patterson, D.G., Jr.; et al. Predictors of serum chlorinated pesticide concentrations among prepubertal Russian boys. Environ. Health Perspect. 2013, 121, 1372–1377. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Zhang, Y.; Zhao, Y.G.; Cheng, H.L.; Muhammad, N.; Chen, W.S.; Zeng, X.Q.; Zhu, Y. Fast determination of fipronil and its metabolites in seafood using PRiME pass-through cleanup followed by isotope dilution UHPLC-MS/MS. Anal. Methods 2018, 10, 1673–1679. [Google Scholar] [CrossRef]
- Bettinetti, R.; Quadroni, S.; Boggio, E.; Galassi, S. Recent DDT and PCB contamination in the sediment and biota of the Como Bay (Lake Como, Italy). Sci. Total Environ. 2016, 542, 404–410. [Google Scholar] [CrossRef] [PubMed]
- Ferreira, V.B.; Estrella, L.F.; Alves, M.G.R.; Gallistl, C.; Vetter, W.; Silva, T.T.C.; Malm, O.; Torres, J.P.M.; Abadio-Finco, F.D.B. Residues of legacy organochlorine pesticides and DDT metabolites in highly consumed fish from the polluted Guanabara Bay, Brazil: Distribution and assessment of human health risk. J. Environ. Sci. Health 2020, 55, 30–41. [Google Scholar] [CrossRef]
- Li, Y.; Lohmann, R.; Zou, X.; Wang, C.; Zhang, L. Air-water exchange and distribution pattern of organochlorine pesticides in the atmosphere and surface water of the open Pacific ocean. Environ. Pollut. 2020, 265, 114956. [Google Scholar] [CrossRef] [PubMed]
- Lim, L.; Bolstad, H.M. Organophosphate insecticides: Neurodevelopmental effects. Encycl. Environ. Health 2019, 2, 785–791. [Google Scholar]
- Matsuo, N. Discovery and development of pyrethroid insecticides. Proc. Jpn. Acad. 2019, 95, 378–400. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Ramchandra, A.M.; Chacko, B.; Victor, P.J. Pyrethroid poisoning. Indian J. Crit. Care Med. Peer-Rev. Off. Publ. Indian Soc. Crit. Care Med. 2019, 23 (Suppl. 4), S267. [Google Scholar] [CrossRef]
- Ulusoy, S.; Özden, Ö.; Päpke, O. Organochlorine pesticide and polychlorinated biphenyl levels of horse mackerel (Trachurus sp.) caught from Marmara Sea coastal sites. Marine Biological Association of the United Kingdom. J. Mar. Biol. Assoc. UK 2017, 97, 401. [Google Scholar] [CrossRef]
- Beyer, J.; Green, N.W.; Brooks, S.; Allan, I.J.; Ruus, A.; Gomes, T.; Brate, I.L.N.; Schøyen, M. Blue mussels (Mytilus edulis spp.) as sentinel organisms in coastal pollution monitoring: A review. Mar. Environ. Res. 2017, 130, 338–365. [Google Scholar] [CrossRef]
- Campillo, J.A.; Fernández, B.; García, V.; Benedicto, J.; León, V.M. Levels and temporal trends of organochlorine contaminants in mussels from Spanish Mediterranean waters. Chemosphere 2017, 182, 584–594. [Google Scholar] [CrossRef] [PubMed]
- Milun, V.; Grgas, D.; Radman, S.; Štefanac, T.; Ibrahimpašić, J.; Landeka Dragičević, T. Organochlorines Accumulation in Caged Mussels Mytilus galloprovincialis—Possible Influence of Biological Parameters. Appl. Sci. 2020, 10, 3830. [Google Scholar] [CrossRef]
- Jeon, H.J.; Lee, Y.H.; Kim, M.J.; Choi, S.D.; Park, B.J.; Lee, S.E. Integrated biomarkers induced by chlorpyrifos in two different life stages of zebrafish (Danio rerio) for environmental risk assessment. Environ. Toxicol. Pharm. 2016, 43, 166–174. [Google Scholar] [CrossRef] [PubMed]
- Alonso, M.B.; Feo, M.L.; Corcellas, C.; Gago-Ferrero, P.; Bertozzi, C.P.; Marigo, J.; Flach, L.; Meirelles, A.C.O.; Carvalho, V.L.; Azevedo, A.F.; et al. Toxic heritage: Maternal transfer of pyrethroid insecticides and sunscreen agents in dolphins from Brazil. Environ. Pollut. 2015, 207, 391–402. [Google Scholar] [CrossRef] [PubMed]
- Barbosa, A.P.M.; Méndez-Fernandez, P.; Dias, P.S.; Santos, M.C.O.; Taniguchi, S.; Montone, R.C. Transplacental transfer of persistent organic pollutants in La Plata dolphins (Pontoporia blainvillei; Cetartiodactyla, Pontoporiidae). Sci. Total Environ. 2018, 631, 239–245. [Google Scholar] [CrossRef] [PubMed]
- Raina, R. Chemical Analysis of Pesticides Using GC/MS, GC/MS/MS, and LC/MS/MS. In Pesticides—Strategies for Pesticides Analysis; InTech: Rijeka, Croatia, 2011; p. 105. [Google Scholar]
- Cunha, S.C.; Fernandes, J.O.; Oliveira, M.B.P. Comparison of matrix solid-phase dispersion and liquid–liquid extraction for the chromatographic determination of fenthion and its metabolites in olives and olive oils. Food Addit. Contam. 2007, 24, 156–164. [Google Scholar] [CrossRef] [PubMed]
- Viñas, L.; Pérez-Fernández, B.; Soriano, J.A.; López, M.; Bargiela, J.; Alves, I. Limpet (Patella sp.) as a biomonitor for organic pollutants. A proxy for mussel? Mar. Pollut. Bull. 2018, 133, 271–280. [Google Scholar] [CrossRef] [PubMed]
- Cunha, S.C.; Trabalón, L.; Jacobs, S.; Castro, M.; Fernandez-Tejedor, M.; Granby, K.; Verbeke, W.; Kwadijk, C.; Ferrari, F.; Robbens, J.; et al. UV-filters and musk fragrances in seafood commercialized in Europe Union: Occurrence, risk and exposure assessment. Environ. Res. 2018, 161, 399–408. [Google Scholar] [CrossRef] [PubMed]
- Chang, H.Y.; Yang, W.C.; Xue, Y.J.; Tsai, M.Y.; Wang, J.H.; Chang, G.R. Phthalates and organophosphorus insecticide residues in shrimp determined by liquid/gas chromatography–tandem mass spectrometry and a health risk assessment. Mar. Pollut. Bull. 2019, 144, 140–145. [Google Scholar] [CrossRef] [PubMed]
- Mijangos, L.; Ziarrusta, H.; Zabaleta, I.; Usobiaga, A.; Olivares, M.; Zuloaga, O.; Etxebarria, N.; Prieto, A. Multiresidue analytical method for the determination of 41 multiclass organic pollutants in mussel and fish tissues and biofluids by liquid chromatography coupled to tandem mass spectrometry. Anal. Bioanal. Chem. 2019, 411, 493–506. [Google Scholar] [CrossRef] [PubMed]
- Preedy, V.R.; Watson, R. (Eds.) Olives and Olive Oil in Health and Disease Prevention; Academic Press: Cambridge, MA, USA, 2020. [Google Scholar]
- De Paula Filho, F.J.; Marins, R.V.; de Lacerda, L.D.; Aguiar, J.E.; Peres, T.F. Background values for evaluation of heavy metal contamination in sediments in the Parnaíba River Delta estuary, NE/Brazil. Mar. Pollut. Bull. 2015, 2, 424–428. [Google Scholar] [CrossRef] [PubMed]
- Santos, T.A.; Gonçalves, T.S.; Nascimento, P.S.D.; Fernandes, C.A.F.; Cunha, F.E.D.A. Seasonal variation on diet of juvenile Elops saurus Linnaeus, 1766 (Ladyfish) in the Parnaiba River Delta. Acta Limnol. Bras. 2020, 32, e11. [Google Scholar] [CrossRef]
- Mello, F.V.; Cunha, S.C.; Fogaça, F.H.; Alonso, M.B.; Torres, J.P.M.; Fernandes, J.O. Occurrence of pharmaceuticals in seafood from two Brazilian coastal areas: Implication for human risk assessment. Sci. Total Environ. 2022, 803, 149744. [Google Scholar] [CrossRef]
- Da Silva, L.C.; Martins, M.V.A.; Castelo, W.F.L.; Saibro, M.B.; Rangel, D.; Pereira, E.; Bergamaschi, S.; Mello-Sousa, S.H.; Varela, J.; Laut, L.; et al. Trace metals enrichment and potential ecological risk in sediments of the Sepetiba Bay (Rio de Janeiro, SE Brazil). Mar. Pollut. Bull. 2022, 177, 113485. [Google Scholar] [CrossRef] [PubMed]
- Molisani, M.M.; Marins, R.V.; Machado, W.; Paraquetti, H.H.M.; Bidone, E.D.; Lacerda, L.D. Environmental changes in Sepetiba bay, SE Brazil. Reg. Environ. Chang. 2004, 4, 17–27. [Google Scholar]
- Mello, F.V.; Roscales, J.L.; Guida, Y.S.; Menezes, J.F.; Vicente, A.; Costa, E.S.; Jiménez, B.; Torres, J.P.M. Relationship between legacy and emerging organic pollutants in Antarctic seabirds and their foraging ecology as shown by δ13C and δ15N. Sci. Total Environ. 2016, 573, 1380–1389. [Google Scholar] [CrossRef] [PubMed]
- Wongmaneepratip, W.; Leong, M.; Yang, H. Quantification and risk assessment of pyrethroid residues in seafood based on nanoparticle-extraction approach. Food Control 2022, 133, 108612. [Google Scholar] [CrossRef]
- Petrarca, M.H.; Fernandes, J.O.; Marmelo, I.; Marques, A.; Cunha, S.C. Multi-analyte gas chromatography-mass spectrometry method to monitor bisphenols, musk fragrances, ultraviolet filters, and pesticide residues in seafood. J. Chromatogr. A 2022, 1663, 462755. [Google Scholar] [CrossRef] [PubMed]
- Kaczyński, P.; Łozowicka, B.; Perkowski, M.; Szabuńko, J. Multiclass pesticide residue analysis in fish muscle and liver on one-step extraction-cleanup strategy coupled with liquid chromatography tandem mass spectrometry. Ecotoxicol. Environ. Saf. 2017, 138, 179–189. [Google Scholar] [CrossRef]
- European Commission, Document N0. SANTE/12682/2019, Analytical Quality Control and Method Validation Procedures for Pesticide Residues Analysis in Food and Feed, 2020. Available online: https://www.eurl-pesticides.eu/userfiles/file/EurlALL/AqcGuidance_SANTE_2019_12682.pdf (accessed on 25 November 2022).
- Choi, M.; Lee, I.S.; Jung, R.H. Rapid determination of organochlorine pesticides in fish using selective pressurized liquid extraction and gas chromatography–mass spectrometry. Food Chem. 2016, 205, 1–8. [Google Scholar] [CrossRef] [PubMed]
- Stanley, J.; Preetha, G. Pesticide Toxicity to Fishes: Exposure, Toxicity and Risk Assessment Methodologies. In Pesticide Toxicity to Non-Target Organisms; Springer: Dordrecht, The Netherlands, 2016. [Google Scholar]
- Al-Ghanim, K.A.; Mahboob, S.; Vijayaraghavan, P.; Al-Misned, F.A.; Kim, Y.O.; Kim, H.J. Sub-lethal effect of synthetic pyrethroid pesticide on metabolic enzymes and protein profile of non-target Zebra fish, Danio rerio. Saudi J. Biol. Sci. 2020, 27, 441–447. [Google Scholar] [CrossRef]
- USEPA. Reregistration Eligibility Decision: Alachlor; United States Environmental Protection Agency: Washington, DC, USA, 1998. Available online: http://www3.epa.gov/pesticides/chem_search/reg_actions/reregistration/red_PC-090501_1-Dec-98.pdf (accessed on 19 November 2022).
- Rusiecki, J.A.; Baccarelli, A.; Bollati, V.; Tarantini, L.; Moore, L.E.; Bonefeld-Jorgensen, E.C. Global. DNA hypomethylation is associated with high serum-persistent organic pollutants in Greenlandic Inuit. Environ. Health Perspect. 2008, 116, 1547–1552. [Google Scholar] [CrossRef] [PubMed]
- Jan, I.; Dar, A.A.; Mubashir, S.; Alam Wani, A.; Mukhtar, M.; Sofi, K.A.; Dar, I.H.; Sofi, J.A. Quantification, dissipation behavior and risk assessment of ethion in green pea by gas chromatography-electron capture detector. J. Sep. Sci. 2018, 41, 1990–1994. [Google Scholar] [CrossRef] [PubMed]
- Mali, G.V. Toxicological study of bifenthrin and its metabolites on earthworm (Eisenia fetida). Nat. Environ. Pollut. Technol. 2019, 18, 1387–1391. [Google Scholar]
- Jayaraj, R.; Megha, P.; Sreedev, P. Organochlorine pesticides, their toxic effects on living organisms and their fate in the environment. Interdiscip. Toxicol. 2016, 9, 90–100. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Rocha, A.C.; Camacho, C.; Eljarrat, E.; Peris, A.; Aminot, Y.; Readman, J.W.; Boti, V.; Nannou, C.; Marques, A.; Nunes, M.L.; et al. Bioaccumulation of persistent and emerging pollutants in wild sea urchin Paracentrotus lividus. Environ. Res. 2018, 161, 354–363. [Google Scholar] [CrossRef] [PubMed]
- Gadelha, J.R.; Rocha, A.C.; Camacho, C.; Eljarrat, E.; Peris, A.; Aminot, Y.; Readman, J.W.; Boti, V.; Nannou, C.; Kapsi, M.; et al. Persistent and emerging pollutants assessment on aquaculture oysters (Crassostrea gigas) from NW Portuguese coast (Ria De Aveiro). Sci. Total Environ. 2019, 666, 731–742. [Google Scholar] [CrossRef]
- Riaz, G.; Tabinda, A.B.; Kashif, M.; Yasar, A.; Mahmood, A.; Rasheed, R.; Khan, M.I.; Iqbal, J.; Siddique, S.; Mahfooz, Y. Monitoring and spatiotemporal variations of pyrethroid insecticides in surface water, sediment, and fish of the river Chenab Pakistan. Environ. Sci. Pollut. Res. 2018, 25, 22584–22597. [Google Scholar] [CrossRef]
- Ismail, M.; Ali, R.; Shahid, M.; Khan, M.A.; Zubair, M.; Ali, T.; Mahmood Khan, Q. Genotoxic and hematological effects of chlorpyrifos exposure on freshwater fish Labeo rohita. Drug Chem. Toxicol. 2018, 41, 22–26. [Google Scholar] [CrossRef]
- Olsvik, P.A.; Larsen, A.K.; Berntssen, M.H.; Goksøyr, A.; Karlsen, O.A.; Yadetie, F.; Sanden, M.; Kristensen, T. Effects of agricultural pesticides in aquafeeds on wild fish feeding on leftover pellets near fish farms. Front. Genet. 2019, 10, 794. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Lopes, T.O.M.; Passos, L.S.; Vieira, L.V.; Pinto, E.; Dorr, F.; Scherer, R.; Salustriano, N.A.; Carneiro, M.T.W.D.; Postay, L.F.; Gomes, L.C. Metals, arsenic, pesticides, and microcystins in tilapia (Oreochromis niloticus) from aquaculture parks in Brazil. Environ. Sci. Pollut. Res. 2020, 27, 20187–20200. [Google Scholar] [CrossRef] [PubMed]
- Martins, M.F.; Costa, P.G.; Bianchini, A. Contaminant screening and tissue distribution in the critically endangered Brazilian guitarfish Pseudobatos horkelii. Environ. Pollut. 2020, 265, 114923. [Google Scholar] [CrossRef] [PubMed]
- Nicklisch, S.C.; Bonito, L.T.; Sandin, S.; Hamdoun, A. Geographic differences in persistent organic pollutant levels of yellowfin tuna. Environ. Health Perspect. 2017, 125, 067014. [Google Scholar] [CrossRef] [Green Version]
- Klinčić, D.; Romanić, S.H.; Katalinić, M.; Zandona, A.; Čadež, T.; Sarić, M.M.; Sarić, T.; Aćimov, D. Persistent organic pollutants in tissues of farmed tuna from the Adriatic Sea. Mar. Pollut. Bull. 2020, 158, 111413. [Google Scholar] [CrossRef] [PubMed]
- Klinčić, D.; Romanić, S.H.; Kljaković-Gašpić, Z.; Tičina, V. Legacy persistent organic pollutants (POPs) in archive samples of wild Bluefin tuna from the Mediterranean Sea. Mar. Pollut. Bull. 2020, 155, 111086. [Google Scholar] [CrossRef] [PubMed]
- Munschy, C.; Bely, N.; Héas-Moisan, K.; Olivier, N.; Pollono, C.; Hollanda, S.; Bodin, N. Tissue-specific bioaccumulation of a wide range of legacy and emerging persistent organic contaminants in swordfish (Xiphias gladius) from Seychelles, Western Indian Ocean. Mar. Pollut. Bull. 2020, 158, 111436. [Google Scholar] [CrossRef] [PubMed]
- Miranda, D.A.; Yogui, G.T. Polychlorinated biphenyls and chlorinated pesticides in king mackerel caught off the coast of Pernambuco, northeastern Brazil: Occurrence, contaminant profile, biological parameters and human intake. Sci. Total Environ. 2016, 569, 1510–1516. [Google Scholar] [CrossRef]
- Kilercioglu, B.G.; Cengizler, I.; Daglioglu, N.; Kilercioglu, S. Organochlorine Pesticides and Polychlorinated Biphenyls in Blue Crabs Callinectes sapidus (Rathbun, 1896) from Akyatan Lagoon in the Eastern Mediterranean Region of Turkey. Mediterr. Mar. Sci. 2018, 19, 376–382. [Google Scholar] [CrossRef]
- Saber, T.M.; Khedr, M.H.; Darwish, W.S. Residual levels of organochlorine pesticides and heavy metals in shellfish from Egypt with assessment of health risks. Slov. Vet. Res. 2018, 55, 101–113. [Google Scholar] [CrossRef] [Green Version]
- Khallaf, E.A.; Authman, M.M.; Alne-na-ei, A.A. Evaluation of organochlorine and organophosphorus pesticides residues in the sediment and muscles of Nile tilapia Oreochromis niloticus (Linnaeus, 1758) fish from a River Nile Canal, Egypt. Int. J. Environ. Stud. 2018, 75, 443–465. [Google Scholar] [CrossRef]
- Qian, Z.; Luo, F.; Wu, C.; Zhao, R.; Cheng, X.; Qin, W. Indicator polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in seafood from Xiamen (China): Levels, distributions, and risk assessment. Environ. Sci. Pollut. Res. 2017, 24, 10443–10453. [Google Scholar] [CrossRef]
- Chang, G.R. Persistent organochlorine pesticides in aquatic environments and fishes in Taiwan and their risk assessment. Environ. Sci. Pollut. Res. 2018, 25, 7699–7708. [Google Scholar] [CrossRef]
- Zhang, X.; Wu, X.; Lei, B.; Jing, Y.; Zhang, X.; Fang, X.; Yu, Y. Transplacental transfer characteristics of organochlorine pesticides in paired maternal and cord sera, and placentas and possible influencing factors. Environ. Pollut. 2018, 233, 446–454. [Google Scholar] [CrossRef]
- Moraes, B. Global Scenario with Research Involving Agricultural Contaminants in Fish Endocrine System. Thesis. IFGoiano. 2019. Available online: https://repositorio.ifgoiano.edu.br/handle/prefix/588 (accessed on 13 February 2022).
Target Compounds | Log Kow | Transition m/z | Collision Energy (KV) | |
---|---|---|---|---|
Lindane | 3.72 | 218.8> 181> 180.9> | 183 109 145 | 5 30 12 |
Chlorpyriphos-methyl | 4.31 | 288> 286> | 93 271 270.0 | 15 26 16 |
Chlorpyriphos | 4.96 | 318.8> 314> 313.8> 28.8> | 286 258 272.9 | 5 14 15 |
Fipronil | 4.00 | 367> | 228 225 224 213 | 30 25 20 30 |
Ethion | 5.07 | 231> | 175 129 | 5 25 |
Aldrin | 6.50 | 298> 263> 257> | 263 191 193 222 | 8 30 12 |
Chlordene | 5.57 | 230> | 195 160 | 25 40 |
HCB | 5.73 | 283.9> 284> | 248.8 213.9 142 | 25 35 50 |
Mirex | 6.89 | 272> 271.9> | 237 167 235 116.9 | 20 40 15 25 |
Bifenthrin | 6.00 | 166> 181> 182> | 165 166 167 | 16 25 12 |
Permethrin | 6.50 | 183.1> 183> 163> | 168.1 153.1 115.2 77.1 127 | 15 25 38 5 |
Alachlor | 3.52 | 270> 238> | 161.5 | 20 |
Vinclozolin | 3.10 | 187 | 145.0 172.2 | 15 |
Lean Fish (μg kg−1 dw) | Fatty Fish (μg kg−1 dw) | Mussel (μg kg−1 dw) | |||||||
---|---|---|---|---|---|---|---|---|---|
10 | 80 | 320 | 20 | 120 | 270 | 20 | 120 | 400 | |
Lindane | 1.7 | 1.0 | 5.4 | 43.8 | 22.3 | 27.3 | 6.5 | 12.8 | 4.3 |
Chlorpyrifos-methyl | 0.8 | 2.3 | 3.2 | 15.8 | 40.6 | 32.3 | 26.6 | 12.6 | 7.5 |
Chlorpyrifos | 0.4 | 1.5 | 5.8 | 40.0 | 16.0 | 20.4 | 33.0 | 13.4 | 2.4 |
Fipronil | 5.8 | 5.4 | 41.0 | 33.5 | 8.8 | 18.7 | 20.12 | 7.4 | 6.0 |
Ethion | 0.7 | 2.6 | 15.4 | 36.9 | 20.5 | 14.5 | 18.16 | 80.0 | 7.5 |
Aldrin | 1.2 | 2.2 | 5.7 | 29.4 | 14.6 | 14.9 | 16.9 | 10.9 | 9.3 |
Chlordene | 3.4 | 2.5 | 4.0 | 25.5 | 14.3 | 23.8 | 9.4 | 10.4 | 9.0 |
HCB | 1.9 | 2.5 | 4.2 | 41.3 | 7.2 | 14.3 | 16.6 | 15.8 | 3.6 |
Mirex | 2.6 | 1.2 | 3.0 | 22.7 | 24.2 | 30.4 | 23.4 | 26.4 | 44.7 |
Bifenthrin | 1.1 | 1.3 | 2.4 | 21.6 | 26.4 | 19.1 | 8.4 | 6.8 | 3.6 |
Permethrin | 10.1 | 3.1 | 2.2 | 16.8 | 26.9 | 32.9 | 11.1 | 20.5 | 30.6 |
Alachlor | 0.9 | 2.3 | 2.1 | - | - | - | 25.0 | 105.3 | 31.9 |
Vinclozolin | 3.3 | 3.8 | 4.0 | 7.2 | 9.3 | 20.1 | 17.8 | 16.0 | 6.6 |
10 μg kg−1 dw | 80 μg kg−1 dw | 320 μg kg−1 dw | ||||
---|---|---|---|---|---|---|
Recovery (%) | RSD (%) | Recovery (%) | RSD (%) | Recovery (%) | RSD (%) | |
Lindane | 81.0 | 1.2 | 81.9 | 2.6 | 102.5 | 5.5 |
Chlorpyrifos-me | 85.7 | 0.2 | 44.3 | 58.1 | 101.7 | 1.9 |
Chlorpyrifos | 55.3 | 8.0 | 89.6 | 2.5 | 103.1 | 1.6 |
Fipronil | 45.3 | 18.4 | 77.9 | 14.2 | 81.8 | 18.9 |
Ethion | 103.4 | 4.9 | 84.9 | 7.2 | 94.5 | 4.9 |
Aldrin | 46.3 | 2.2 | 96.9 | 3.8 | 104.6 | 10.5 |
Chlordene | 50.3 | 14.5 | 100.8 | 4.6 | 99.4 | 1.5 |
HCB | 98.1 | 4.8 | 92.1 | 4.0 | 99.9 | 4.6 |
Mirex | 7.3 | 7.8 | 101.9 | 0.8 | 103.9 | 1.3 |
Bifenthrin | 35.1 | 10.3 | 98.3 | 3.3 | 99.1 | 1.4 |
Permethrin | 89.6 | 12.2 | 120.8 | 21.9 | 113.6 | 9.7 |
Alachlor | 59.3 | 0.1 | 88.9 | 1.8 | 98.6 | 1.5 |
Vinclozolin | 44.4 | 10.1 | 102.0 | 3.5 | 111.9 | 4.4 |
20 μg kg−1 dw | 120 μg kg−1 dw | 270 μg kg−1 dw | ||||
---|---|---|---|---|---|---|
Recovery (%) | RSD (%) | Recovery (%) | RSD (%) | Recovery (%) | RSD (%) | |
Lindane | 69.6 | 12.3 | 84.9 | 10.5 | 79.6 | 12.0 |
Chlorpyrifos-me | 88.5 | 14.6 | 74.2 | 10.2 | 71.7 | 25.0 |
Chlorpyrifos | 97.2 | 7.3 | 109.1 | 11.1 | 86.3 | 24.4 |
Fipronil | 105.3 | 0.9 | 87.3 | 3.7 | 92.4 | 8.9 |
Ethion | 85.5 | 2.3 | 79.4 | 38.2 | 68.5 | 64.2 |
Aldrin | 89.3 | 2.4 | 87.9 | 1.9 | 82.7 | 39.8 |
Chlordene | 74.7 | 1.3 | 90.5 | 37.2 | 71.3 | 48.9 |
HCB | 85.4 | 11.2 | 103.5 | 10.4 | 89.3 | 5.6 |
Mirex | 65.9 | 0.3 | 71.5 | 64.4 | 57.8 | 79.3 |
Bifenthrin | 79.8 | 1.0 | 88.1 | 47.1 | 62.8 | 66.2 |
Permethrin | 64.7 | 0.6 | 55.1 | 70.4 | 39.4 | 121.2 |
Vinclozolin | 95.7 | 0.4 | 82.5 | 6.6 | 75.6 | 21.7 |
20 μg kg−1 dw | 120 μg kg−1 dw | 400 μg kg−1 dw | ||||
---|---|---|---|---|---|---|
Recovery (%) | RSD (%) | Recovery (%) | RSD (%) | Recovery (%) | RSD (%) | |
Lindane | 106.3 | 2.7 | 97.0 | 4.3 | 99.5 | 5.5 |
Chlorpyrifos-me | 115.5 | 12.5 | 105.9 | 7.5 | 99.0 | 14.9 |
Chlorpyrifos | 114.2 | 5.4 | 100.4 | 2.3 | 102.8 | 20.0 |
Fipronil | 107.4 | 3.2 | 74.5 | 6.0 | 77.1 | 28.8 |
Ethion | 91.8 | 9.1 | 88.5 | 7.5 | 96.6 | 4.2 |
Aldrin | 102.7 | 10.0 | 111.5 | 9.3 | 10.0 | 7.0 |
Chlordene | 108.7 | 18.3 | 64.8 | 9.0 | 86.3 | 14.7 |
HCB | 170.3 | 9.2 | 93.0 | 3.6 | 97.2 | 10.7 |
Mirex | 105.7 | 40.3 | 63.4 | 44.8 | 51.3 | 92.2 |
Bifenthrin | 99.1 | 5.7 | 98.0 | 3.6 | 101.4 | 10.6 |
Permethrin | 370.8 | 35.6 | 106.1 | 30.6 | 50.5 | 165.7 |
Alachlor | 99.3 | 2.6 | 95.4 | 31.9 | 70.6 | 3.9 |
Vinclozolin | 131.3 | 34.8 | 83.3 | 6.6 | 109.9 | 10.5 |
Lean Fish (μg kg−1 dw) | Fatty Fish (μg kg−1 dw) | Mussel (μg kg−1 dw) | ||||
---|---|---|---|---|---|---|
LOD | LOQ | LOD | LOQ | LOD | LOQ | |
Lindane | 1.5 | 4.5 | 8.2 | 24.9 | 0.1 | 0.4 |
Chlorpyrifos-me | 0.5 | 1.5 | 12.5 | 37.9 | 7.0 | 21.2 |
Chlorpyrifos | 4.3 | 13.2 | 10.4 | 31.4 | 6.9 | 20.8 |
Fipronil | 1.9 | 5.7 | 20.3 | 61.4 | 15.9 | 48.3 |
Ethion | 21.2 | 64.4 | 12.8 | 38.5 | 1.5 | 4.6 |
Aldrin | 6.3 | 18.9 | 13.3 | 40.2 | 6.0 | 18.3 |
Chlordene | 9.5 | 28.7 | 10.4 | 31.5 | 9.0 | 27.2 |
HCB | 0.4 | 1.3 | 10.6 | 32.0 | 21.0 | 63.2 |
Mirex | 12.1 | 36.6 | 11.9 | 36.1 | 0.1 | 0.4 |
Bifenthrin | 12.3 | 37.2 | 12.9 | 30.1 | 37.2 | 39.1 |
Permethrin | 17.2 | 52.3 | 11.54 | 35.0 | 280.1 | 484.7 |
Alachlor | 5.2 | 15.7 | - | - | 0.5 | 1.4 |
Vinclozolin | 8.4 | 25.3 | 16.3 | 49.4 | 0.5 | 1.4 |
Found Analyte | Class | Seafood Species | Concentrations |
---|---|---|---|
Alachlor | Herbicide | seabass (n = 4) | 6.8 to 32.4 μg kg−1 |
mussels (n = 5) | 0.7 to 33.4 μg kg−1 | ||
clams (n = 18) | 0.5 to 93.1 μg kg−1 | ||
parati (n = 3) | 8.9; 9.0 and 420.4 μg kg−1 | ||
Ethion | organophosphorus | parati (n = 1) | 211.2 μg kg−1 |
mussels (n = 3) | <LOQ (4.6 μg kg−1), 12.9 and 15.1 μg kg−1 | ||
clams (n = 13) | <LOQ to 44.5 μg kg−1 | ||
Permethrin | Pyrethroid | clams (n = 2) | <LOQ |
Bifenthrin | parati (n = 4) | <LOQ to 43.4 μg kg−1 | |
mullet (n = 23) | <LOQ | ||
clams (n = 2) | <LOQ and 42.2 μg kg−1 |
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Miranda, J.A.T.; Fogaça, F.H.S.; Cunha, S.C.; Alonso, M.B.; Torres, J.P.M.; Fernandes, J.O. Agrochemical Residues in Fish and Bivalves from Sepetiba Bay and Parnaiba River Delta, Brazil. Int. J. Environ. Res. Public Health 2022, 19, 15790. https://doi.org/10.3390/ijerph192315790
Miranda JAT, Fogaça FHS, Cunha SC, Alonso MB, Torres JPM, Fernandes JO. Agrochemical Residues in Fish and Bivalves from Sepetiba Bay and Parnaiba River Delta, Brazil. International Journal of Environmental Research and Public Health. 2022; 19(23):15790. https://doi.org/10.3390/ijerph192315790
Chicago/Turabian StyleMiranda, Joyce Aparecida Tavares, Fabíola Helena S. Fogaça, Sara C. Cunha, Mariana Batha Alonso, João Paulo M. Torres, and José Oliveira Fernandes. 2022. "Agrochemical Residues in Fish and Bivalves from Sepetiba Bay and Parnaiba River Delta, Brazil" International Journal of Environmental Research and Public Health 19, no. 23: 15790. https://doi.org/10.3390/ijerph192315790