Especiaçao do cobre em águas naturais : influencia de fatores associados r urbanizaçao

Orientador: Marco Tadeu GrassiTese (doutorado) - Universidade Federal do Paraná, Setor de Ciencias Exatas, Programa de Pós-Graduaçao em Química. Defesa: Curitiba, 2005Inclui bibliografiaResumo: Neste trabalho, foi avaliada a dinâmica e o comportamento do cobre em amostras de águas superficiais de rios localizados na Região Metropolitana de Curitiba (RMC). Durante um ano, foram realizadas coletas mensais nos Rios Iraí e Iguaçu, em pontos localizados à montante e jusante da cidade de Curitiba, respectivamente, como forma de avaliar o efeito da urbanização sobre aspectos tais como o aporte, a partição, a especiação e o comportamento do cobre, do ponto de vista geoquímico. Por meio da determinação de parâmetros físicos, químicos e hidrológicos, foi evidenciado um grau mais elevado de deterioração da qualidade das águas do Rio Iguaçu devido ao processo de urbanização. Neste rio também foram determinados os teores mais elevados de cobre total recuperável. A identificação das principais fontes de aporte do cobre para os rios estudados foi obtida por meio do tratamento multivariado dos dados. Desta forma, foi possível observar influências sazonais e espaciais no aporte do cobre para ambos os rios. Durante o período de maior pluviosidade, fontes difusas, tais como a drenagem urbana, exerceram um papel fundamental no aporte do cobre para estes corpos aquáticos. Entretanto, durante o período de menor pluviosidade, fontes pontuais foram as principais fontes de aporte do cobre, principalmente para o Rio Iguaçu, que também apresentou níveis mais elevados de cloreto e carbono orgânico dissolvido decorrentes, provavelmente, do aporte de esgoto bruto e tratado nas águas deste rio. Resultados obtidos para a distribuição do cobre na coluna de água revelaram que no Rio Iraí, o metal permaneceu preferencialmente na fração dissolvida, enquanto que no Rio Iguaçu, níveis mais elevados do cobre foram encontrados na fração particulada. A distribuição do metal em ambos os rios foi governada por processos distintos. No Rio Iraí, acredita-se que a presença de quantidades mais elevadas de colóides inorgânicos foi importante para a permanência do metal na fração dissolvida, enquanto que no Rio Iguaçu, o cobre permaneceu na fração particulada devido à presença de sólidos em suspensão ricos em matéria orgânica humificada. A avaliação da capacidade de complexação dos rios frente ao cobre mostrou resultados distintos para ambos os rios. Enquanto que no Rio Iraí foi detectada a presença de matéria orgânica com sítios disponíveis à complexação, no Rio Iguaçu foi observada a presença de matéria orgânica de baixa reatividade. Utilizando procedimentos baseados na espectrofotometria de fluorescência molecular, também foi possível identificar diferenças quanto às características dos ligantes orgânicos presentes na fração dissolvida de amostras dos rios estudados. Neste caso, também foi observada a presença de matéria orgânica de baixa reatividade nas amostras do Rio Iguaçu, principalmente durante o período de menor precipitação.Abstract: Copper behavior and dynamics in water bodies located in Curitiba's Metropolitan Region were evaluated in this work. Samples of Iraí and Iguaçu rivers were collected in points sited upstream and downstream the City of Curitiba, respectively, during a 12-months period. By this sampling regime we collected information regarding the influence of urban processes on copper loads, partition, speciation, and behavior under the geochemical viewpoint. Through systematic determinations of aquatic parameters we verified a high degree of pollution in Iguaçu River due to urbanization processes. Principal Component Analysis indicated seasonal and spatial effects on copper concentration and loads in both environments. During the rainy season, nonpoint sources such as urban runoff are believed to be the major source of copper in both cases. In contrast, during the lower precipitation period, the discharge of raw sewage seems to be the primary source of copper to the Iguaçu River, which also exhibited higher total metal concentrations. Partition and speciation analyses revealed that in Iguaçu River, copper was preferably bound to the particulate matter. This association seems to be enhanced due to the presence of humic substances covering the suspended particles of this river. On the opposite, in the Iraí River copper was preferably found in the dissolved phase due to a possible role of inorganic colloids. The evaluation of copper complexation demonstrated the presence of available ligands in the dissolved organic matter from Iraí River. In Iguaçu River, however, we observed the existence of low reactive organic matter in the dissolved phase. By using molecular fluorescence determinations we were able to perceive differences in the characteristics of the dissolved organic matter from both water bodies. In addiction, it was possible to observe that the dissolved organic matter from Iguaçu River exhibited low reactivity, mainly during the less precipitation period

Drugs of abuse in waters and wastewaters : occurrence, analytical determination and forensic applications

Drugs of abuse are commonly used outside medical or legal settings where their production, marketing and consumption are subject to legal summons and/or intervention. Classified as emerging contaminants, these substances have been recently detected in samples of environmental concern, such as waters and wastewaters. This review presents the state-of-the-art on the methodological approaches used in sample preparation, the main techniques applied in analytical determination at trace levels, as well as the use of information related to the drug or its metabolite concentration in sewage samples to empirically estimate the consumption of drugs of abuse in a city or region

Wastewater-based epidemiology of cocaine in the Brazilian Federal District : spatial distribution, weekly variation and sample preservation strategies

The distribution of consumed cocaine in the Brazilian Federal District (FD) was estimated using the wastewater-based epidemiology (WBE) approach. Sewage samples from eight wastewater treatment plants were analyzed for cocaine (COC) and benzoylecgonine (BE) using solid-phase extraction followed by liquid chromatography-mass spectrometry. The highest per capita consumption was noticed for the northern area of the Brazilian Capital (1162 mg day-1 1000 inh‑1) being 32% higher than the average consumption rate of the investigated region. In this area, a day-to-day investigation revealed an average cocaine consumption of 1800 mg day-1 1000 inh-1 during the weekend, i.e., more than 50% higher than weekdays. An annual street-grade cocaine load of about 2 ton was estimated for the FD considering previous information on the actual purity of seized street drugs as well as consumers between 15 and 64 years old. Sample preservation strategies were also investigated in order to expand the WBE approach to other Brazilian areas. Sample acidification to pH 2.0 presented the smallest relative errors for COC (+11%) and BE (−4%) after a period of three days under typical transport conditions practiced by the Brazilian national postal service

Seasonal and spatial distribution of caffeine, atrazine, atenolol and DEET in surface and drinking waters from the Brazilian Federal District

Selected emerging contaminants in water samples from the Brazilian capital were investigated by liquid chromatography-mass spectrometry after solid-phase extraction. In Paranoá Lake, an urban reservoir that will be used to produce drinking water, caffeine was the most abundant contaminant found (average of 53 ng L-1), followed by atenolol (34 ng L-1), N, N -diethyl-meta -toluamide (DEET, 12 ng L-1) and atrazine (3.8 ng L-1). The role of wastewaters discharges could not be evidenced probably due to the water flow and circulation in the lake. However, higher concentrations were detected during the dry season suggesting the presence of point sources, except for atrazine. In source waters, concentrations were lower in comparison with Paranoá Lake waters. Environmental risk assessment shows the need for further surveys for atrazine. For drinking waters, only caffeine and atrazine were detected at average concentrations of 8.6 and 3.2 ng L-1, respectively. No risk for human health was observed

Illicit drugs, metabolites and adulterants in wastewater : monitoring community drug abuse in the brazilian Federal District during the 2014 Soccer World Cup

A multiresidue method was developed to estimate community drug use during two weekends of the 2014 Soccer World Cup via wastewater analyses. Five of the 16 investigated substances were detected in all eight samples. Benzoilecgonine (BE), the major cocaine metabolite, was the most abundant substance (1.9 ± 0.3 to 4.2 ± 0.2 μg L-1) followed by anhydroecgonine (AE) (1.5 ± 0.2 to 2.6 ± 0.2 μg L-1), phenacetin (PHE) (0.62 ± 0.06 to 1.3 ± 0.1 μg L-1), levamisole (LEV) (0.5 ± 0.2 to 1.23 ± 0.09 μg L-1), and cocaine (COC) (0.46 ± 0.07 to 0.8 ± 0.1 μg L-1). COC and BE levels suggested a human consumption origin for the investigated drugs. AE/BE ratios revealed a significant use of smoked crack/free base cocaine. Relationships between the adulterants PHE and LEV evidenced a higher use of crack cocaine in the South-Wing WWTP region. An estimative for cocaine use revealed slightly higher drug consumption during the Soccer World Cup weekends in comparison with a typical weekend in 2012

Assessing Cocaine Use Patterns in the Brazilian Capital by Wastewater-Based Epidemiology

This is the postprint (accepted manuscript) version of the article published by Taylor & Francis in the International Journal of Environmental Analytical Chemistry on December, 10th 2018. Available on-line: http://www.tandfonline.com//10.1080/03067319.2018.1554743The levels of cocaine (COC) and its metabolites benzoylecgonine (BE) and cocaethylene (COE) in wastewater samples from Brasilia, Brazil, were determined using liquid chromatography coupled to hybrid quadrupole-time-of-flight mass spectrometry. The former metabolite was used to estimate cocaine consumption using a country-tuned correction factor that considers BE excretion rates for different routes of administration as well as the fraction of crack users in Brazil. A day-to-day analysis during a week indicates higher cocaine use in weekends with peaks on Sunday in both southern (7385 ± 121 mg day−1 1000 inhab−1) and northern (3566 ± 171 mg day−1 1000 inhab−1) areas of Brasilia. A significant high cocaine use was also observed in the Carnival Day of 2018 (6229 ± 219 mg day−1 1000 inhab−1). COE/BE ratios were used to assess COC and alcohol co-consumption since COE is produced during the co-consumption of both substances. Higher ratios were also observed during the weekend. However, higher ratios on Saturdays rather than Sundays may be explained by the decrease of BE excretion during the co-consumption with alcohol, which may lead to an underestimation of the cocaine use estimates on Saturdays, as well as by different patterns of co-consumption by powder and crack users, where the latter usually drink lower amounts of alcohol. Our data suggest that only 3% of cocaine was seized by the local Technical Police during the studyThis work was supported by the Federal District Research Foundation under Grant [193.000.916/ 2015]; the Spanish Agencia Estatal de Investigación under Grant [CTM2017-84763-C3-2-R]; the Galician Council of Culture, Education and Universities under Grants [ED431C2017/36]; IGM postdoctoral contract, Plan Galego I2C-Modalidade B, ED481D 2017/003; and FEDER/ERDFS

Profiling cocaine residues and pyrolytic products in wastewater by mixed‐mode liquid chromatography–tandem mass spectrometry

This is the peer reviewed version of the following article: González‐Mariño, I, Estévez‐Danta, A, Rodil, R, et al. Profiling cocaine residues and pyrolytic products in wastewater by mixed‐mode liquid chromatography–tandem mass spectrometry. Drug Test Anal. 2019; 11: 1018– 1027, which has been published in final form at https://doi.org/10.1002/dta.2590. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived VersionsThis work provides a new analytical method for the determination of cocaine, its metabolites benzoylecgonine and cocaethylene, the pyrolytic products anhydroecgonine and anhydroecgonine methyl ester, and the pharmaceutical levamisole in wastewater. Samples were solid‐phase extracted and extracts analyzed by liquid chromatography–tandem mass spectrometry using, for the first time in the illicit drug field, a stationary phase that combines reversed‐phase and weak cation‐exchange functionalities. The overall method performance was satisfactory, with limits of detection below 1 ng/L, relative standard deviations below 21%, and percentages of recovery between 93% and 121%. Analysis of 24‐hour composite raw wastewater samples collected in Santiago de Compostela (Spain) and Brasilia (Brazil) highlighted benzoylecgonine as the compound showing the highest population‐normalized mass loads (300–1000 mg/day/1000 inhabitants). In Brasilia, cocaine and levamisole loads underwent an upsurge on Sunday, indicating a high consumption, and likely a direct disposal, of cocaine powder on this day. Conversely, the pyrolytic product resulting from the smoke of crack, anhydroecgonine methyl ester, and its metabolite anhydroecgonine were relatively stable over the four days, agreeing with a non‐recreational‐associated use of crackThis work was financially supported by Consellería de Cultura, Educación e Ordenación Universitaria, Xunta de Galicia (ED431C2017/36 and IGM postdoctoral contract, Plan Galego I2C‐Modalidade B, ED481D 2017/003), Ministerio de Economía y Competitividad (project no. CTM2017‐84763‐C3‐2‐R), the Federal District Research Foundation (project no. 193.000.916/2015), and FEDER/ERDFS

Polybrominated diphenyl ethers (PBDE) as persistent contaminants : origin, behavior in the environment and analytical strategies

Flame retardants are substances mixed with numerous materials to inhibit the combustion process, reducing risks and damages caused by fires. Among these substances, polybrominated diphenyl ethers (PBDEs) have been widely used for decades due to their low cost and high efficiency. However, since they are mixed and not chemically bonded to the materials, PBDEs can be released over time being transported through numerous pathways until they reach soils and aquatic systems, where they can accumulate in sediments and biota. Due to their high chemical stability, an essential feature for flame retardants, they are considered persistent contaminants. Several studies report the presence of PBDEs in atmospheric and aquatic particulate matter, sediments, soils and biological matrices such as marine animals, tissues and human fluids. In Brazil, little is known about the use and commercialization of PBDEs, as well as their levels in different environmental compartments. Thus, this review provides an overview of the origin of PBDEs in the environment as well as information inherent to the understanding of the behavior and presence of this contaminants of recent interest in different environmental compartments. Finally, the manuscript also brings state-of-the-art analytical approaches used for environmental sampling, preservation, preparation and sample analysis