Fernando F. Sodré

A preliminary nationwide survey of the presence of emerging contaminants in drinking and source waters in Brazil

This is the first nationwide survey of emerging contaminants in Brazilian waters. One hundred drinking water samples were investigated in 22 Brazilian state capitals. In addition, seven source water samples from two of the most populous regions of the country were evaluated. Samples were collected from June to September of 2011 and again during the same period in 2012. The study covered emerging contaminants of different classes, including hormones, plasticizers, herbicides, triclosan and caffeine. The analytical method for the determination of the compounds was based on solid-phase extraction followed by analysis via liquid chromatography electrospray triple-quadrupole mass spectrometry (LC-MS/MS). Caffeine, triclosan, atrazine, phenolphthalein and bisphenol A were found in at least one of the samples collected in the two sampling campaigns. Caffeine and atrazine were the most frequently detected substances in both drinking and source water. Caffeine concentrations in drinking water ranged from 1.8ngL-1 to values above 2.0μgL-1 while source-water concentrations varied from 40ngL-1 to about 19μgL-1. For atrazine, concentrations were found in the range from 2.0 to 6.0ngL-1 in drinking water and at concentrations of up to 15ngL-1 in source water. The widespread presence of caffeine in samples of treated water is an indication of the presence of domestic sewage in the source water, considering that caffeine is a compound of anthropogenic origin.

Estimating cocaine consumption in the Brazilian Federal District (FD) by sewage analysis

This is the first report on the occurrence of cocaine (COC) and benzoylecgonine (BE) residues in six samples collected from different wastewater treatment plants (WTP) located in the Brazilian Federal District (FD). Concentrations of BE in the influent sewage were used to calculate cocaine consumption (kg year-1 per 1000 inhabitants) for each region attended by the WTP from two sampling campaigns (March and June, 2010). Among the WTP studied, samples from Samambaia showed higher concentrations (from 3866 to 2477 ng L-1 of BE and 805 to 579 ng L-1 of COC) and doses per inhabitants (more than 13 doses inhabitant-1 per year). The extrapolation to the whole FD population points out to an annual consumption reaching 1.0 ton of free base cocaine, or 1.1 tons of cocaine hydrochloride. The work also addresses the influence of the cocaine presentation form (free base or hydrochloride) and the integration with chemical profiling results in a more realistic estimate, mainly concerning the viewpoints of forensics and law enforcement.

Evaluating Copper Behavior in Urban Surface Waters Under Anthropic Influence. A Case Study from the Iguaçu River, Brazil

The goal of this work was to investigate the changes in copper behavior in Iguaçu River, a body of water strongly affected by urban inputs. This work was carried out in a subtropical Brazilian watershed suffering with high loads of raw sewage discharges from the Metropolitan Region of Curitiba. A comparison between sampling sites located upstream and downstream from the urban region revealed that human inputs are able to modify the water chemistry of the river in a short distance basis, that is, approximately nine miles. Probably, the most important alterations were the creation of an anaerobic environment as well as the enhancement of humic-coated suspended solids. These two aspects were determinant to explain the high concentrations observed for particulate copper (57% of total recoverable copper) and dissolved copper sulfide species (13%) in the water column. Copper in the sediment was also higher in the downstream site, probably due to the sedimentation of the Cu-enriched particles. However, copper sulfides at the bottom sediment may also be a potential source for the metal in the water column due to the creation of anaerobic conditions in both compartments. Labile copper concentration was not affected by the changes in water chemistry. Despite the fact that sewage discharges motivate the enhancement of organic matter, but not the increase in potential complexing agents, additional ligands such as chloride, carbonates, and anthropogenic dissolved organic ligands can be now computed as a part of the labile fraction.

Variations on Copper Bioavailability in Soil Treated With Copper-Enriched Sewage Sludge

Copper behavior and bioavailability in a red Latosol treated with Cu-enriched sewage sludge were investigated. Results showed that sewage sludge increases nutrient and organic matter concentration in the soil. In sludge-amended treatments, bioavailability to lettuce plants was reduced due formation of organic complexes. In this case, plant productivity was affected only by soil acidity. Phytotoxicity was noticed in treatments without sludge and with high amounts of copper. Metal levels in roots, instead of in plant shoots, show a good fit with bioavailable copper estimated using the Mehlich-1 solution, commonly used in routine analyses, even at high metal levels.

Drogas de abuso em águas naturais e residuárias urbanas: ocorrência, determinação e aplicações forenses

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.

Phytotoxicity and distribution of copper in tropical soil amended with sewage sludge and copper sulfate

Abstract A greenhouse experiment was conducted to evaluate phytotoxicity and distribution of Cu in a tropical soil amended with sewage sludge (Sw) and copper sulfate (CuSO4.5H2O). Samples of a clay soil from the State of Paraná, Brazil were collected at depth of 0–20; 20–40 and 40–60 cm, and brought to the laboratory to be properly accommodated in experimental units (PVC tubes). The Cu treatments were performed by the application of Sw (10 t ha-1) amended with Cu (SB-T), and by CuSO4. H2O (WB-T). Lettuce plants were cultivated in the amended soil in order to predict the toxicity of the Cu. The experiment was conducted for 70 days, and then the lettuce plants and soil samples were collected for analysis. A sequential method was used to separate soil Cu into following fractions: exchangeable, amorphous iron oxide bound, crystalline iron oxide bound, organic matter bound and residual bound. The experimental results showed that Fe, Zn, K, P, Cu and organic matter amounts of the soil increased with the treatment SB-T. The toxic phyto-available Cu content in the soil for the lettuce plants was 80.00 mg kg-1. A percolation study showed that the Cu contents were larger for the first 20 cm of depth, indicating that the metal was not transported down the soil profile. The Cu content of different fractions declined in an order residual > amorphous iron oxide > crystalline iron oxide > organic matter > exchangeable, regardless of treatment performed. Additionally, the Cu contents added from treatments were determined mainly in amorphous iron oxide fraction.

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 1000 inh) 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 1000 inh 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 Paranoa 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 Paranoa 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.

Copper and lead adsorption as influenced by organic matter in soils from a tropical toposequence with different chemical and mineralogical attributes

ABSTRACT The aim of this work was to investigate the influence of the organic matter on copper and lead adsorption in soils with different physiochemical and mineralogical attributes. Suspensions (pH 6.0) of a Latosol, a Neosol and a Vertisol containing increasing amounts of copper or lead were used to obtain sorption isotherms while identical experiments were carried out with the soils previously treated with H2O2 to remove organic matter (OM). For the undisturbed soils, L-type and H-type isotherms were predominant for copper and lead respectively, showing that lead interacts more strongly with adsorption sites. For both metals, the non-linear Freundlich adsorption model revealed higher concentration of adsorption sites for Vertisol due to 2:1 clays. For the OM-removed soils, C-type isotherms were observed for copper with the permanence of less stable and more homogeneous sites. For this metal, a high correlation (R2 = 0.997) was observed between the decrease of adsorbent sites and the loss of organic carbon, evidencing the central role of organic matter on copper complexation, while lead may be able to interact efficiently with both organic matter and soil minerals.

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) followed by anhydroecgonine (AE) (1.5 ± 0.2 to 2.6 ± 0.2 μg L), phenacetin (PHE) (0.62 ± 0.06 to 1.3 ± 0.1 μg L), levamisole (LEV) (0.5 ± 0.2 to 1.23 ± 0.09 μg L), and cocaine (COC) (0.46 ± 0.07 to 0.8 ± 0.1 μg L). 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.