Chronopotentiometric stripping analysis using gold electrodes, an efficient technique for mercury quantification in natural waters

This paper proposes a simple methodology for mercury quantification in natural water by stripping chronopotentiometry at constant current, using gold (film) electrodes constructed from recordable CDs in stationary cell. The proposed method allows the direct measurement of labile mercury in natural waters. To quantify total mercury, a robust and low cost UV irradiation system was developed for the degradation of organic constituents of water. The proposed system presents such advantages as excellent sensitivity, low cost, versatility, and smaller dimensions (portability for on-field applications) when compared with other techniques (ICP, GFAAS, fluorimetry) traditionally utilized for mercury quantification. A large linear region of responses was observed, situated over the range 0.02 - 200 μ g L-1. Various experimental parameters were optimized and the system allowed quantifications in natural samples, with detection limit of 8 ng L-1 and excellent reproducibility (RSD of 1.4% for 48 repetitive measurements using a 10 μ g L-1 mercury solution). Different metal ions were evaluated, including copper, as possible interferences on stripping mercury signals. Applications of the new method were demonstrated for the analysis of certified and groundwater samples spiked with a known amount of mercury and for the quantification of methylmercury in synthetic oceanic water, originally utilized for fishes contamination experiment.

Analysis of aromatic amines in surface waters receiving wastewater from a textile industry by liquid chromatographic with electrochemical detection

A high performance liquid chromatography ( HPLC) method with electrochemical detection (ED) was developed for the determination of benzidine, 3,3-dimethylbenzidine, o-toluidine and 3,3-dichlorobenzidine in the wastewater of the textile industry. The aromatic amines were eluted on a reversed phase column Shimadzu Shimpack C-18 using acetonitrile + ammonium acetate (1 x 10(-4) mol L-1) at a ratio 46: 54 v/v as mobile phase, pumped at a flow rate of 1.0 mL min(-1). The electrochemical oxidation of the aromatic amines exhibits well-defined peaks at a potential range of +0.45 to +0.78 V on a glassy carbon electrode. Optimum working potentials for amperometric detection were from 0.70 V to +1.0 V vs. Ag/AgCl. Analytical curves for all the aromatic amines studied using the best experimental conditions present linear relationship from 1 x 10(-8) mol L-1 to 1.5 x 10(-5) mol L-1, r = 0.99965, n = 15. Detection limits of 4.5 nM (benzidine), 1.94 nM (o-toluidine), 7.69 nM (3,3-dimethylbenzidine), and 5.15 nM (3,3-dichlorobenzidine) were achieved, respectively. The detection limits were around 10 times lower than that verified for HPLC with ultra violet detection. The applicability of the method was demonstrated by the determination of benzidine in wastewater from the textile industry dealing with an azo dye processing plant.

Use of diffusive gradients in thin films and tangential flow ultrafiltration for fractionation of Al(III) and Cu(II) in organic-rich river waters

Diffusive gradients in thin films (DGT) and tangential-flow ultrafiltration (TF-UF) were combined for fractionation of Al and Cu in river water containing high content of dissolved organic carbon. A procedure based on ultrafiltration data is proposed to determine diffusion coefficients of the analytes in water samples and model solutions containing both free metal (M) and complex (metal - humic substance). Aiming to evaluate the accuracy of the proposed approach, the DGT results were compared with those from a protocol for determination of labile Al and Cu based on solid phase extraction (SPE). Good agreement between data from DGT and SPE were attained for model solutions. For analysis of real organic-rich water samples, differences between DGT and SPE measurements were consistent with the time-scales of the techniques. The concentration of labile Al determined by DGT were lower than the total dissolved concentrations (determined by inductively coupled plasma mass spectrometry) and exceeded the ultrafiltered concentration, indicating that inorganic Al species (species small enough to pass through 1 kDa membrane) were minor species as compared with Al organic complexes. For both Al and Cu, there were species not measured by DGT as they are not sufficiently labile. (C) 2007 Elsevier B.V. All rights reserved.

Seed dispersal by fishes in tropical and temperate fresh waters: The growing evidence

Fruit-eating by fishes represents an ancient (perhaps Paleozoic) interaction increasingly regarded as important for seed dispersal (ichthyochory) in tropical and temperate ecosystems. Most of the more than 275 known frugivorous species belong to the mainly Neotropical Characiformes (pacus, piranhas) and Siluriformes (catfishes), but cypriniforms (carps, minnows) are more important in the Holarctic and Indomalayan regions. Frugivores are among the most abundant fishes in Neotropical floodplains where they eat the fruits of a wide variety of trees and shrubs. By consuming fruits, fishes gain access to rich sources of carbohydrates, lipids and proteins and act as either seed predators or seed dispersers. With their often high mobility, large size, and great longevity, fruit-eating fishes can play important roles as seed dispersers and exert strong influences on local plant-recruitment dynamics and regional biodiversity. Recent feeding experiments focused on seed traits after gut passage support the idea that fishes are major seed dispersers in floodplain and riparian forests. Overfishing, damming, deforestation and logging potentially diminish ichthyochory and require immediate attention to ameliorate their effects. Much exciting work remains in terms of fish and plant adaptations to ichthyochory, dispersal regimes involving fishes in different ecosystems, and increased use of nondestructive methods such as stomach lavage, stable isotopes, genetic analyses and radio transmitters to determine fish diets and movements. (C) 2011 Elsevier Masson SAS. All rights reserved.

Determination of labile inorganic and organic species of Al and Cu in river waters using the diffusive gradients in thin films technique

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The Araguaia fold belt, Brazil: A reactivated Brasiliano-Pan-African cycle (550 Ma) geosuture

The Araguaia-Tocantins geosuture, which separates the Araguaia Fold Belt (AFB) from the Archean Amazonian Craton, was active in the late Middle Proterozoic. The Baixo Araguaia Supergroup was deposited, consisting of the Estrondo Group (lower quartzites with intercalated schists), Xambioá Formation (schists), and Canto da Vazante Formation (upper feldspathic schists); and the Tocantins Group consisting of the Couto Magalhaës Formation (phyllites, quartzites, slates, limestones, and metacherts) and Pequizeiro Formation (upper chlorite schists); and associated mafic-ultramafic bodies. The deformational history includes four regional phases of deformation within this supracrustal sequence: recumbent folds with vergence to the west; refolding with a N-S trend; an intense crenulation episode; and late thrusting from east to west. Metamorphism is of intermediate or intermediate-high pressure type with garnet, biotite, chlorite, and sericite isograds succeeded by a slightly or non-metamorphosed zone, from east to west. Rocks surrounding sparse gneissic-cored domes contain isograds of staurolite, kyanite, and fibrolite. These isograds are believed to be associated with the 1100 Ma Uruaçuano event. The Brasiliano Orogeny strongly affected the AFB with displacements due to transcurrent reactivation of great and old faults of the basement, slight folding in the supracrustal sequence, intrusion of small granite bodies, and development of domes with associated normal faults. The area underlain by the Estrondo Group was uplifted at this time, causing the deposition of the Rio das Barreiras polymictic conglomerate of the central area. K-Ar and Rb-Sr analyses date this thermo-tectonic event at 550 ± 100 Ma. The Archean basement is exposed in the cores of domes as a granite-gneiss association, the Colméia complex, which shows thermo-tectonic features that may be interpreted as polycyclic imprints (Jequié, Transamazonian?, Uruaçuano, and Brasiliano Events). © 1989.

Measuring fluoride concentration in mineral waters in the Araraquara region, Brazil

It has been shown that people of all ages can benefit from the topical and systemic effects of water fluoridation. However, the increase in consumption of bottled water, either to substitute for or supplement consumption of water from public sources, has implications for safe fluoride supplementation. Taking that into consideration, in 1995 we analyzed the fluoride content in 31 commercial brands of mineral water in the region of Araraquara, state of Sao Paulo, Brazil. Fluoride concentration as determined by our analysis was compared to the concentration of fluoride specified on each label. Only 25% of the products studied listed the fluoride concentration on their labels. In addition, among 31 mineral water brands, 26 listed the date when the chemical analysis to determine chemical composition had been performed. Of these, 20 had not been put through the annual chemical analysis determined by Brazilian law. Based on these results, if the mineral waters tested had been the only source of drinking water, fluoride supplementation would have been necessary in 69% of the samples analyzed. In the case of children up to 6 years of age who use products containing fluoride, such as topical gels, mouthwashes or toothpastes, supplementation should be recommended only if commercially bottled water is the only source of water used, not only for drinking but for cooking as well.

Analysis of rain quality data from the South African interior

Rain acidity may be ascribed to emissions from power station stacks, as well as emissions from other industry, biomass burning, maritime influences, agricultural influences, etc. Rain quality data are available for 30 sites in the South African interior, some from as early as 1985 for up to 14 rainfall seasons, while others only have relatively short records. The article examines trends over time in the raw and volume weighted concentrations of the parameters measured, separately for each of the sites for which sufficient data are available. The main thrust, however, is to examine the inter-relationship structure between the concentrations within each rain event (unweighted data), separately for each site, and to examine whether these inter-relationships have changed over time. The rain events at individual sites can be characterized by approximately eight combinations of rainfall parameters (or rain composition signatures), and these are common to all sites. Some sites will have more events from one signature than another, but there appear to be no signatures unique to a single site. Analysis via factor and cluster analysis, with a correspondence analysis of the results, also aid interpretation of the patterns. This spatio-temporal analysis, performed by pooling all rain event data, irrespective of site or time period, results in nine combinations of rainfall parameters being sufficient to characterize the rain events. The sites and rainfall seasons show patterns in these combinations of parameters, with some combinations appearing more frequently during certain rainfall seasons. In particular, the presence of the combination of low acetate and formate with high magnesium appears to be increasing in the later rainfall seasons, as does this combination together with calcium, sodium, chloride, potassium and fluoride. As expected, sites close together exhibit similar signatures. Copyright © 2002 John Wiley & Sons, Ltd.

Investigation of the Genotoxic Potential of the Waters of a River Receiving Tannery Effluents by Means of the in vitro Comet Assay

The comet assay has been described as an efficient tool for the detection of changes in the DNA molecule of cells exposed to contaminating agents in vivo and in vitro. The possible environmental contamination due to the persistence of chromium residues from tannery effluents was determined in the waters of the Córrego dos Bagres stream, Municipal district of Franca/SP, by the comet assay on CHO-K1 cells. Water samples were collected during the four seasons of the year 2001 at three distinct stations along the river. The data suggest that the comet test showed good sensitivity for the environmental monitoring of these waters and indicated that this test can be efficient for the determination of the quality of waters contaminated with effluents containing heavy metal residues such as chromium.

Structural and geochronological studies of the Médio Coreaú domain, NE Brazil: Constraints on Brasiliano/Pan-African tectonic evolution in the NW part of the Borborema Province

Recent structural investigations and geochronological studies of rocks from the Médio Coreaú domain in the NW part of northeast Brazil's Borborema Province provide important constraints on the tectonic evolution of the region both preceeding and during the assembly of West Gondwana. Field observations of structural features and fabrics have revealed the presence of four distinct deformational phases in the MCD: D1, D2, D3 and D4. Only the early Paleoproterozoic gneisses record the D1 tectonic event and its preservation is cryptic owing to strong overprinting by the subsequent tectonic phases. The D2, D3 and D4 events affected younger supracrustal rocks and Neoproterzoic magmatic units, and U-Pb geochronological constraints show that all of these tectonic phases represent deformational events that occurred during Brasiliano collision between the West African craton and the NW part of the Borborema Province. The D2 phase, lasting between ca. 622 and 591 Ma, represents a frontal collision stage, which generated NW verging thrust-nappe systems, low-angle foliation, high-grade metamorphism and crustal anatexis. Transition to a strike-slip regime (D3) occurred at around 591 Ma when the region entered a phase of escape tectonics. During this time, the motion of crustal blocks towards NE and E was accommodated along numerous anastomosing shear zones. Syntectonic emplacement of granitoid plutons took place in transtensional domains of the shear zone system. The intrusion of late tectonic granitoids and rapid uplift and cooling of the orogen around 560 Ma as a result of D4 transpressional movements marked the end of the D3 transcurrent regime. These findings show that only the early Paleoproterozoic gneisses in the Médio Coreaú domain are polycyclic in nature. Rather than representing distinct orogenic events, the D2, D3 and D4 tectonic phases are a manifestation of progressive deformational events that developed in response to changes in the regional stress field during convergence and collision between the Borborema Province and its surrounding cratons.

Vertical migration during tidal transport of megalopae of Necora puber in coastal shallow waters during daytime

For meroplanktonic larvae that must settle in coastal areas, their successful return to the shore is determined largely by physical transport processes; however, many organisms perform vertical movements to aid successful recruitment. In this study, daytime tidal vertical migration of megalopae of the velvet swimming crab Necora puber was investigated across two different exposures in the shallow waters of Plymouth Sound. Crabs were collected using a plankton net at the surface and near the bottom during flood and ebb tides. Distribution of the pelagic postlarvae was patchy and the abundance varied spatially in tens and thousands of metres. In temporal scales, the annual pattern was dominated by low occurrence of megalopae, punctuated by episodic peaks of high abundance. Most megalopae were collected at the surface irrespective of the tidal phase. The effect of wave exposure on the vertical migration of megalopae was not clear, although there was a general higher abundance of megalopae on exposed shores. Daytime abundance in the water column appears to be regulated by the tidal cycle, as megalopae were more abundant during flood than ebb tides. Although the megalopae do not appear to make large vertical migrations, this behaviour should produce a net shoreward transport. © 2005 Elsevier Ltd. All rights reserved.

Multiresidue determination of herbicides in environmental waters from Primavera do Leste region (Middle West of Brazil) by SPE-GC-NPD

A study on the presence of herbicides, namely simazine, metribuzin, metolachlor, trifluralin, atrazine and two metabolites, deisopropylatrazine (DIA) and deethylatrazine (DEA), was performed in ground and surface waters from Primavera do Leste region, Mato Grosso state (Middle West of Brazil). The analytical procedure was based on solid-phase extraction (SPE) with Sep-Pak C18 disposable cartridges and ethyl acetate for elution solvent. Residue levels were determined by gas chromatography with nitrogen-phosphorus detection. For most of the pesticides average recoveries at different fortification levels were >with relative standard deviation < The recoveries of DIA and trifluralin in water were 25% and 56%, respectively, which were attributed to the incomplete retention of DIA and strong retention on the sorbing material and high volatility of trifluralin. Detection limits ranged from 0.023 to 0.088 μg L-1. This method was applied for the analysis of 5 superficial water samples and 28 groundwater samples, in places used for human consumption without previous treatment, collected in Primavera do Leste, Mato Grosso, Brazil. Results indicated that the highest level of contamination in a water sample was 1.732 μg L-1 for metolachlor, while metribuzin was the most frequently detected herbicide with maximum concentration of 0.351 μg L-1. ©2006 Sociedade Brasileira de Química.

Seasonal behavior of mercury species in waters and sediments from the Negro River Basin, Amazon, Brazil

Total (HgT), reactive (HgR) and organic (Hg ORG) mercury species have been quantified in non-filtered waters collected from the Negro River Basin, Amazon (from January/2002 through January/2004), in both black and white water bodies. Black waters presented the highest HgT, HgORG and HgR concentration (29.1 ng L-1, 1.63 ng L-1 and 3.9 ng L-1, respectively), while, white waters presented the lowest HgT, Hg ORG and HgR concentration (8.8 ng L-1, 0.49 ng L-1 and 1.2 ng L-1, respectively). An inverse correlation between HgT and the water level over the basin was obtained, although the HgORG concentration has increased in the first rainy months and then decreased as the water level rose. Total mercury in surface sediments (0-10 cm) ranged from 70 to 271 mg kg-1 being the methylmercury 0.47-1.79 % of this stock. The results indicate that HgR and the labile dissolved organic matter were introduced into the aquatic environment during the flooding season, especially in the earlier stages, thus contributing to mercury methylation. ©2007 Sociedade Brasileira de Química.

Environmental parameters and antimicrobial susceptibility of enterobacteriaceae isolated from estuarine waters of São Vicente, São Paulo State, Brazil

Diseases transmitted by water consists a serious public health problem and enterobacteria are the main group of microorganisms responsible for outbreaks in humans. Such pathogenic bacteria proliferate in water polluted by domestic and industrial sewage and reach the population through seawater contact. The aim of the present work was to study environmental parameters as well as to identify Enterobacteriaceae species and their antimicrobial susceptibility in water samples collected from the estuarine area of São Vicente city (São Paulo State, Brazil). Strains were identified by using traditional biochemical tests described in literature and antimicrobial susceptibility tests were carried out using the disk diffusion method. Out of 26 samples, Escherichia coli was the most frequent species (40.1%), followed by Citrobacter, Enterobacter and Klebsiella. The most effective drugs against the tested microorganisms were gentamycin, netilmicin, ciprofloxacin and cefepime. Since these bacteria are commonly found in seashore contaminated by sewage effluents, it can be concluded that estuarine waters of São Vicente are polluted and potentially capable of causing diseases and spreading pathogenic bacteria to human communities.