Development of a high sensitive automatic setup for screening of microcystins in surface waters by employing a LED-based photometric detector

In this manuscript, an automatic setup for screening of microcystins in surface waters by employing photometric detection is described. Microcystins are toxins delivered by cyanobacteria within an aquatic environment, which have been considered strongly poisonous for humans. For that reason, the World Health Organization (WHO) has proposed a provisional guideline value for drinking water of 1 mu g L-1. In this work, we developed an automated equipment setup, which allows the screening of water for concentration of microcystins below 0.1 mu g V. The photometric method was based on the enzyme-linked immunosorbent assay (ELISA) and the analytical signal was monitored at 458 nm using a homemade LED-based photometer. The proposed system was employed for the detection of microcystins in rivers and lakes waters. Accuracy was assessed by processing samples using a reference method and applying the paired t-test between results. No significant difference at the 95% confidence level was observed. Other useful features including a linear response ranging from 0.05 up to 2.00 mu g L-1 (R-2 =0.999) and a detection limit of 0.03 mu g L-1 microcystins were achieved. (C) 2011 Elsevier B.V. All rights reserved.

Variability in light absorption and scattering of phytoplankton in Patagonian waters: Role of community size structure and pigment composition

Intense phytoplankton blooms were observed along the Patagonian shelf-break with satellite ocean color data, but few in situ optical observations were made in that region. We examine the variability of phytoplankton absorption and particulate scattering coefficients during such blooms on the basis of field data. The chlorophyll-a concentration, [Chla], ranged from 0.1 to 22.3 mg m−3 in surface waters. The size fractionation of [Chla] showed that 80% of samples were dominated by nanophytoplankton (N-group) and 20% by microphytoplankton (M-group). Chlorophyll-specific phytoplankton absorption coefficients at 440 and 676 nm, a*ph(440) and a*ph(676), and particulate scattering coefficient at 660 nm, b*p(660), ranged from 0.018 to 0.173, 0.009 to 0.046, and 0.031 to 2.37 m2 (mg Chla)−1, respectively. Both a*ph(440) and a*ph(676) were statistically higher for the N-group than M-group and also considerably higher than expected from global trends as a function of [Chla]. This result suggests that size of phytoplankton cells in Patagonian waters tends to be smaller than in other regions at similar [Chla]. The phytoplankton cell size parameter, Sf, derived from phytoplankton absorption spectra, proved to be useful for interpreting the variability in the data around the general inverse dependence of a*ph(440), a*ph(676), and b*p(660) on [Chla]. Sf also showed a pattern along the increasing trend of a*ph(440) and a*ph(676) as a function of the ratios of some accessory pigments to [Chla]. Our results suggest that the variability in phytoplankton absorption and scattering coefficients in Patagonian waters is caused primarily by changes in the dominant phytoplankton cell size accompanied by covariation in the concentrations of accessory pigments.

Temporal, diel and spatial variability of decapod larvae from St Paul`s Rocks, an equatorial oceanic island of Brazil

Temporal, spatial and diel variation in the distribution and abundance of organisms is an inherent property of ecological systems. The present study describes these variations and the composition of decapod larvae from the surface waters of St Paul`s Rocks. The expeditions to the archipelago were carried out in April, August and November 2003, March 2004 and May 2005. Surface plankton samples were collected during the morning and dusk periods, inside the inlet and in increasing distances around the archipelago (similar to 150, 700 and 1500 m). The identification resulted in 51 taxa. Seven species, six genera and larvae of the families Pandalidae and Portunidae were identified for the first time in the area. The mean larval density varied from zero to 150.2 +/- 69.6 individuals 100 m(-3) in the waters surrounding the archipelago and from 1.7 +/- 3.0 to 12,827 +/- 15,073 individuals 100 m(-3) inside the inlet. Significant differences on larval density were verified between months and period of the day, but not among the three sites around the archipelago. Cluster and non-metric multidimensional scaling analysis indicated that the decapod larvae community was divided into benthic and pelagic assemblages. Indicator species analysis (ISA) showed that six Brachyura taxa were good indicators for the inlet, while three sergestids were the main species from the waters around the archipelago. These results suggest that St Paul`s Rocks can be divided into two habitats, based on larval composition, density and diversity values: the inlet and the waters surrounding the archipelago.

Impacts of interruption of the Agulhas leakage on the tropical Atlantic in coupled ocean-atmosphere simulations

In this paper we use a coupled ocean-atmosphere model to investigate the impact of the interruption of Agulhas leakage of Indian ocean water on the tropical Atlantic, a region where strong coupled ocean-atmosphere interactions occur. The effect of a shut down of leakage of Indian ocean water is isolated from the effect of a collapse of the MOC. In our experiments, the ocean model is forced with boundary conditions in the southeastern corner of the domain that correspond to no interocean exchange of Indian ocean water into the Atlantic. The southern boundary condition is taken from the Levitus data and ensures an MOC in the Atlantic. Within this configuration, instead of warm and salty Indian ocean water temperature (cold) and salinity (fresh) anomalies of southern ocean origin propagate into the South Atlantic and eventually reach the equatorial region, mainly in the thermocline. This set up mimics the closure of the ""warm water path"" in favor of the ""cold water path"". As part of the atmospheric response, there is a northward shift of the intertropical convergence zone (ITCZ). The changes in trade winds lead to reduced Ekman pumping in the equatorial region. This leads to a freshening and warming of the surface waters along the equator. Especially in the Cold Tongue region, the cold and fresh subsurface anomalies do not reach the surface due to the reduced upwelling. The anomaly signals are transported by the equatorial undercurrent and spread away from the equator within the thermocline. Part of the anomaly eventually reaches the Tropical North Atlantic, where it affects the Guinea Dome. Surprisingly, the main effect at the surface is small on the equator and relatively large at the Guinea Dome. In the atmosphere, the northward shift of the ITCZ is associated with a band of negative precipitation anomalies and higher salinities over the Tropical South Atlantic. An important implication of these results is that the modified water characteristics due to a shut down of the Agulhas leakage remain largely unaffected when crossing the equatorial Atlantic and therefore can affect the deepwater formation in the North Atlantic. This supports the hypothesis that the Agulhas leakage is an important source region for climate change and decadal variability of the Atlantic.

Nutrient distributions over the Southwestern South Atlantic continental shelf from Mar del Plata (Argentina) to Itajai (Brazil): Winter-summer aspects

Nutrient distributions observed at some depths along the continental shelf from 27 degrees 05`S (Brazil) to 39 degrees 31`S (Argentina) in winter, 2003 and summer, 2004 related to salinity and dissolved oxygen (mL L-1) and saturation (%) data showed remarkable influences of fresh water discharge over the coastal region and in front of the La Plata estuary. In the southern portion of the study area different processes were verified. Upwelling processes caused by ocean dynamics typical of shelf break areas, eddies related to surface dynamics and regeneration processes confirmed by the increase of nutrients and the decrease of dissolved and saturation oxygen data were verified. High silicate concentrations in the surface waters were identified related to low salinities (minimum of 21.22 in winter and 21.96 in summer), confirming the importance of freshwater inputs in this region, especially in winter. Silicate concentration range showed values between 0.00 and 83.52 mu M during winter and from 0.00 to 41.16 mu M during summer. Phosphate concentrations worked as a secondary trace of terrestrial input and their values varied from 0.00 to 3.30 mu M in winter and from 0.03 to 2.26 mu M in summer; however, in shallow waters, phosphate indicated more clearly the fresh water influence. The most important information given by nitrate concentrations was the presence of water from SACW upwelling that represents a new source of nutrients for marine primary production. Nitrate maximum values reached 41.96 M in winter and 33.10 mu M in summer. At a depth similar to 800m, high nitrate, phosphate and silicate concentrations were related to Malvinas Current Waters, Subantarctic Shallow Waters and Antarctic Atlantic Intermediate Waters (AAIW). Dissolved oxygen varied from 3.41 to 7.06 mL L-1 in winter and from 2.65 to 6.85 mL L-1 in summer. The percentage of dissolved oxygen saturation in the waters showed values between 48% and 113% in winter and from 46% to 135% in summer. The most important primary production was verified in the summer, and situations of undersaturation were mainly observed below 50 m depth and at some points near the coast. The anti-correlation between nutrients and dissolved oxygen which showed evident undersaturation also revealed important potential sites of remineralization processes. The nutrient behaviours showed some aspects of the processes that occur over the Southwestern South Atlantic continental shelf and in their land-sea interfaces between Mar del Plata and Itajai.

An integrated approach to evaluate emerging contaminants in drinking water

The chemical stock of emerging contaminants in Brazilian drinking water is of great interest due to the poor water quality at surface water intakes. In addition, little is known about the effect of some contaminants, such as endocrine disrupting chemicals (EDCs), which may be present in both raw and treated water. The aim of this work was to evaluate selected emerging contaminants in Brazilian waters using both chemical and biological analyses. Sampling sites were established in different municipalities based upon raw water quality data. Estrone, 17 beta-estradiol, estriol, 17 alpha-ethinylestradiol, bisphenol A, 4-n-octylphenol and 4-n-nonylphenol were determined in the samples by liquid chromatography-tandem mass spectrometry. A yeast assay using a Saccharomyces cerevisiae bioluminescent bioreporter was used to evaluate the estrogenic activity of the water samples. The first integrated results revealed similarities between the two individual approaches, since higher values for the bioassay were accompanied by significant concentrations of some selected compounds in surface water samples. No estrogenicity was observed for drinking water samples. Our results also indicate that the usual paradigm of evaluating water quality by measuring selected EDCs in a given water sample via chemical analysis, needs to be reviewed since the observed estrogenicity of a water sample is now a better guiding parameter to the selection of samples and substances to be chemically investigated in further analysis. So far, the data bank produced in this work, i.e., the comparison between chemical burden and observed estrogenicity, is not yet sufficiently robust to fully guide this decision. (C) 2011 Elsevier B.V. All rights reserved.

Development of methodology for determination of pesticides residue in water by SPE/HPLC/DAD

To boost crop yield, sugarcane growers are using increasing amounts of pesticides to combat insects and weeds. But residues of these compounds can pollute water resources, such as lakes, rivers and aquifers. The present paper reports the results of a study of water samples from the Feijao River, which is the source of drinking water for the city of Sao Carlos, Sao Paulo, Brazil. The samples were evaluated for the presence of four leading pesticides - ametryn, atrazine, diuron and fipronil - used on sugarcane, the dominant culture in the region. The samples were obtained from three points along the river: the headwaters, along the middle course of the river and just before the municipal water intake station. The pesticides were extracted from the water samples by solid-phase extraction (SPE) and then analyzed by liquid chromatography with diode array detection (LC-DAD). The analytical method was validated by traditional methods, obtaining recovery values between 90 and 95%, with precision deviations inferior to 2.56%, correlation coefficients above 0.99 and detection and quantification limits varying from 0.02 to 0.05 mg L-1 and 0.07 to 0.17 mg L-1, respectively. No presence of residues of the pesticides was detected in the samples, considering the detection limits of the method employed.

Hydrochemical variability at the Upper Paraguay Basin and Pantanal wetland

Compartmentalization is a prerequisite to understand large wetlands that receive water from several sources. However, it faces the heterogeneity in space and time, resulting from physical, chemical and biological processes that are specific to wetlands. The Pantanal is a vast seasonally flooded continental wetland located in the centre of South America. The chemical composition of the waters that supply the Pantanal (70 rivers) has been studied in order to establish a compartmentalization of the wetland based on soil-water interactions. A PCA-based EMMA (End-Members Mixing Analysis) procedure shows that the chemistry of the rivers can be viewed as a mixture of 3 end-members, influenced by lithology and land use, and delimiting large regions. Although the chemical composition of the end-members changed between dry and wet seasons, their spatial distribution was maintained. The results were extended to the floodplain by simple tributary mixing calculation according to the hydrographical network and to the areas of influence for each river when in overflow conditions. The resulting map highlights areas of high geochemical contrast on either side of the river Cuiaba in the north, and of the rivers Aquidauana and Abobral in the south. The PCA-based treatment on a sampling conducted in the Nhecolandia, a large sub region of the Pantanal, allowed the identification and ordering of the processes that control the geochemical variability of the surface waters. Despite an enormous variability in electrical conductivity and pH, all data collected were in agreement with an evaporation process of the Taquari River water, which supplies the region. Evaporation and associated saline precipitations (Mg-calcite, Mg-silicates K-silicates) explained more than 77% of the total variability in the chemistry of the regional surface water sampling.

Influence of urban activities on polycyclic aromatic hydrocarbons in precipitation: Distribution, sources and depositional flux in a developing metropolis, Fortaleza, Brazil

We measured polycyclic aromatic hydrocarbons (PAHs) in bulk precipitation in the Fortaleza metropolitan area, Ceara, Brazil, for the first time. Because little information is available concerning PAHs in tropical climatic regions, we assessed their spatial distribution and possible sources and the influence of urban activities on the depositional fluxes of PAHs in bulk precipitation. The concentrations of individual and total PAHs (Sigma(PAHs)) in bulk precipitation ranged from undetectable to 133.9 ng.L-1 and from 202.6 to 674.8 ng.L-1, respectively. The plume of highest concentrations was most intense in a zone with heavy automobile traffic and favorable topography for the concentration of emitted pollutants. The depositional fluxes of PAHs in bulk precipitation calculated in this study (undetectable to 0.87 mu g.m(-2).month(-1)) are 4 to 27 times smaller than those reported from tourist sites and industrial and urban areas in the Northern Hemisphere. Diagnostic ratio analyses of PAH samples showed that the major source of emissions is gasoline exhaust, with a small percentage originating from diesel fuel. Contributions from coal and wood combustion were also found. Major economic activities appear to contribute to pollutant emissions. (C) 2011 Elsevier B.V. All rights reserved.