Water quality assessment of the Tubarão River through chemical analysis and biomarkers in the Neotropical fish Geophagus brasiliensis

The Tubarão River rises in Santa Catarina, Brazil, and has been historically affected by coal mining activities around its springhead. To evaluate its water conditions, an investigation regarding a possible decontamination gradient associated with the increased river flow toward the estuary, as well as the influence of seasonality over this gradient was performed through a series of biomarkers (vitellogenin, comet assay, lipid peroxidation, protein carbonylation, gluthatione, gluthatione S-transferase, acetylcholinesterase, light microscopy in liver, and scanning electron microscopy in gills) and chemical analysis (polycyclic aromatic hydrocarbons (PAHs) in bile and metal analysis in sediment) in the cichlid Geophagus brasiliensis. Two collections (summer and winter) were made in four distinct sites along the river, while sediments were sampled between those seasons. As expected, the contamination linked exclusively to mining activities was not observed, possibly due to punctual inputs of contaminants. The decontamination gradient was not observed, although seasonality seemed to have a critical role in the responses of biomarkers and availability of contaminants. In the summer, the fish presented higher histopathological damages and lower concentrations of PAHs, while in the winter they showed both higher genetic damage and accumulation of PAHs. The Tubarão suffers impacts from diverse activities, representing health risks for wild and human populations.     

Development,validation, and application of a method for the GC-MS analysis of fipronil and three of its degradation products in samples of water,soil, and sediment

A method for the identification and quantification of pesticide residues in water, soil, and sediment samples has been developed, validated, and applied for the analysis of real samples. The specificity was determined by the retention time and the confirmation and quantification of analyte ions. Linearity was demonstrated over the concentration range of 20 to 120 µg L^?1, and the correlation coefficients varied between 0.979 and 0.996, depending on the analytes. The recovery rates for all analytes in the studied matrix were between 86% and 112%. The intermediate precision and repeatability were determined at three concentration levels (40, 80, and 120 µg L^?1), with the relative standard deviation for the intermediate precision between 1% and 5.3% and the repeatability varying between 2% and 13.4% for individual analytes. The limits of detection and quantification for fipronil, fipronil sulfide, fipronil-sulfone, and fipronil-desulfinyl were 6.2, 3.0, 6.6, and 4.0 ng L^?1 and 20.4, 9.0, 21.6, and 13.0 ng L^?1, respectively. The method developed was used in water, soil, and sediment samples containing 2.1 mg L^?1 and 1.2% and 5.3% of carbon, respectively. The recovery of pesticides in the environmental matrices varied from 88.26 to 109.63% for the lowest fortification level (40 and 100 µg kg^?1), from 91.17 to 110.18% for the intermediate level (80 and 200 µg kg^?1), and from 89.09 to 109.82% for the highest fortification level (120 and 300 µg kg^?1). The relative standard deviation for the recovery of pesticides was under 15%.     

Effect of ozonization in degradation of trifluralin residues in aqueous and food matrices

Abstract

This study investigates the oxidation of trifluralin residues during ozonation in aqueous and food matrices (tomato). Domestic ozonation equipment with average production of 23.9?mg O₃ L^?1 h^?1 was used in the tests. Modern chromatographic systems (SPME-GC-IT/MS/MS and QuEChERS-GC-IT/MS/MS) were applied for extraction and detection of trifluralin residue in fortified samples of ultrapure water, tap water, superficial water and tomato fruit. The samples were submitted to the ozonation process during 0, 5, 10 and 20?min. Treatment at 5?min was able to degrade 71.5% of herbicide trifluralin in surface water. The removal (%) in ultrapure water reached 83.4% after 20?min of ozonation. The degradation of trifluralin in fortified tomato samples (0.025–0.1?mg kg^?1) were conducted with ozonation at 20?min, and it ranged from 84.4 to 92.7%. After treatment, levels of trifluralin in tomato remained within the established MRLs to EU, USEPA and ANVISA (Brazil). The data provided evidence that ozone is effective for removing trace trifluralin from water and foods.     

Characterization of Fine Particulate Matter Produced by Combustion of Residual Fuel Oil

ABSTRACT

Combustion experiments were carried out on four different residual fuel oils in a 732-kW boiler. PM emission samples were separated aerodynamically by a cyclone into fractions that were nominally less than and greater than 2.5 |j.m in diameter. However, examination of several of the samples by computer-controlled scanning electron microscopy (CCSEM) revealed that part of the PM_2.5 fraction consists of carbonaceous cenospheres and vesicular particles that range up to 10 |j.m in diameter. X-ray absorption fine structure (XAFS) spectroscopy data were obtained at the S, V, Ni, Fe, Cu, Zn, and As K-edges and at the Pb L-edge. Deconvolution of the X-ray absorption near edge structure (XANES) region of the S spectra established that the dominant molecular forms of S present were sulfate (26-84% of total S) and thiophene (13-39% of total S). Sulfate was greater in the PM_2.5 samples than in the PM₂₅₊ samples. Inorganic sulfides and elemental sulfur were present in lower percentages. The Ni XANES spectra from all of the samples agreed fairly well with that of NiSO₄, while most of the V spectra closely resembled that of vanadyl sulfate (VO?SO₄?xH₂O). The other metals investigated (i.e., Fe, Cu, Zn, and Pb) also were present predominantly as sulfates. Arsenic was present as an arsen-ate (As⁺⁵). X-ray diffraction patterns of the PM_2.5 fraction exhibit sharp lines due to sulfate compounds (Zn, V, Ni, Ca, etc.) superimposed on broad peaks due to amorphous carbons. All of the samples contain a significant organic component, with the loss on ignition (LOI) ranging from 64 to 87% for the PM_2.5 fraction and from 88 to 97% for the PM_2.5+ fraction. Based on ¹³C nuclear magnetic resonance (NMR) analysis, the carbon is predominantly condensed in graphitic structures. Aliphatic structure was detected in only one of seven samples examined.     

In Situ Monitoring of the Mutagenic Effects of the Gaseous Emissions of a Solid Waste Incinerator in Metropolitan São Paulo,Brazil, Using the Tradescantia Stamen-Hair Assay

ABSTRACT

The present work was designed to determine the potential genotoxicity at the vicinity of a solid waste incinerator in the metropolitan area of Sâo Paulo, using the Tradescantia stamen-hair bioassay. Experiments were carried out between December 1998 and April 1999 in four regions (40 pots of plants per site) selected on the basis of their pollution levels predicted by theoretical modeling of the dispersion of the incinerator's plume. The exposure sites were defined as follows: highest level (incinerator); a high level (museum) located 1.5 km from the emission point; a moderate level (school, at a distance of 3.5 km from the incinerator); and a control (at Jaguariuna countryside). The difference in genotoxicity among the groups was statistically significant (p < 0.001). The frequency of mutations observed in the countryside was significantly lower [2.25 ± 1.55, mean ± SD (standard deviation)] than that of the sites close to the incinerator. The frequency of mutations measured at the school (3.70 ± 1.36) was significantly lower than that measured at both the museum (4.89 ± 1.12) and the incinerator (5.69 ± 1.34). In conclusion, we found a positive correlation between the spatial distribution of the emissions of the incinerator located in an urban area and the mutagenic events measured by the Tradescantia stamen-hair assay. The in situ approach employed in this study was simple, efficient, and of low cost. No air or chemical extraction of pollutants was necessary for genotoxicity testing as required by other assays.     

Modeling Inorganic Aerosols and Their Response to Changes in Precursor Concentration in Mexico City

Abstract

Based on data from the 1997 Investigación sobre Materia Particulada y Deterioro Atmosférico-Aerosol and Visibility Evaluation Research (IMADA-EVER) campaign and the inorganic aerosol model ISORROPIA, the response of inorganic aerosols to changes in precursor concentrations was calculated. The aerosol behavior is dominated by the abundance of ammonia and thus, changes in ammonia concentration are expected to have a small effect on particle concentrations. Changes in sulfate and nitrate are expected to lead to proportional reductions in inorganic fine particulate matter (PM_2.5). Comparing the predictions of ISORROPIA with the observations, the lowest bias and error are achieved when the aerosols are assumed to be in the efflorescence branch. Including crustal species reduces the bias and error for nitrate but does not improve overall model performance. The estimated response of inorganic PM_2.5 to changes in precursor concentrations is affected by the inclusion of crustal species in some cases, although average responses are comparable with and without crustal species. Observed concentrations of particle chloride suggest that gas phase concentrations of hydrogen chloride may not be negligible, and future measurement campaigns should include observations to test this hypothesis. Our ability to model aerosol behavior in Mexico City and, thus, design control strategies, is constrained primarily by a lack of observations of gas phase precursors. Future campaigns should focus in particular on better understanding the temporal and spatial distribution of ammonia concentrations. In addition, gas phase observations of nitric acid are needed, and a measure of particle water content will allow stable versus metastable aerosol behavior to be distinguished.     

Wildland–Urban Interface Fires and Socioeconomic Conditions: A Case Study of a Northwestern Patagonia City

In many regions of the world, fires are primarily of anthropogenic origin. In northwestern Patagonia, the number of fires is not correlated with meteorological variables, but is concentrated in urban areas. This study was conducted in the wildland–urban interface (WUI) area of San Carlos de Bariloche (Patagonia, Argentina), within the Nahuel Huapi National Park. WUI fires are particularly problematic because, besides people and goods, they represent a danger to protected areas. We studied the relationship between fire records and socioeconomic indicators within the WUI of San Carlos de Bariloche. We conducted a Multiple Correspondence Factorial Analysis and an Ascendant Hierarchical Classification of the city neighborhoods. The results show that the neighborhoods in Bariloche can be divided into three classes: High Socioeconomic Fire Risk neighborhoods, including neighborhoods with the highest fire rates, where people have low instruction level, high levels of unsatisfied basic needs and high unemployment levels; Low Socioeconomic Fire Risk neighborhoods, that groups neighborhoods which present the opposite characterization, and Moderate Socioeconomic Fire Risk neighborhoods, which are more heterogeneous. Once neighborhoods were classified, a Socioeconomic Fire Risk map was generated, supplementing the existing WUI Fire Danger map. Our results emphasize the relevance of socioeconomic variables to fire policies.     

Can Volunteers Collect Data that are Comparable to Professional Scientists? A Study of Variables Used in Monitoring the Outcomes of Ecosystem Rehabilitation

Having volunteers collect data can be a cost-effective strategy to complement or replace those collected by scientists. The quality of these data is essential where field-collected data are used to monitor progress against predetermined standards because they provide decision makers with confidence that choices they make will not cause more harm than good. The integrity of volunteer-collected data is often doubted. In this study, we made estimates of seven vegetation attributes and a composite measure of six of those seven, to simulate benchmark values. These attributes are routinely recorded as part of rehabilitation projects in Australia and elsewhere in the world. The degree of agreement in data collected by volunteers was compared with those recorded by professional scientists. Combined results showed that scientists collected data that was in closer agreement with benchmarks than those of volunteers, but when data collected by individuals were analyzed, some volunteers collected data that were in similar or closer agreement, than scientists. Both groups’ estimates were in closer agreement for particular attributes than others, suggesting that some attributes are more difficult to estimate than others, or that some are more subjective than others. There are a number of ways in which higher degrees of agreement could be achieved and introducing these will no doubt result in better, more effective programs, to monitor rehabilitation activities. Alternatively, less subjective measures should be sought when developing monitoring protocols. Quality assurance should be part of developing monitoring methods and explicitly budgeted for in project planning to prevent misleading declarations of rehabilitation success.     

River Restoration in Spain: Theoretical and Practical Approach in the Context of the European Water Framework Directive

River restoration is becoming a priority in many countries because of increasing the awareness of environmental degradation. In Europe, the EU Water Framework Directive (WFD) has significantly reinforced river restoration, encouraging the improvement of ecological status for water bodies. To fulfill the WFD requirements, the Spanish Ministry of the Environment developed in 2006 a National Strategy for River Restoration whose design and implementation are described in this paper. At the same time many restoration projects have been conducted, and sixty of them have been evaluated in terms of stated objectives and pressures and implemented restoration measures. Riparian vegetation enhancement, weir removal and fish passes were the most frequently implemented restoration measures, although the greatest pressures came from hydrologic alteration caused by flow regulation for irrigation purposes. Water deficits in quantity and quality associated with uncontrolled water demands seriously affect Mediterranean rivers and represent the main constraint to achieving good ecological status of Spanish rivers, most of them intensively regulated. Proper environmental allocation of in-stream flows would need deep restrictions in agricultural water use which seem to be of very difficult social acceptance. This situation highlights the need to integrate land-use and rural development policies with water resources and river management, and identifies additional difficulties in achieving the WFD objectives and good ecological status of rivers in Mediterranean countries.