Sources of potentially toxic elements and organic pollutants in an urban area subjected to an industrial impact

Urban and industrial development has caused a major impact on environmental soil quality. This work assesses the extent and severity of contamination in a small urban area subjected to an industrial impact and identifies the major anthropogenic inputs. Twenty-six soil samples were collected from agricultural and urban sites, and concentrations of potentially toxic elements (As, Cd, Cu, Cr, Fe, Mn, Ni, Pb and Zn), PAHs and PCBs, were determined. In spite of the low median concentrations observed, some sites represent a potential hazard for human health and ecosystems. Concentrations of contaminants were higher than those found in a nearby city, indicating that the study area is affected by the surrounding industry. The use of multivariate statistical analyses allowed for the identification of the main factors controlling the variability of potentially toxic elements and organic pollutants in the soils. The presence of Cr, Fe, Mn and Ni was associated with geogenic inputs, and Cu, Pb, Zn, As, PAHs and PCBs were associated with anthropogenic inputs. Industry and traffic were the most important anthropogenic sources. Soil characteristics were identified as important factors controlling the spatial variability of elements, both from recognised natural and anthropogenic origin. Differences between land uses were observed, which may be attributed to both management practices and proximity to sources.     

Impact of intensive horticulture practices on groundwater content of nitrates, sodium, potassium, and pesticides

A monitoring program of nitrate, nitrite, potassium, sodium, and pesticides was carried out in water samples from an intensive horticulture area in a vulnerable zone from north of Portugal. Eight collecting points were selected and water-analyzed in five sampling campaigns, during 1 year. Chemometric techniques, such as cluster analysis, principal component analysis (PCA), and discriminant analysis, were used in order to understand the impact of intensive horticulture practices on dug and drilled wells groundwater and to study variations in the hydrochemistry of groundwater. PCA performed on pesticide data matrix yielded seven significant PCs explaining 77.67% of the data variance. Although PCA rendered considerable data reduction, it could not clearly group and distinguish the sample types. However, a visible differentiation between the water samples was obtained. Cluster and discriminant analysis grouped the eight collecting points into three clusters of similar characteristics pertaining to water contamination, indicating that it is necessary to improve the use of water, fertilizers, and pesticides. Inorganic fertilizers such as potassium nitrate were suspected to be the most important factors for nitrate contamination since highly significant Pearson correlation (r = 0.691, P < 0.01) was obtained between groundwater nitrate and potassium contents. Water from dug wells is especially prone to contamination from the grower and their closer neighbor's practices. Water from drilled wells is also contaminated from distant practices.     

Bias Correction Techniques to Improve Air Quality Ensemble Predictions: Focus on O3 and PM Over Portugal

Five air quality models were applied over Portugal for July 2006 and used as ensemble members. Each model was used, with its original set up in terms of meteorology, parameterizations, boundary conditions and chemical mechanisms, but with the same emission data. The validation of the individual models and the ensemble of ozone (O₃) and particulate matter (PM) is performed using monitoring data from 22 background sites. The ensemble approach, based on the mean and median of the five models, did not improve significantly the skill scores due to large deviations in each ensemble member. Different bias correction techniques, including a subtraction of the mean bias and a multiplicative ratio adjustment, were implemented and analysed. The obtained datasets were compared against the individual modelled outputs using the bias, the root mean square error (RMSE) and the correlation coefficient. The applied bias correction techniques also improved the skill of the individual models and work equally well over the entire range of observed O₃ and PM values. The obtained results revealed that the best bias correction technique was the ratio adjustment with a 4-day training period, demonstrating significant improvements for both analysed pollutants. The increase in the ensemble skill found comprehends a bias reduction of 88 % for O₃, and 92 % for PM10, and also a decrease in 23 % for O₃ and 43 % for PM10 in what concerns the RMSE. In addition, a spatial bias correction approach was also examined with successful skills comparing to the uncorrected ensemble for both pollutants.     

Evaluation of diffusive gradients in thin films technique (DGT) for measuring Al, Cd, Co, Cu, Mn, Ni, and Zn in Amazonian rivers

Studies concerning the lability and bioavailability of trace metals have played a prominent role in the search for contamination of water resources. This work describes the first application yet of the diffusive gradients in thin films technique (DGT) to the determination of the fraction of free plus labile metals in waters from the Amazon Basin. Due to the complexity of the use of DGT for samples with low ionic strength and high organic matter content (characteristic of Amazonian rivers), a new analytical procedure was developed. The method is based on the determinations of apparent diffusion coefficients (D_ap) in the laboratory, by performing deployments in samples collected in the corresponding sites of study. The D_ap thereby determined is then used for in situ measurements. The suitability of the proposed approach for determination of labile Al, Cd, Co, Cu, Mn, Ni, and Zn in the Amazon River and Rio Negro (English: Black River) was evaluated. Except for Co, Mn (in a deployment at Rio Negro), Ni and Zn (in a deployment at Amazon River), labile in situ measurements were lower or similar to dissolved concentrations, indicating suitability of the proposed approach.     

Handling of Astyanax sp. for biomonitoring in Cangüiri Farm within a fountainhead (Iraí River Environment Preservation Area) through the use of genetic biomarkers

Aquatic environmental pollution may cause biodiversity loss. Thus, monitoring studies are very important because fish health reflects both quality and sustainability of the environment, as well as of the individuals that live there. In the present report, genetic biomarkers (piscine micronucleus test; comet assay with blood, liver, and kidney cells) were used in specimens of Astyanax sp. to analyze the contamination level of the Cangüiri Farm through biomonitoring. The Cangüiri Farm, the old school farm of the Federal University of Paraná, is inside the Iraí River Environment Preservation Area, created in 1996 to preserve the sources of public water supply in Curitiba and metropolitan area. We verified that the fishes collected within the Cangüiri Farm area presented high damage levels, showing more environment contamination when compared to the specimens collected in the Costa Ecologic Park, used as reference in the present report. The results indicate that the Cangüiri Farm, which is inside an environment protection area, created especially for the protection of the fountainhead for water supply, may be contaminated. These toxic residues, which were remarkably persistent in the environment, are possibly derived from agricultural activities in the wider area. Thus, we suggest the analysis of the area with other biomarkers and for a longer time period.     

Major inputs and mobility of potentially toxic elements contamination in urban areas

Soil quality in urban areas is affected by anthropogenic activities, posing a risk to human health and ecosystems. Since the pseudo-total concentrations of potentially toxic elements may not reflect their potential risks, the study of element mobility is very important on a risk assessment basis. This study aims at characterising the distribution and major sources of 34 elements in two Portuguese urban areas (Lisbon and Viseu), with different geological characteristics, industrial and urban development processes. Furthermore, the potential availability of As, Co, Cr, Cu, Ni, Pb and Zn was assessed, by measuring the fraction easily mobilised. Lisbon is enriched in elements of geogenic and anthropogenic origin, whereas in the smaller city, the high levels observed are mainly related to a geogenic origin. Background values can be more relevant than the dimension of the city, even when anthropogenic components may be present, and this parameter should be considered when comparing results from different cities. Regarding the potential available fraction, a high variability of results was observed for elements and for sampling sites with an influence of the soil’s general characteristics. Elements showing very high concentrations due to geological reasons presented, in general, a low mobility and it was not dependent on the degree of contamination. For elements with major anthropogenic origin, only Zn was dependent on the pseudo-total content. Yet, the highest available fractions of some elements, both with major geogenic and anthropogenic origin, were observed in specific contaminated samples. Therefore, a site-specific evaluation in urban soils is important due to the high spatial variability and heterogeneity.     

The problem of using fixed-area subsampling methods to estimate macroinvertebrate richness: a case study with Neotropical stream data

Subsampling has been widely applied in the laboratory to process freshwater macroinvertebrate samples. Currently, many governmental agencies and research groups apply the fixed-count approach, targeting a number of individuals per sample, and at the same time keeping track of the number of quadrats (fraction of the sample) processed. However, fixed-area methods are still in use. The objective of this paper was to evaluate the reliability of macroinvertebrate taxonomic richness estimates developed from processing a standard number of subsampling quadrats (i.e., fixed-area approaches). We used a dataset from 18 tropical stream sites experiencing three different levels of human disturbance (most-, intermediate-, and least-disturbed). With 12 quadrats processed (half the sample), the collection curves started to stabilize, and for more than half of the sites studied, it was possible to sample at least 80 % of the total taxonomic richness of the sample. However, we observed that the minimum number of quadrats to achieve 80 % of taxonomic richness was strongly negatively correlated with the number of individuals collected in each site: the fewer the individuals in a sample, the greater the processed proportion of that sample needed to represent it properly. Thus our results indicate that for any given areal subsampling effort (any fixed fraction of the sample), samples with different numbers of individuals will be represented differently in terms of the proportion of the total number of taxa of the whole samples, those with greater numbers being overestimated and those with fewer numbers being underestimated. Therefore, we do not recommend the use of fixed-area subsampling methods alone if the main purpose is to measure and analyze taxonomic richness; instead, we encourage researchers to use fixed-count approaches for this purpose.     

Mercury pollution in Ria de Aveiro (Portugal): a review of the system assessment

The Ria de Aveiro (Portugal) is a coast al lagoon adjacent to the Atlantic Ocean and it has an inner bay (Laranjo bay) that received a highly contaminated effluent discharged by a mercury cell chlor-alkali plant from the 1950s until 1994. The aim of this study is to review in a holistic way several research studies that have been carried out in the Ria de Aveiro, in order to evaluate the remobilization of the mercury accumulated within the system and the recovery of the lagoon. The spatial distribution of the total mercury in the surrounding terrestrial environment has also been considered. Results indicate that the main mercury contamination problems in the Ria de Aveiro are confined to the Laranjo bay. Mercury export to the coastal waters and its impact on the nearshore compartments (water column, sediment and biota) are low. No direct effects of the mercury from nearby industrial activities were detected in Aveiro's urban soils, although historical mercury contamination is still affecting soil quality in the immediate vicinity of the chlor-alkali plant, located in Estarreja. Moreover, macrophyte harvesting for human direct or indirect use and the consumption of mussels, crabs and the sea bass from the Laranjo bay may constitute a health risk. Further studies focusing on developing skills for the restoration of the ecosystem are presently underway.     

Use of neural networks for monitoring surface water quality changes in a neotropical urban stream

This paper reports the using of neural networks for water quality analysis in a tropical urban stream before (2002) and after sewerage building and the completion of point-source control-based sanitation program (2003). Mathematical modeling divided water quality data in two categories: (a) input of some in situ water quality variables (temperature, pH, O2 concentration, O2 saturation and electrical conductivity) and (b) water chemical composition (N-NO2(-); N-NO3(-); N-NH4(+) Total-N; P-PO4(3-); K+; Ca2+; Mg+2; Cu2+; Zn2+ and Fe+3) as the output from tested models. Stream water data come from fortnightly sampling in five points along the Ipanema stream (Southeast Brazil, Minas Gerais state) plus two points downstream and upstream Ipanema discharge into Doce River. Once the best models are consistent with variables behavior we suggest that neural networking shows potential as a methodology to enhance guidelines for urban streams restoration, conservation and management.     

Detection of hormones in surface and drinking water in Brazil by LC-ESI-MS/MS and ecotoxicological assessment with <Emphasis Type="Italic">Daphnia magna</Emphasis>

The growing use of pharmaceutical drug is mainly due to several diseases in human and in animal husbandry. As these drugs are discharged into waterways via wastewater, they cause a major impact on the environment. Many of these drugs are hormones; in which even at low concentrations can alter metabolic and physiological functions in many organisms. Hormones were found in surface water, groundwater, soil, and sediment at concentrations from nanograms to milligrams per liter of volume—quantities known to cause changes in the endocrine system of aquatic organisms. This study aimed to develop a methodology for hormone detection (estriol, estrone, 17β-estradiol, 17α-ethinylestradiol, progesterone, and testosterone) on surface and treated water samples. Sample toxicity was assessed by ecotoxicology tests using Daphnia magna. A liquid chromatograph coupled to a mass spectrometer with an electrospray ionization source (LC-ESI-MS/MS) was used for the analysis. The results showed that samples were contaminated by the hormones estriol, estrone, progesterone, 17β-estradiol, and 17α-ethinylestradiol during the sampling period, and the highest concentrations measured were 90, 28, 26, 137, and 194 ng·L^?1, respectively. This indicates the inflow of sewage containing these hormones at some points in the Piracicaba River in the State of Sao Paulo—Brazil. Results indicated little toxicity of the hormone estriol in D. magna, indicating that chronic studies with this microcrustacean are necessary.