Analysis and comparison of wellhead protection areas delimitation methods applying a stochastic MODFLOW model as a reference.

Sustainable use of groundwater while maintaining economic and social development is a major challenge, and the implementation of wellhead protection areas (WHPA) for public supply wells has been applied as an instrument to overcome it. This study analyzes the WHPA delineation methods: calculated fixed radius (CFR) and two solutions of the WhAEM software (USEPA, 2018), one analytical and one semi-analytical. We compare their results with WHPAs generated by a stochastic three-dimensional MODFLOW-MODPATH model in two scenarios: eight pumping wells operating simultaneously and a single well pumping, both at the same public drinking water supply wellfield located on a coastal plain in Jaguaruna County, south Brazil. For the specific hydrogeological settings, all methods produced satisfactory results when delineating a 50-day time-of-travel (TOT) WHPA for a single well. However, as TOT increases, uncertainties are introduced, and the precision of the results is reduced. Multiple well pumping simultaneously presented similar issues regarding uncertainties caused by three-dimensional flow complexities resulting from well interferences. Despite being the simplest method applied in terms of hydrogeological data needs, the CFR method demonstrated reliability in its results. Additionally, we present an analysis comparing the dimensions of the capture zone with the 10- and 20-year TOT WHPAs, indicating that managing the entire capture zone is the best way to protect groundwater against conservative contaminants. Finally, we compare WHPA generated by a stochastic and a deterministic model to understand how uncertainties can affect model results.

Occurrence and distribution of per-and polyfluoroalkyl substances (PFAS) in surface and groundwaters in an urbanized and agricultural area, Southern Brazil.

Per- and polyfluoroalkyl substances, known as PFAS, are emerging contaminants detected in surface water, groundwater, drinking water, air, and food. Due to its chemical stability and high hydrophobicity, these compounds are used as surfactants, surface protectors, flame retardants, textile impregnation, fire-fighting foam, and pesticides and may be a risk for human health in the long-term exposure. Currently, a little research has been carried out for these compounds in Brazil. In this study, the concentration and distribution of 23 PFAS were analyzed in groundwater samples collected from water wells in urbanized areas and in surface water samples from Porto Alegre, one of the biggest cities in Brazil. The total concentrations of PFAS (ΣPFAS) in a groundwater sample varied between 22 and 718 ng L-1. Eleven PFAS species were detected in groundwater, including PFOA, PFHxA, PFPeA, PFBA, PFDA, PFNA, and PFOS. Most of PFAS were quantified in samples located in the aquifer formed by medium to coarse sands intercalated with silty-sandy lenses and low organic matter content that could facilitate the percolation of these compounds. The total concentrations of PFAS (ΣPFAS) in a surface water sample varied between 11 and 17 ng L-1. Ten species were founded in surface water being PFOA, PFOS, and PFHpA the most dominant. Considering all the samples, PFOA was the predominant species in the study. In addition, tributary water bodies had higher concentrations of PFAS than the main water body (Guaiba Lake) probably due dilution process.

Unraveling the occurrence of contaminants of emerging concern in groundwater from urban setting: A combined multidisciplinary approach and self-organizing maps.

In recent decades, changes in human behavior and new technologies have introduced thousands of new compounds into the environment called "contaminants of emerging concern" (CEC). These compounds have been detected in different environmental compartments such as soil, surface water, air, and groundwater. The presence of these contaminants in groundwater may pose risks to human health when used as potable water. In some urban areas in Brazil, groundwater is normally consumed without previous treatment. This study aimed to use statistical analysis by self-organizing maps (SOM) to evaluate the trends of CEC in urban groundwater systems. A total of 23 CEC compounds including pesticides, pharmaceuticals, and hormones were determined in groundwater samples using solid phase extraction and liquid chromatography-mass spectrometry. The CEC most frequently detected were atrazine and degradation products, fipronil, simazine, tebuconazole, hexazinone, and caffeine in concentrations up to 300 ng L-1. All studied compounds were detected in groundwater at least in one sample. Patterns in the data through SOM have shown a strong positive correlation between atrazine, hexazinone, simazine, tebuthiuron, 2-hydroxyatrazine, and 17ß-estradiol. The hormones estrone and testosterone also show a positive correlation due to their similar chemical properties. On the other hand, caffeine was detected in 90% of the samples, likely due to a population habit of taking daily a hot drink made of yerba mate associated with low rates of treated domestic sewage in the study area.

Transport of emerging contaminants: a column experimental study in granitic, gneissic, and quaternary alluvial soils from Porto Alegre, Southern Brazil.

Emerging contaminants is a topic that has been in evidence, especially in the last decades. These compounds are pesticides, pharmaceuticals, and personal care products that are present in several locations, mainly in large urban centers. The aim of this work was to investigate the fate of seven compounds (atrazine, simazine, ametrine, tebuthiuron, 2,4-D, fipronil, and diclofenac) using leaching column experiments to evaluate accumulation and transfer in 5 different types of urban soils from Porto Alegre, Southern Brazil. Chemical analyses were carried out through liquid chromatography tandem mass spectrometry (LC-MS/MS). The results showed that the soil derived from quaternary sediments, with well-sorted sandy sediments, was the one in which the contaminants had higher mobility. This soil also has a pH above the average of the others in the city, a factor that may also be responsible for less retention of substances. Tebuthiuron is the substance with the greatest leaching potential overall. Column experiments are a relevant tool to understand the behavior of emerging contaminants in soils and implications on the population health.

Combining lead isotopes and cluster analysis to distinguish the Guarani and Serra Geral Aquifer Systems and contaminated waters in a highly industrialized area in Southern Brazil.

The Rio dos Sinos Watershed area is located at the Middle-West region of the Rio Grande do Sul State, Southern Brazil, along thirty two municipalities and affecting 1.5 million inhabitants and many important industrial centers. Three main aquifers are recognized in the study area: the unconfined-fractured Serra Geral Aquifer System, the porous Guarani Aquifer System, and the Permian Aquitard. This study aims to understand groundwater, surface water and human activity interactions in the Rio dos Sinos Watershed, evaluating the application of stable lead isotopic ratios analyzed for this propose. Thirty six groundwater samples, 8 surface water samples and 5 liquid effluents of tanneries and landfills samples were measured using a Thermal Ionization Mass Spectrometer Thermo-Finnigan and a Neptune Multi-Collector Inductively Coupled Plasma Mass Spectrometer. Groundwater isotopic ratios have a wider range compared to the surface water, with less radiogenic averages 208Pb/204Pb = 38.1837 vs 38.4050 (standard deviation = 0.2921 vs 0.1343) and 206Pb/204Pb = 18.2947 vs 18.4766 (standard deviation = 0.2215 vs 0.1059), respectively. Industrial liquid effluents (tanneries and industrial landfill) have averages 208Pb/204Pb = 38.1956 and 206Pb/204Pb = 18.3169, distinct from effluent samples of domestic sanitary landfill (averages 208Pb/204Pb = 38.2353 and 206Pb/204Pb = 18.6607). Hierarchical cluster analysis led to distinguish six groups of groundwater, representing the three aquifers that occur in the area, two clusters suggesting groundwater mixtures and one demonstrating a highly contaminated groundwater. By analyzing the cluster results and wells' stratigraphic profiles it was possible to distinguish the different aquifers in the area. The Serra Geral Aquifer System has 206Pb/204Pb ratios between 18.4718 and 18.7089; 207Pb/204Pb between 15.6692 and 15.6777; 208Pb/204Pb between 38.6826 and 38.7616; 207Pb/206Pb between 0.8372 and 0.8623; 208Pb/206Pb between 2.0671 and 2.0964 and the Guarani Aquifer System has a wider range (208Pb/204Pb ranged from 37.9393 to 38.1279 and 206Pb/204Pb ranged from 18.0892 to 18.3217). Water mixing of these two aquifer systems is reflected by transitional results. The results confirm that the hierarchical cluster analysis of lead isotopes is a useful tool to discriminate different aquifer conditions, reflecting mostly the influence of the natural lead isotopic composition of the aquifers instead of the anthropogenic activities (urban and industrial), except when the groundwater is highly contaminated by human activity.

Radon emissions related to the granitic Precambrian shield in southern Brazil.

The equivalent uranium (eU) activity concentration was analysed in selected granite samples at several sites in Porto Alegre, Southern Brazil, to obtain information on the radon ((222)Rn) generation by the aquifer rock matrices. Radon analyses of ground water and soil samples were also performed. Several samples exhibited a dissolved (222)Rn activity concentration exceeding the World Health Organization maximum limit of 100 Bq l(-1). The dissolved radon content in ground waters from the Fractured Precambrian Aquifer System exhibited a direct significant correlation with the eU in the rock matrices, which is a typical result of water-rock interactions. Variation in the soil's porosity was confirmed as an important factor for (222)Rn release, as expected, due to its gaseous nature. Thus, although the calcic-alkaline to alkaline Precambrian granitoid rocks of the study area are important reservoirs for underground resources, they can release high amounts of radon gas into the liquid phase.

Hydrogeochemistry and statistical analysis applied to understand fluoride provenance in the Guarani Aquifer System, Southern Brazil.

High fluoride concentrations (up to 11 mg/L) have been reported in the groundwater of the Guarani Aquifer System (Santa Maria Formation) in the central region of the state of Rio Grande do Sul, Southern Brazil. In this area, dental fluorosis is an endemic disease. This paper presents the geochemical data and the combination of statistical analysis (Principal components and cluster analyses) and geochemical modeling to achieve the hydrogeochemistry of the groundwater and discusses the possible fluoride origin. The groundwater from the Santa Maria Formation is comprised of four different geochemical groups. The first group corresponds to a sodium chloride groundwater which evolves to sodium bicarbonate, the second one, both containing fluoride anomalies. The third group is represented by calcium bicarbonate groundwater, and in the fourth, magnesium is the distinctive parameter. The statistical and geochemical analyses supported by isotopic measurements indicated that groundwater may have originated from mixtures of deeper aquifers and the fluoride concentrations could be derived from rock/water interactions (e.g., desorption from clay minerals).

Definição de níveis aceitáveis baseados no risco para hidrocarbonetos no Município de Porto Alegre segundo a metodologia RBCA / Definition of risk-based screening levels to hydrocarbons in Porto Alegre municipality according to the RBCA methodology

O presente estudo definiu valores de NABR (Níveis Aceitáveis Baseados no Risco) para hidrocarbonetos no Município de Porto Alegre, de acordo a metodologia RBCA, adotando-se dados hidrogeológicos dos compartimentos Embasamento Cristalino alterado e Depósitos Sedimentares Quaternários. Os parâmetros de exposição adequados à população do município, bem como dados de toxicidade dos compostos selecionados, foram definidos a partir de fontes bibliográficas e bancos toxicológicos disponíveis. As tabelas de referência geradas são, em geral, mais restritivas para o Embasamento Cristalino em relação aos Depósitos Sedimentares. Comparados às tabelas de referência da Cetesb, os valores correspondentes a Porto Alegre são inferiores, resultando na necessidade de investigações ambientais mais detalhadas em áreas impactadas por hidrocarbonetos.

This study defined RBSL (Risk Based Screening Levels) values to hydrocarbons in Porto Alegre, Southern Brazil. The values were obtained through the RBCA methodology, using hydrogeological data from the Crystalline Altered Basement and the Quaternary Sedimentary Deposits. The exposure parameters appropriate to the urban population, as well as toxicity data of selected compounds, were obtained from bibliographical sources and toxicological databases. The reference tables demonstrated that the Crystalline Altered Basement values, in general, are more restrictive than those from the Quaternary Sedimentary Deposits. In comparison to Cetesb's reference tables, the values in Porto Alegre are lower, resulting in the need of more detailed environmental investigations in hydrocarbons polluted areas.

Fluoride characterization by principal component analysis in the hydrochemical facies of Serra Geral Aquifer System in Southern Brazil

Principal component analysis is applied to 309 groundwater chemical data information from wells in the Serra Geral Aquifer System. Correlations among seven hydrochemical parameters are statistically examined. A four-component model is suggested and explains 81 percent of total variance. Component 1 represents calcium-magnesium bicarbonated groundwaters with long time of residence. Component 2 represents sulfated and chlorinated calcium and sodium groundwaters; Component 3 represents sodium bicarbonated groundwaters; and Component 4 is characterized by sodium sulfated with high fluoride facies. The components' spatial distribution shows high fluoride concentration along analyzed tectonic fault system and aligned on northeast direction in other areas, suggesting other hydrogeological fault systems. High fluoride concentration increases according to groundwater pumping depth. The Principal Component Analysis reveals features of the groundwater mixture and individualizes water facies. In this scenery, it can be determined hydrogeological blocks associated with tectonic fault system here introduced.

A Análise de Componentes Principais foi aplicada em 309 dados químicos de águas subterrâneas de poços do Sistema Aqüífero Serra Geral. Correlações entre sete parâmetros hidroquímicos foram examinadas através da estatística. O modelo de quatro componentes foi utilizado por explicar 81 por cento da variância total. A Componente 1 é representada por águas cálcio-magnesianas com longo tempo de residência, a Componente 2 representa águas bicarbonatadas sulfatadas e cloretadas, a Componente 3 representa águas bicarbonatadas sódicas e a Componente 4 é caracterizada por águas de fácies sódica e sulfatada com alto fluoreto. A distribuição espacial das componentes mostra águas com concentrações anômalas ao longo dos sistemas tectônicos de falhas, analisados e alinhados a NE em algumas áreas, sugerindo outros sistemas de falhas hidrogeológicos. As concentrações de fluoreto aumentam de acordo com a profundidade de bombeamento das águas. A Análise de Componentes Principais revelou feições de mistura e individualizou diferentes fácies de águas subterrâneas. Neste cenário, é possível determinar blocos hidrogeológicos associados com os sistemas tectônicos de falhas introduzidos no presente trabalho.

Fluoride characterization by principal component analysis in the hydrochemical facies of Serra Geral Aquifer System in Southern Brazil.

Principal component analysis is applied to 309 groundwater chemical data information from wells in the Serra Geral Aquifer System. Correlations among seven hydrochemical parameters are statistically examined. A four-component model is suggested and explains 81% of total variance. Component 1 represents calcium-magnesium bicarbonated groundwaters with long time of residence. Component 2 represents sulfated and chlorinated calcium and sodium groundwaters; Component 3 represents sodium bicarbonated groundwaters; and Component 4 is characterized by sodium sulfated with high fluoride facies. The components' spatial distribution shows high fluoride concentration along analyzed tectonic fault system and aligned on northeast direction in other areas, suggesting other hydrogeological fault systems. High fluoride concentration increases according to groundwater pumping depth. The Principal Component Analysis reveals features of the groundwater mixture and individualizes water facies. In this scenery, it can be determined hydrogeological blocks associated with tectonic fault system here introduced.

Anomalous fluoride concentration in groundwater - is it natural or pollution? A stable isotope approach.

Fluoride anomalies (up to 11 mg/l) have been detected in groundwater of the central region of Rio Grande do Sul State, Southern Brazil, in an area where fluorosis is endemic. Two hypotheses are investigated concerning the fluoride origin: lithochemical affiliation from regional rock or contamination by fertilisers application. These hypotheses are discussed based on the stable isotope data of water, nitrate, and sulphate, which indicates that the local precipitation is the main groundwater recharge source. The isotopic composition of groundwater sulphate is similar to that of fertiliser sulphate. However, a conclusive assignment of groundwater sulphate to fertiliser origin is not indicated because further possible sulphate sources fall into the same isotopic range. In contrast, the isotopic composition of dissolved nitrate suggests that there is no direct relationship to the use of NPK fertilisers. Hence, an origin of the high fluoride content in groundwater related to long-term rock-water interactions seems likely.

Fluoride distribution in the environment along the gradient of a phosphate-fertilizer production emission (southern Brazil).

Airborne fluoride was determined in the rainwater, surface soil and groundwater along a gradient of emission of a phosphate fertilizer factory in Rio Grande, southern Brazil. Concentrations of fluoride in rainwater and groundwater achieved 3 mg l(-1) and 5 mg l(-1), respectively, and were dependent on pH. The fluoride deposited from emissions accumulated in a superficial horizon of soil in quantities comparable to those in the manufactured end-products--up to 23,000 mg kg(-1). Fluoride distribution in the environment is controlled by physical-chemical parameters of emission, rain intensity and soil properties. The highest fluoride concentrations were registered at a close distance of up to 2 km from the factory. The distribution of fluoride in groundwater resembled the same distribution in rainwater due to the high permeability of the local soils. Fluoride penetration to the groundwater also depended on the type of vegetation cover. The groundwater in woodland areas was less affected by contamination of fluoride than in the grassland areas, most probably because of the influence of eucalyptus throughfall, which increases the pH of wet precipitates.

Metal contamination of vineyard soils in wet subtropics (southern Brazil).

The vine-growing areas in Brazil are the dampest in the world. Copper maximum value registered in this study was as much as 3200 mg kg(-1), which is several times higher than reported for vineyard soils in temperate climates. Other pesticide-derived metals accumulate in the topsoil layer, surpassing in the old vineyards the background value several times for Zn, Pb, Cr and Cd. Copper is transported to deeper soils' horizons and can potentially contaminate groundwater. The soils from basaltic volcanic rocks reveal the highest values of Cu extracted with CaCl(2), demonstrating a high capacity of copper transference into plants. When evaluating the risks of copper's toxic effects in subtropics, the soils from rhyolitic volcanic rocks are more worrisome, as the Cu extracted with ammonium acetate 1M surpasses the toxic threshold as much as 4-6 times.

The effect of emissions of fertilizer production on the environment contamination by cadmium and arsenic in southern Brazil.

The distribution of cadmium and arsenic in rainwater, surface soil and groundwater in a zone of influence of emissions of a phosphate fertilizer factory has been investigated. The analysis of rainwater along a wind line shows that cadmium in the soluble form precipitates close to emission source, whereas arsenic migrates further and also in the soluble form precipitates at a greater distance. The pH controls the distribution of cadmium and arsenic in rain and groundwater. Concentration of soluble cadmium along the impact line increases with reduction of pH and arsenic, contrary to the increase of pH. Concentrations of cadmium and arsenic in surface soil correlate well among themselves near to emission point. In a zone of confluence of emissions with sea air at a distance from the factory there is sedimentation of arsenic on a geochemical barrier and formation of a separate anomaly in soil.