Assessment of River-Aquifer Interaction and Nitrogen Contamination in an Agricultural Zone Located in the Guarani Aquifer System Outcrop Area.

The excessive use of nitrogen fertilizers is responsible for an increase in nitrate concentrations in water bodies, which in the future could led to an irreversible contamination compromising the water resource quality. In this way, understand the water movement within a watershed and evaluate the impacts related to agricultural practices is relevant for water management, especially in an environmental fragile region, such as the outcrop area of the Guarani Aquifer. Water samples from a small watershed located at the Guarani Aquifer region in São Paulo state, representing surface water and groundwater discharge in riverbeds from two creeks, as well as groundwater (springs and wells) were collected for isotopic ratios (δ18O e δ2H) and nitrate determination. The results indicated that the river flow is mostly supplied by groundwater discharge, and despite the observed concentrations of nitrate in groundwater reaching the creeks, the current scenario indicate contamination in the surface water, above the regulatory levels. Therefore, the expansion in sugarcane production increases the possibility that the released nitrate reaches high levels in the future in this watershed.

Assessment of the changes in contributions from water sources to streamflow induced by urbanization in a small-sized catchment in Southeastern Brazil using the dual stable isotopes of water (18O and 2H).

Urban growth often results in changes in the urban hydrological cycle, causing impacts on water availability in densely populated regions. The water isotopologues can provide relevant information about the origin of water under different hydrogeological scenarios, aiding to implement better strategies for water conservation in coupled natural-urbanized environments. In this study, the isotopic compositions of multiple water sources were assessed in a pristine (Ipanema National Forest, FLONA) and an urbanized (Lavapés catchment, SOR) watershed located in the Sorocaba River basin (State of São Paulo, Southeastern Brazil), seeking to understand the causes of isotopic variability and to determine the relative contribution from different sources to streamflow, using the Bayesian mixing model approach. Differences in isotopic composition were observed, as FLONA yielded the most depleted water (ca. -7.5 ‰ [Formula: see text]18O for surface and groundwater and ca. + 11.0 ‰ d-excess), while SOR yielded the most enriched water (ca. -5.5‰ [Formula: see text]18O for surface and groundwater and -3.8‰ [Formula: see text]18O for the water supply system), with evidence of evaporation (ca. + 8.2 ‰ d-excess). The differences observed in isotopic compositions are related to a combination of different factors, such as geological framework, groundwater recharge, and evaporation associated with the Itupararanga water reservoir. Both in FLONA and SOR, groundwater discharge is the most important factor that regulates streamflow. However, in SOR, losses from the water supply system were almost constant along the year, representing an important contribution. The results presented here highlight the use of isotope hydrology techniques to solve problems related to urban hydrology.

Speciation analysis of inorganic arsenic in river water by Amberlite IRA 910 resin immobilized in a polyacrylamide gel as a selective binding agent for As(V) in diffusive gradient thin film technique.

In this study, a method is proposed for the selective retention of As(V) using diffusive gradient in thin film (DGT) samplers containing a strongly basic anion exchange resin (Amberlite IRA 910) supported on a polyacrylamide gel. In addition, the total arsenic content is determined by ferrihydrite gel discs. Subsequently, the concentration of As(III) was obtained by determining the difference between the total As and As(V). DGT experiments showed linear accumulation of As(V) (up to 280 ng) until a deployment time of 8 h deployment (R(2) > 0.99). The retention of As(V) was appropriate (97.9-112.3%) between pH 5 and 9. For a solution with an ionic strength ranging from 0.001 to 0.05 mol L(-1), the As(V) uptake ranged from 90-120%. The proposed method was applied for the speciation of arsenic in river water. For the analysis of spiked samples collected at the Furnas stream, the recoveries of total arsenic content ranged between 103.9% and 118.8%. However, the recoveries of As(III) and As(V) were 43.3-75.2% and 147.3-153.4%, respectively. These differences were probably because of the oxidation of As(III) to As(V) during deployments. For spiked samples collected at the Ribeirão Claro, the recoveries of dissolved As(III), As(V) and As(T) were 103.1%, 108.0% and 106.3%, respectively. Thus, the DGT technique with Amberlite IRA 910 resin as the binding phase can be employed for the in situ redox speciation of inorganic arsenic.

Stable isotopes reveal groundwater to river connectivity in a mesoscale subtropical watershed.

The Corumbataí River basin (São Paulo, Brazil) has a critical situation regarding water availability due to the intensive use to support agriculture and urbanization, requiring scientific information to face water demand. The aim of this study is to present a hydrological characterization based on the analysis of seasonal isotope variations (rainfall, groundwater, and surface water) and hydrometric data. Results indicate that baseflow contribution varies from 50 % to 70 % of the total flow, and water isotopic composition denotes a seasonal regime marked by the mixing of surface and groundwater in the wet period and groundwater discharge during the dry season. The results presented indicated the strong seasonal connection between atmospheric inputs and water movement across the basin, which poses an urgent need to diversify monitoring methods and create feasible regional and political regulations to control the effects on basin water resilience in the face of climate change and growing demand.

Geochemical evolution, residence times and recharge conditions of the multilayered Tubarão aquifer system (State of São Paulo - Brazil) as indicated by hydrochemical, stable isotope and 14C data.

The Tubarão aquifer system constitutes a very complex, multilayered aquifer enclosed in the Paraná basin (central-southern part of Brazil). Despite the relatively low productivity of wells, groundwater represents an important source of water for the very populated and industrialized zones of the State of São Paulo. An extensive water sampling campaign was carried out followed by hydrochemical and isotopic (δ 2H, δ 18O, δ 13C and 14C) studies, aiming at a better understanding of the aquifer's geochemical evolution, recharge processes, and its groundwater residence times. Two main hydrochemical facies were recognized and divide the aquifer in two portions. The shallow portion - the active hydrological zone of the aquifer - is characterized by the Ca-HCO3 water type, evolving as a system open to atmospheric CO2. Mean residence times are typically lower than 5000 years. The lower portion is mostly characterized by the stagnant, Na-HCO3 water type, evolving under closed system conditions. Residence times average up to 15,000 years, but can reach 44,000 years, which indicates the exploitation of (possibly non-renewable) fossil waters. This study contributes to the establishment of proper policies regarding the sustainable groundwater exploitation of the Tubarão aquifer system.

Residual biomass of coffee as a binding agent in diffusive gradients in thin-films technique for Cd, Cu, Ni, Pb and Zn measurement in waters.

Spent coffee grounds (SCG) immobilized in agarose gel are proposed as a novel binding agent for application in the Diffusive Gradients in Thin films (DGT) technique for the determination of Cd, Cu, Ni, Pb and Zn in waters. The SCG-agarose gel was characterized by Scanning Electron Microscopy, Energy Dispersive X-ray Spectrometry and Porosimetry by nitrogen adsorption. Elution of analytes from the binding agent was effectively performed with 2 mol L-1 HCl. The effects of key DGT parameters (e.g. immersion time, ionic strength and pH) were evaluated with a deployment of DGT devices (DGT-SCG) in synthetic solutions with ionic strengths between 0.005 mol L-1 and 0.1 mol L-1 and within a pH range of 3.5-8.0. The results were in excellent agreement with the predicted theoretical curve for mass uptake. Consistent results were found for solutions with ionic strengths between 0.005 mol L-1 and 0.1 mol L-1 and within a pH range of 3.5-8.0. The DGT-SCG performance was also evaluated in two spiked river water samples (Corumbataí and Piracicaba river) with satisfactory uptake values (CDGT-SCG/Csol) between 0.74 and 1.53. The proposed DGT-SCG opens opportunities for using residual biomass as binding phase in the DGT technique, showing low costs in production and complying with "green" technology approaches.

Data Descriptor: Daily observations of stable isotope ratios of rainfall in the tropics.

We present precipitation isotope data (δ2H and δ18O values) from 19 stations across the tropics collected from 2012 to 2017 under the Coordinated Research Project F31004 sponsored by the International Atomic Energy Agency. Rainfall samples were collected daily and analysed for stable isotopic ratios of oxygen and hydrogen by participating laboratories following a common analytical framework. We also calculated daily mean stratiform rainfall area fractions around each station over an area of 5° x 5° longitude/latitude based on TRMM/GPM satellite data. Isotope time series, along with information on rainfall amount and stratiform/convective proportions provide a valuable tool for rainfall characterisation and to improve the ability of isotope-enabled Global Circulation Models to predict variability and availability of inputs to fresh water resources across the tropics.

Controls over spatial and seasonal variations on isotopic composition of the precipitation along the central and eastern portion of Brazil.

Based on Global Network Isotopes in Precipitation (GNIP) isotopic data set, a review of the spatial and temporal variability of δ18O and δ2H in precipitation was conducted throughout central and eastern Brazil, indicating that dynamic interactions between Intertropical and South Atlantic Convergence Zones, Amazon rainforest, and Atlantic Ocean determine the variations on the isotopic composition of precipitation over this area. Despite the seasonality and latitude effects observed, a fair correlation with precipitation amount was found. In addition, Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) air mass back trajectories were used to quantify the factors controlling daily variability in stable isotopes in precipitation. Through a linear multiple regression analysis, it was observed that temporal variations were consistent with the meteorological parameters derived from HYSPLIT, particularly precipitation amount along the trajectory and mix depth, but are not dependent on vapour residence time in the atmosphere. These findings also indicate the importance of convective systems to control the isotopic composition of precipitation in tropical and subtropical regions.

Elemental and isotopic determination of lead (Pb) in particulate matter in the Brazilian city of Goiânia (GO) using ICP-MS technique.

The toxic metal lead (Pb) can be harmful to human health in various manners, but is also considered as a distinguished tracer of environmental pollution since the relative abundance of its four stable isotopes with the atomic masses of 204, 206, 207, and 208 varies with the emission source. This study is focused on the Pb concentrations and isotope ratios in the particulate matter of the Brazilian city of Goiânia in order to determine the main Pb emission sources. Particulate matter samples were collected on clean Teflon filters during rainy and dry season in 2014 in the center of Goiânia city near main roads with a high traffic volume. Pb concentrations as well as stable Pb isotope ratios of the particulate matter samples were analyzed by inductively coupled plasma-mass spectrometry. To apply this analytical technique successfully, it was necessary to optimize parameters in case of acquisition time, detector dead time, and mass discrimination, which affect the measurement accuracy and precision. Results showed that Pb concentrations in Goiânia were different between rainy and dry season. Pb concentrations showed higher values and less variation in dry season than in rainy season. Pb isotope ratios demonstrated significant variations between dry and rainy season. An enrichment of 206Pb isotopes related to 207Pb and 208Pb isotopes was observed in dry season. However, the comparison of the obtained isotopic Pb signature with data of potential Pb sources from previous studies indicated that traffic-related sources should be considered as main Pb source in the particulate matter of Goiânia. These assumptions were incorporated by the calculation of the contribution factor of Pb coming from traffic-related sources by applying binary mixing equations.

Caracterização hidrogeoquímica de águas subterrâneas utilizadas para abastecimento público na porção nordeste do Sistema Aquífero Guarani / Hydrogeochemical characterization of groundwater for public supply in the Northeastern portion of the Guarani Aquifer System

RESUMO O Sistema Aquífero Guarani (SAG) compreende um dos mais importantes aquíferos do mundo, tanto pela grande reserva quanto pela qualidade de suas águas subterrâneas. Entretanto, nem todas as regiões, nas quais o SAG é utilizado no abastecimento público, possuem estudos a respeito do quimismo de suas águas e de sua associação com a geologia. Este trabalho apresenta a caracterização hidrogeoquímica das águas subterrâneas do SAG utilizadas no abastecimento público em São Carlos, São Paulo, região nordeste do SAG, por meio de amostras provenientes de 27 poços tubulares profundos. A captação de água subterrânea é proveniente principalmente do SAG. Entretanto, também é possível verificar a presença das formações Botucatu, Piramboia, Serra Geral, Itaqueri, Adamantina e sedimentos cenozoicos. Apesar de pouco mineralizadas, verifica-se variabilidade iônica na composição das águas subterrâneas, evidenciada na distribuição espacial da condutividade elétrica na área de estudo. Os resultados hidroquímicos apontam para a existência de quatro fácies hidroquímicas: bicarbonatadas mistas, bicarbonatadas cálcicas, bicarbonatadas sódicas e sódica fluoretada, em ordem decrescente de representatividade. A heterogeneidade geológica interfere na concentração de íons na água, por meio da dissolução mineral, e possibilita a mistura das águas subterrâneas. A análise de componentes principais constatou que 62,7% da variabilidade total do conjunto amostral é explicada, principalmente, por dois fatores. O primeiro grupo de variáveis representa 38,7% da variabilidade, atribuída principalmente aos íons provenientes da dissolução de minerais (HCO3−, Ca2+, Na+, Mg2+) e aos parâmetros relacionados a esse processo (pH e condutividade elétrica). O segundo revelou 24% da variabilidade total, que pode estar associado a origens antrópicas, como a presença dos íons Cl−, N-NO3−, SO42-, F− e K+.

ABSTRACT The Guarani Aquifer System (GAS) comprises one of the most important aquifers in the world due to its large water reserve and its groundwater quality. However, some regions that comprise the GAS groundwater for human supply are not thoroughly characterized on water chemistry and its relation with the local geology. This work presents the hydrogeochemical characterization of groundwater from the northeast region of the GAS used for human public supply in São Carlos (São Paulo, Brazil) based on samples from 27 deep boreholes. The groundwater exploration occurs mainly from GAS. However, it is also possible to verify the presence of the Botucatu, Piramboia, Serra Geral, Itaqueri, Adamantina, and Cenozoic sediments. Although little mineralized, there is a large ionic variability in the groundwater composition, also evidenced by spatial distribution of the electrical conductivity in the research area. These results explain four hydrochemical water types: mixed bicarbonate; calcium bicarbonate; sodium bicarbonate; and sodium fluoride, in decreasing order of representativeness. The concentration of ions in groundwater reflects the geological heterogeneity, through mineral dissolution and possible groundwater mixing. A Principal Component Analysis demonstrated that 62.7% of the total sample set variability is explained by two main factors. The first one represents 38.7% of the variability; mainly attributed to ions from minerals dissolution (HCO3−, Ca2+, Na+, Mg2+) and parameters related to this process (pH and electrical conductivity). The second group showed 24.0% of the total variability, which may be associated with anthropic activities origins, such as the presence of Cl−, N-NO3−, SO42-, F−, and K+.

In situ redox speciation analysis of chromium in water by diffusive gradients in thin films using a DE81 anion exchange membrane.

A method for the in situ redox speciation analysis of chromium in water by the diffusive gradients in thin films (DGT) technique using a DE81 anion exchange membrane was successfully developed. For the selective uptake of Cr(VI), a DGT device containing an anion exchange membrane DE81 (cellulose acetate chromatographic paper) was used (DE81-DGT), while selective uptake of Cr(III) was carried out using DGT devices containing the Chelex-100 resin (Chelex-100-DGT). A correlation coefficient of 0.993 was obtained for the linearity of the immersion curves (mass versus time) using DE81-DGT. The diffusion coefficient values for Cr(VI) through the agarose diffusive layer were equal to 4.89±0.5×10(-6)cm(2)s(-1) and 3.95±0.02×10(-6)cm(2)s(-1) (T=23±1°C, I=0.03molL(-1) NaNO3) were obtained by using diffusion cell and immersion curves, respectively. The retention of Cr(VI) by the DE81 membrane in a synthetic sample and river water was not affected by the pH over a wide range 4-9). Recoveries of Cr(VI) between 90% and 120% from solutions of ionic strength ranging from 0.01 to 0. 5molL(-1) NaNO3 were achieved. Finally, the redox speciation analysis of Cr(III) and Cr(VI) in spiked river water and synthetic samples was performed with recoveries greater than 80% and 87% by using Chelex-100-DGT and DE81-DGT devices, respectively. Those results were in excellent agreement with the diphenylcarbazide spectrophotometric method.