How much rainwater contributes to a spring discharge in the Guarani Aquifer System: insights from stable isotopes and a mass balance model.

Outcrops play an important role in groundwater recharge. Understanding groundwater origins, dynamics and its correlation with different water sources is essential for effective water resources management and planning in terms of quantity and quality. In the case of the Guarani Aquifer System (GAS) outcrop areas are particularly vulnerable to groundwater pollution due to direct recharge processes. This study focuses on the Alto Jacaré-Pepira sub-basin, a watershed near Brotas, a city in the central region of the state of São Paulo, Brazil, where groundwater is vital for supporting tourism, agriculture, urban water supply, creeks, river and wetlands. The area has a humid tropical climate with periods of both intense rainfall and drought, and the rivers remain perennial throughout the year. Therefore, the aim of this study is to investigate the interconnections between a spring and its potential sources of contribution, namely rain and groundwater, in order to elucidate the relationships between the different water sources. To achieve this, on-site monitoring of groundwater depth, rainfall amount, and stable isotope ratios (deuterium (2H) and oxygen-18 (18O)) from rain, spring discharge, and a monitoring well was carried out from 2013 to 2021. The results indicate that the mean and standard deviations for δ18O in rainwater exhibit higher variability, resulting in -4.49 ± 3.18 ‰ VSMOW, while δ18O values from the well show minor variations, similar to those of the spring, recording -7.25 ± 0.32 ‰ and -6.94 ± 0.28 ‰ VSMOW, respectively. The mixing model's outcomes reveal seasonal variations in water sources contribution and indicate that groundwater accounts for approximately 80 % of spring discharge throughout the year. Incorporating stable isotopes into hydrological monitoring provides valuable data for complementing watershed analysis. The values obtained support the significance of the aquifer as a primary source, thereby offering critical insights into stream dynamics of the region.

Toxoplasma gondii Exposure and Dietary Habits of Two Sympatric Carnivores in the Valdivian Temperate Rainforest, Southern Chile.

Toxoplasma gondii, a parasitic protozoan, may infect most warm-blooded animals, including humans and carnivores. Our study focused on alien-invasive American minks (Neogale vison) and domestic cats (Felis catus) in the Valdivian Temperate Rainforest, Chile. The main goal was to investigate the relationship between their dietary habits and T. gondii exposure in the Valdivia River watershed. To detect T. gondii exposure, blood serum samples from 49 domestic cats and 40 American minks were analyzed using an ELISA, and stable isotope analysis of δ15N and δ13C from vibrissae was performed to determine the dietary habits of both species. Relationships between T. gondii exposure and dietary habits were explored using generalized linear mixed-effects models. American minks that were T. gondii seropositive exhibited a broader prey range compared to seropositive domestic cats, with minimal dietary overlap between the two groups. Exposure of domestic cats to T. gondii had no significant association with any isotope value or prey item in their diet. In American minks, we found a positive and significant association between the proportion of Domestic chicken (Gallus gallus domesticus) in the diet and high δ15N values with T. gondii exposure. This suggests that domestic species prey related to anthropogenic areas, and the consumption of high-trophic-level prey, may contribute to T. gondii exposure in American minks. Conversely, contrary to previous hypotheses, consumption of rodents showed no significant association with T. gondii exposure in either species. Our findings emphasize the importance of further research to investigate trophic interactions in the transmission dynamics of T. gondii in the Valdivian Temperate Rainforest.

Sediment source fingerprints of natural processes and anthropogenic pressures: A contribution to manage the Paraopeba River basin impacted by the B1 tailings dam collapse.

Understanding the origins of sediment transport in river systems is crucial for effective watershed management, especially after catastrophic events. This information is essential for the development of integrated strategies that guarantee water security in river basins. The present study aimed to investigate the rupture of the B1 tailings dam of the Córrego do Feijão mine, which drastically affected the Brumadinho region (Minas Gerais, Brazil). To address this issue, a confluence-based sediment fingerprinting approach was developed through the SedSAT model. Uncertainty was assessed through Monte Carlo simulations and Mean Absolute Error (MAE). Estimates of the overall average contributions of each tributary were quantified for each station and annually during the period 2019-2021. It was observed that the sampling point PT-09, closest to the dam breach, contributed to almost 80% of the Paraopeba River in 2019. Despite the dredging efforts, this percentage increased to 90% in 2020 due to the need to restore the highly degraded area. Additionally, the main tributaries contributing to sediment increase in the river are Manso River "TT-03" (almost 36%), associated with an area with a high percentage of urban land use, and Cedro stream "TT-07" (almost 71%), whose geology promotes erosion, leading to higher sediment concentration. Uncertainties arise from the limited number of available tracers, variations caused by dredging activities, and reduced data in 2020 due to the pandemic. Parameters such as land use, riparian vegetation degradation, downstream basin geology, and increased precipitation are key factors for successfully assessing tributary contributions to the Paraopeba River. The obtained results are promising for a preliminary analysis, allowing the quantification of key areas due to higher erosion and studying how this disaster affected the watershed. This information is crucial for improving decision-making, environmental governance, and the development of mitigating measures to ensure water security. This study is pioneering in evaluating this methodology in watersheds affected by environmental disasters, where restoration efforts are ongoing.

Sewage contamination assessment in an urbanized tropical estuary in Northeast Brazil using elemental, isotopic and molecular proxies.

The Capibaribe Estuarine System (CES) is a tropical estuary located within a densely populated metropolitan region in the Brazilian Northeast, providing multiple ecosystem services including artisanal fisheries, tourism, and navigation. A significant load of domestic and industrial effluents is causing visible environmental degradation that needs to be characterized. This study evaluated the degree of contamination by domestic sewage and the relative contribution of organic carbon (OC) sources in sediments, measuring carbon-to-nitrogen atomic (C/N)a ratios, δ13C of OC, and linear alkylbenzene concentrations (LAB). The SIAR mixing model indicated that estuarine phytoplankton and sewage contribute 73% and 22% to OC, respectively, based on sedimentary (C/N)a ratios that varied from 8.5 to 13, and δ13C ranging from -25.21 to -21.63‰. This suggests that eutrophication of CES is triggered by sewage inflow. The CES was moderately contaminated by LAB, and the highest concentrations observed in the inner portion, from 287 to 1349 ng g-1 dry weight, suggests the retention of sewage. The mixing isotopic model indicated a significant dilution process of sewage-derived OC by estuarine phytoplankton. The lowest LAB in the lower estuary (317-320 ng g-1 dw) probably resulted from marine dilution. Principal component analysis demonstrated that mud regulates sedimentary OC content, and that the sewage plume regulates sedimentary LAB. High degradation of LAB isomers probably reflects the net heterotrophic condition of this system, also suggesting these compounds are introduced into CES partially degraded. Our results pointed out that degraded OM is a result of chronic and long-term sewage input. Considering the implications of sewage pollution to environmental and public health, there is an urgent need of better policies to improve domestic effluent treatment capacity, reducing contamination of estuarine environments.

Lead Isotopic Constraints on the Provenance of Antarctic Dust and Atmospheric Circulation Patterns Prior to the Mid-Brunhes Event (~430 kyr ago).

A lead (Pb) isotopic record, covering the two oldest glacial-interglacial cycles (~572 to 801 kyr ago) characterized by lukewarm interglacials in the European Project for Ice Coring in Antarctica Dome C ice core, provides evidence for dust provenance in central East Antarctic ice prior to the Mid-Brunhes Event (MBE), ~430 kyr ago. Combined with published post-MBE data, distinct isotopic compositions, coupled with isotope mixing model results, suggest Patagonia/Tierra del Fuego (TdF) as the most important sources of dust during both pre-MBE and post-MBE cold and intermediate glacial periods. During interglacials, central-western Argentina emerges as a major contributor, resulting from reduced dust supply from Patagonia/TdF after the MBE, contrasting to the persistent dominance of dust from Patagonia/TdF before the MBE. The data also show a small fraction of volcanic Pb transferred from extra-Antarctic volcanoes during post-MBE interglacials, as opposed to abundant transfer prior to the MBE. These differences are most likely attributed to the enhanced wet removal efficiency with the hydrological cycle intensified over the Southern Ocean, associated with a poleward shift of the southern westerly winds (SWW) during warmer post-MBE interglacials, and vice versa during cooler pre-MBE ones. Our results highlight sensitive responses of the SWW and the associated atmospheric conditions to stepwise Antarctic warming.

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.

Application of remote sensing to analyze the loss of natural vegetation in the Jalapão Mosaic (Brazil) before and after the creation of protected area (1970-2018).

This study aims to map the changes in land use and land cover between 1970 and 2018, analyzing the influence of the protected area s (PAs) in the Cerrado biome, specifically in the area of the Jalapão Mosaic. Images from the Landsat 1-MSS, 5-TM, and 8-OLI satellites were used and processed in SPRING and ArcGIS software. The analyses were based on three approaches: (1) the boundary of the Jalapão Mosaic, (2) the PAs, and (3) a comparison between the PAs and their surroundings. The Jalapão Mosaic results demonstrated that 26% (≅ 8410 km2) of the area was burned, and 15.5% (4971 km2) was anthropized in at least one of the analyzed periods. Among the PAs, the Serra Geral do Tocantins Ecological Station (Integral Protection) presented the largest burned area (43.7% ≅ 3095 km2); however, there was no significant increase in the anthropized areas due to fire. Meanwhile, the anthropized areas in the Rio Preto and Serra da Tabatinga Environmental Protection Areas (Sustainable Use) increased by 27.5% and by 75%, respectively, due to agricultural expansion. By analyzing the two groups of PAs and their surroundings, it was observed that the loss of natural vegetation was restrained and fires were less intense in the Integral Protection Units; in the Sustainable Use Units, there was a significant increase in the anthropized areas. Furthermore, over 70% of the anthropized areas occurred in the surrounding areas, thus showing the importance of creating PAs.

Determining nitrate and sulfate pollution sources and transformations in a coastal aquifer impacted by seawater intrusion-A multi-isotopic approach combined with self-organizing maps and a Bayesian mixing model.

Over the past few decades, the La Paz aquifer system in Baja California Sur, Mexico, has been under severe pressure due to overexploitation for urban water supply and agriculture; this has caused seawater intrusion and deterioration in groundwater quality. Previous studies on the La Paz aquifer have focused mainly on seawater intrusion, resulting in limited information on nitrate and sulfate pollution. Therefore, pollution sources have not yet been identified sufficiently. In this study, an approach combining hydrochemical tools, multi-isotopes (δ2HH2O, δ18OH2O, δ15NNO3, δ18ONO3, δ34SSO4, δ18OSO4), and a Bayesian isotope mixing model was used to estimate the contribution of different nitrate and sulfate sources to groundwater. Results from the MixSIAR model revealed that seawater intrusion and soil-derived sulfates were the predominant sources of groundwater sulfate, with contributions of ~43.0% (UI90 = 0.29) and ~42.0% (UI90 = 0.38), respectively. Similarly, soil organic nitrogen (~81.5%, UI90 = 0.41) and urban sewage (~12.1%, UI90 = 0.25) were the primary contributors of nitrate pollution in groundwater. The dominant biogeochemical transformation for NO3- was nitrification. Denitrification and sulfate reduction were discarded due to the aerobic conditions in the study area. These results indicate that dual-isotope sulfate analysis combined with MixSIAR models is a powerful tool for estimating the contributions of sulfate sources (including seawater-derived sulfate) in the groundwater of coastal aquifer systems affected by seawater intrusion.

Estimation of nitrate pollution sources and transformations in groundwater of an intensive livestock-agricultural area (Comarca Lagunera), combining major ions, stable isotopes and MixSIAR model.

The identification of nitrate (NO3-) sources and biogeochemical transformations is critical for understanding the different nitrogen (N) pathways, and thus, for controlling diffuse pollution in groundwater affected by livestock and agricultural activities. This study combines chemical data, including environmental isotopes (δ2HH2O, δ18OH2O, δ15NNO3, and δ18ONO3), with land use/land cover data and a Bayesian isotope mixing model, with the aim of reducing the uncertainty when estimating the contributions of different pollution sources. Sampling was taken from 53 groundwater sites in Comarca Lagunera, northern Mexico, during 2018. The results revealed that the NO3- (as N) concentration ranged from 0.01 to 109 mg/L, with more than 32% of the sites exceeding the safe limit for drinking water quality established by the World Health Organization (10 mg/L). Moreover, according to the groundwater flow path, different biogeochemical transformations were observed throughout the study area: microbial nitrification was dominant in the groundwater recharge areas with elevated NO3- concentrations; in the transition zones a mixing of different transformations, such as nitrification, denitrification, and/or volatilization, were identified, associated to moderate NO3- concentrations; whereas in the discharge area the main process affecting NO3- concentrations was denitrification, resulting in low NO3- concentrations. The results of the MixSIAR isotope mixing model revealed that the application of manure from concentrated animal-feeding operations (∼48%) and urban sewage (∼43%) were the primary contributors of NO3- pollution, whereas synthetic fertilizers (∼5%), soil organic nitrogen (∼4%), and atmospheric deposition played a less important role. Finally, an estimation of an uncertainty index (UI90) of the isotope mixing results indicated that the uncertainties associated with atmospheric deposition and NO3--fertilizers were the lowest (0.05 and 0.07, respectively), while those associated with manure and sewage were the highest (0.24 and 0.20, respectively).

From mountains to cities: a novel isotope hydrological assessment of a tropical water distribution system.

Water use by anthropogenic activities in the face of climate change invokes a better understanding of headwater sources and lowland urban water allocations. Here, we constrained a Bayesian mixing model with stable isotope data (2018-2019) in rainfall (N = 704), spring water (N = 96), and surface water (N = 94) with seasonal isotope sampling (wet and dry seasons) of an urban aqueduct (N = 215) in the Central Valley of Costa Rica. Low δ 18O rainfall compositions corresponded to the western boundary of the study area, whereas high values were reported to the northeastern limit, reflecting the influence of moisture transport from the Caribbean domain coupled with strong orographic effects over the Pacific slope. The latter is well-depicted in the relative rainfall contributions (west versus east) in two headwater systems: (a) spring (68.7 ± 3.4 %, west domain) and (b) stream (55.8 ± 3.9 %, east domain). The aqueduct exhibited a spatial predominance of spring water and surface water during a normal wet season (78.7 %), whereas deep groundwater and spring water were fundamental sources for the aqueduct in the dry season (69.4 %). Our tracer-based methodology can help improve aqueduct management practices in changing climate, including optimal water allocation and reduced evaporative losses in the dry season.

Tracking nitrate and sulfate sources in groundwater of an urbanized valley using a multi-tracer approach combined with a Bayesian isotope mixing model.

Over the past decades, groundwater quality has deteriorated worldwide by nitrate pollution due to the intensive use of fertilizers in agriculture, release of untreated urban sewage and industrial wastewater, and atmospheric deposition. Likewise, groundwater is increasingly polluted by sulfate due to the release of domestic, municipal and industrial wastewaters, as well as through geothermal processes, seawater intrusion, atmospheric deposition, mineral dissolution, and acid rain. The urbanized and industrialized Monterrey valley has a long record of elevated nitrate and sulfate concentrations in groundwater with multiple potential pollution sources. This study aimed to track different sources and transformation processes of nitrate and sulfate pollution in Monterrey using a suite of chemical and isotopic tracers (δ2H-H2O, δ18O-H2O, δ15N-NO3, δ18O-NO3 δ34S-SO4, δ18O-SO4) combined with a probability isotope mixing model. Soil nitrogen and sewage were found to be the most important nitrate sources, while atmospheric deposition, marine evaporites and sewage were the most prominent sulfate sources. However, the concentrations of nitrate and sulfate were controlled by denitrification and sulfate reduction processes in the transition and discharge zones. The approach followed in this study is useful for establishing effective pollution management strategies in contaminated aquifers.

Identifying the composition of commercial Brazilian cat food with stable isotopes of carbon and nitrogen.

Considering the increasing pet owner's concern about the food their pets are consuming, in this study we investigated the origin of the main ingredients in wet and dry foods produced in Brazil using stable isotope ratios of carbon and nitrogen. We concluded that chicken and pork seem to be the dominant ingredients in most of the samples, with larger proportions in wet cat food. Even in pet foods showing 'beef' as the main ingredient on the label, we found a low proportion of bovine products in both wet and dry cat foods. Comparing the contribution of plant-derived products (C3 and C4 plants) and animal-derived products (chicken-pork, bovine and fish), approximately 21 % of cat foods had more than 30 % of ingredients with plant origin in their composition. The high amount of plant-derived products in cat foods found here raises the question whether this should be mentioned on package labels.

Isotopic variation among Amazonian floodplain woody plants and implications for food-web research / Variación isotópica entre plantas leãosas de planicies de inundación del Amazonas e implicaciones para la investigación de red tróficas

Isotopic variation within food sources adds uncertainty to models intended to reconstruct trophic pathways. Understanding this variation is pivotal for planning sampling protocols for food-web research. This study investigates natural variation in C and N stable isotopes among plant species in two western Amazon flooded forests with contrasting watershed biogeochemistry (white-water várzea-forest and black-water igapó-forest). Our objectives were to compare δ13C and δ15N of leaves and fruits between sites; assess the magnitude of within-site variation in δ13C and δ15N of leaves (várzea: 28 spp., igapó: 10 spp.) and fruits (várzea: 22 spp., igapó: 22 spp.); determine within-plant variation in δ13C and δ15N of leaf, wood and fruit tissues; and test whether inter-specific variation in δ13C and δ15N influence the results of a mixing model predicting the contribution of terrestrial C sources to an aquatic consumer. Mean δ13C values of leaves and fruits were not statistically different between the two sites despite regional differences in biogeochemistry and floristic composition. In contrast, mean δ15N of leaves and fruits were significantly lower at the várzea than at the igapó site. The high floristic diversity of both forests was reflected in large within-site interspecific variation in both δ13C and δ15N. Paired comparisons revealed that δ13C of wood and fruits and δ15N of fruits were generally greater than values obtained for leaves from the same plant. The predicted contribution of different carbon sources to the consumer biomass changed between models as a function of source variability. We discuss implications of source variation for designing sampling protocols, interpreting isotopic signatures, and establishing trophic links between plants and consumers. Our findings highlight the importance of in situ sampling to establish reliable primary production baselines for local food webs.

La variación isotópica dentro de fuentes alimenticias aãade incertidumbre a los modelos destinados a reconstruir redes tróficas. La comprensión de esta variación es fundamental para la planificación de protocolos de muestreo para la investigación de redes alimentarias. Este estudio investiga la variación natural en isótopos estables de C y N entre especies de plantas en dos bosques inundables de la Amazonía noroccidental con biogeoquímica de cuenca contrastantes (várzea-bosques de aguas blanca e igapó-bosques de aguas negras). Nuestros objetivos fueron comparar las seãales isotópicas de δ13C y δ15N de hojas y frutos entre bosques; evaluar la magnitud de la variación en la composición isotópica de hojas (várzea: 28 spp., Igapó: 10 spp.) y frutas (várzea:. 22 spp, igapó: 22 spp.) a nivel local; determinar la variación en la composición isotópica de madera, hojas y frutas dentro de una planta; y evaluar si la variación inter-específica en los valores de δ13C y δ15N ejerce influencia sobre los resultados de modelos que predicen la contribución de fuentes de alimentos terrestres a un consumidor acuático. Los valores promedio de δ13C en hojas y frutos no fueron estadísticamente diferentes entre los dos tipos de bosque a pesar de las diferencias regionales en biogeoquímica y composición florística. Por el contrario, los valores promedio de δ15N en hojas y frutos fueron significativamente más bajos en la várzea que en el igapó. La alta diversidad florística de los dos bosques se reflejó en una gran variación inter-específica a nivel local en δ13C y δ15N. Comparaciones pareadas revelaron que los valores de δ13C de madera y frutas y δ15N de frutas fueron generalmente mayores que los valores obtenidos para las hojas de la misma planta. Los resultados sobre la contribución de diferentes fuentes de carbono a la biomasa del consumidor cambió de un modelo a otro en función a la variabilidad isotópica en las fuentes alimenticias. Discutimos las implicaciones de la variación en las fuentes alimenticias para el diseão de los protocolos de muestreo, la interpretación de las seãales isotópicas, y el establecimiento de relaciones tróficas entre plantas y consumidores. Nuestros resultados destacan la importancia de la toma de muestras in situ para establecer líneas de base fiables de producción primaria para las redes tróficas locales.

Sediments in urban river basins: identification of sediment sources within the Lago Paranoá catchment, Brasilia DF, Brazil - using the fingerprint approach.

The development of effective sediment management strategies is a key requirement in tropical areas with fast urban development, like Brasilia DF, Brazil, because of the limited resources available. Accurate identification and management of sediment sources areas, however, is hampered by the dearth of reliable information on the primary sources of sediment. Few studies have attempted to quantify the source of sediment within fast urbanizing, mixed used, tropical catchments. In this study, statistically verified composite fingerprints and a multivariate mixing model have been used to identify the main land use specific sources of sediment deposited in the artificial Lago Paranoá, Central Brazil. Because of the variability of urban land use types within the Lago Paranoá sub-catchments, the fingerprinting approach was additionally undertaking for the Riacho Fundo sub-catchment. The main contributions from individual source types (i.e. surface materials from residential areas, constructions sites, road deposited sediment, cultivated areas, pasture, farm tracks, woodland and natural gullies) varied between the whole catchment and the Riacho Fundo sub-catchment, reflecting the different proportions of land uses. The sediments deposited in the silting zones of the Lago Paranoá originate largely from urban sources (85 ± 4%). Areas with (semi-) natural vegetation and natural gullies contribute 10 ± 2% of the sediment yield. Agricultural sites have only a minor sediment contribution of about 5 ± 4% within the whole catchment. Within the Riacho Fundo sub-catchment there is a significant contribution from urban (53 ± 4%) source, such as residential areas with semi-detached housings (42 ± 3%) with unpaved roads (12 ± 3%) and construction sites (20 ± 3%) and agricultural areas (31 ± 2%). The relative contribution from land use specific sources to the sediment deposition in the silting zone of the Lago Paranoá demonstrated that most of the sediment is derived from sites with high anthropogenic impact.