Nitrate isotopes (δ15N, δ18O) in precipitation: best practices from an international coordinated research project.

Stable isotope ratios of nitrogen and oxygen (15N/14N and 18O/16O) of nitrate (NO3-) are excellent tracers for developing systematic understanding of sources, conversions, and deposition of reactive atmospheric nitrogen (Nr) in the environment. Despite recent analytical advances, standardized sampling of NO3-) isotopes in precipitation is still lacking. To advance atmospheric studies on Nr species, we propose best-practice guidelines for accurate and precise sampling and analysis of NO3- isotopes in precipitation based on the experience obtained from an international research project coordinated by the International Atomic Energy Agency (IAEA). The precipitation sampling and preservation strategies yielded a good agreement between the NO3- concentrations measured at the laboratories of 16 countries and at the IAEA. Compared to conventional methods (e.g., bacterial denitrification), we confirmed the accurate performance of the lower cost Ti(III) reduction method for isotope analyses (15N and 18O) of NO3- in precipitation samples. These isotopic data depict different origins and oxidation pathways of inorganic nitrogen. This work emphasized the capability of NO3- isotopes to assess the origin and atmospheric oxidation of Nr and outlined a pathway to improve laboratory capability and expertise at a global scale. The incorporation of other isotopes like 17O in Nr is recommended in future studies.

Frontiers in páramo water resources research: A multidisciplinary assessment.

Interdisciplinary knowledge is necessary to achieve sustainable management of natural resources. However, research is still often developed in an exclusively disciplinary manner, hampering the capacity to holistically address environmental issues. This study focuses on páramo, a group of high-elevation ecosystems situated around ∼3000 to ∼5000 m a.s.l. in the Andes from western Venezuela and northern Colombia through Ecuador down to northern Peru, and in the highlands of Panama and Costa Rica in Central America. Páramo is a social-ecological system that has been inhabited and shaped by human activity since ∼10,000 years BP. This system is highly valued for the water-related ecosystem services provided to millions of people because it forms the headwaters of major rivers in the Andean-Amazon region, including the Amazon River. We present a multidisciplinary assessment of peer-reviewed research on the abiotic (physical and chemical), biotic (ecological and ecophysiological), and social-political aspects and elements of páramo water resources. A total of 147 publications were evaluated through a systematic literature review process. We found that thematically 58, 19, and 23 % of the analyzed studies are related to the abiotic, biotic, and social-political aspects of páramo water resources, respectively. Geographically, most publications were developed in Ecuador (71 % of the synthesized publications). From 2010 onwards, the understanding of hydrological processes including precipitation and fog dynamics, evapotranspiration, soil water transport, and runoff generation improved, particularly for the humid páramo of southern Ecuador. Investigations on the chemical quality of water generated by páramo are rare, providing little empirical support to the widespread belief that páramo environments generate water of high quality. Most ecological studies examined the coupling between páramo terrestrial and aquatic environments, but few directly assessed in-stream metabolic and nutrient cycling processes. Studies focused on the connection between ecophysiological and ecohydrological processes influencing páramo water balance are still scarce and mainly related to the dominant vegetation in the Andean páramo, i.e., tussock grass (pajonal). Social-political studies addressed páramo governance and the implementation and significance of water funds and payment for hydrological services. Studies directly addressing water use, access, and governance in páramo communities remain limited. Importantly, we found only a few interdisciplinary studies combining methodologies from at least two disciplines of different nature despite their value in supporting decision-making. We expect this multidisciplinary synthesis to become a milestone to foster interdisciplinary and transdisciplinary dialogue among individuals and entities involved in and committed to the sustainable management of páramo natural resources. Finally, we also highlight key frontiers in páramo water resources research, which in our view need to be addressed in the coming years/decades to achieve this goal.

Isotopic composition and major ion concentrations of national and international bottled waters in Costa Rica.

Global bottled water consumption has largely increased (14.35 billion gallons in 2020) [1], [2], [3], [4], [5] during the last decade since consumers are demanding healthier and safer forms of rehydration. Bottled water sources are normally labeled as mountainous and pristine mineral springs (fed by rainfall and snow/glacier melting processes), deep groundwater wells or industrial purified water. The advent of numerous international and national-based bottled water brands has simultaneously raised a worldwide awareness related to the water source and chemical content traceability [6]. Here, we present the first database of stable isotope compositions and reported chemical concentrations from imported and national-based bottled waters in Costa Rica. In total, 45 bottled waters produced in Costa Rica and 31 imported from USA, Europe, Oceania, and other countries of Central America were analyzed for δ18O, δ2H, and d-excess. Chemical compositions were obtained from available bottle labels. National-based bottle waters ranged from -2.47‰ to -10.65‰ in δ18O and from -10.4‰ to -78.0‰ in δ2H, while d-excess varied from +4.2‰ up to +17.0‰. International bottle waters ranged between -2.21‰ and -11.03‰ in δ18O and from -11.3‰ up to -76.0‰ in δ2H, while d-excess varied from +5.0‰ up to +19.1‰. In Costa Rica, only 19% of the brands reported chemical parameters such as Na+, K+, Ca+2, Mg+2, F-, Cl-, NO3 -, SO4 -2, CO3 -2, SiO2, dry residue, and pH; whereas 27% of the international products reported similar parameters. The absence of specific geographic coordinates or water source origin limited a spatial analysis to validate bottled water isotope compositions versus available isoscapes in Costa Rica [7]. This database highlights the potential and relevance of the use of water stable isotope compositions to improve the traceability of bottled water sources and the urgent need of more robust legislation in order to provide detailed information (i.e., water source, chemical composition, purification processes) to the final consumers.

Stable isotopic characterization of nitrate wet deposition in the tropical urban atmosphere of Costa Rica.

Increasing energy consumption and food production worldwide results in anthropogenic emissions of reactive nitrogen into the atmosphere. To date, however, little information is available on tropical urban environments where inorganic nitrogen is vastly transported and deposited through precipitation on terrestrial and aquatic ecosystems. To fill this gap, we present compositions of water stable isotopes in precipitation and atmospheric nitrate (δ18O-H2O, δ2H-H2O, δ15N-NO3-, and δ18O-NO3-) collected daily between August 2018 and November 2019 in a tropical urban atmosphere of central Costa Rica. Rainfall generation processes (convective and stratiform rainfall fractions) were identified using stable isotopes in precipitation coupled with air mass back trajectory analysis. A Bayesian isotope mixing model using δ15N-NO3- compositions and corrected for potential 15N fractionation effects revealed the contribution of lightning (25.9 ± 7.1%), biomass burning (21.8 ± 6.6%), gasoline (19.1 ± 6.4%), diesel (18.4 ± 6.0%), and soil biogenic emissions (15.0 ± 2.6%) to nitrate wet deposition. δ18O-NO3- values reflect the oxidation of NOx sources via the ·OH + RO2 pathways. These findings provide necessary baseline information about the combination of water and nitrogen stable isotopes with atmospheric chemistry and hydrometeorological techniques to better understand wet deposition processes and to characterize the origin and magnitude of inorganic nitrogen loadings in tropical regions.

Isotope composition of carbon dioxide and methane in a tropical urban atmosphere.

This work presents a weekly carbon isotope composition analysis (June 2017-January 2018) of carbon dioxide (CO2) and methane (CH4) in a tropical urban atmosphere (Central Valley, Costa Rica). δ13C values of CO2 and CH4 ranged from -12.2 to -5.9 ‰, and from -51.6 to -46.3 ‰, respectively. Mixing ratios of CO2 and CH4 varied from 384.2 to 528.5 ppmv, and from 1.860 to 2.613 ppmv, respectively. δ13C spatial variation and mixing ratios of CO2 and CH4 were influenced by the atmospheric stability and air circulation patterns in the metropolitan area. Low δ13C values and large mixing ratios were observed in the southwestern area of the valley during the rainiest period (September-November). Preliminary linear relationships between reciprocal CO2 mixing ratios and δ13C values indicate that CO2 emissions in the Central Valley are probably related to respiration processes and fossil fuel combustion, although CO2 enriched in 13C from volcanic degassing was also detected. Under stable atmospheric conditions, CH4 data seems to reflect the influence of emissions near the sampling sites. These preliminary results based on the carbon isotope technique demonstrate potential for carrying out atmospheric studies at tropical urban locations with different terrain characteristics and atmospheric mixing conditions.

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.

Hydrogeological responses in tropical mountainous springs.

This study presents a hydrogeochemical analysis of spring responses (2013-2017) in the tropical mountainous region of the Central Valley of Costa Rica. The isotopic distribution of δ18O and δ2H in rainfall resulted in a highly significant meteoric water line: δ2H = 7.93·Î´18O + 10.37 (r2 = 0.97). Rainfall isotopic composition exhibited a strong amount-dependent seasonality. The isotopic variation (δ18O) of two springs within the Barva aquifer was simulated using the FlowPC program to determine mean transit times (MTTs). Exponential-piston and dispersion distribution functions provided the best-fit to the observed isotopic composition at Flores and Sacramento springs, respectively. MTTs corresponded to 1.23 ± 0.03 (Sacramento) and 1.42 ± 0.04 (Flores) years. The greater MTT was represented by a homogeneous geochemical composition at Flores, whereas the smaller MTT at Sacramento is reflected in a more variable geochemical response. The results may be used to enhance modelling efforts in central Costa Rica, whereby scarcity of long-term data limits water resources management plans.

Deciphering key processes controlling rainfall isotopic variability during extreme tropical cyclones.

The Mesoamerican and Caribbean (MAC) region is characterized by tropical cyclones (TCs), strong El Niño-Southern Oscillation events, and climate variability that bring unique hazards to socio-ecological systems. Here we report the first characterization of the isotopic evolution of a TC (Hurricane Otto, 2016) in the MAC region. We use long-term daily rainfall isotopes from Costa Rica and event-based sampling of Hurricanes Irma and Maria (2017), to underpin the dynamical drivers of TC isotope ratios. During Hurricane Otto, rainfall exhibited a large isotopic range, comparable to the annual isotopic cycle. As Hurricane Otto organized into a Category 3, rapid isotopic depletion coupled with a decrease in d-excess indicates efficient isotopic fractionation within ~200 km SW of the warm core. Our results shed light on key processes governing rainfall isotope ratios in the MAC region during continental and maritime TC tracks, with applications to the interpretation of paleo-hydroclimate across the tropics.

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.

Isotopic composition in precipitation and groundwater in the northern mountainous region of the Central Valley of Costa Rica.

The linkage between precipitation and recharge is still poorly understood in the Central America region. This study focuses on stable isotopic composition in precipitation and groundwater in the northern mountainous region of the Central Valley of Costa Rica. During the dry season, rainfall samples corresponded to enriched events with high deuterium excess. By mid-May, the Intertropical Convergence Zone poses over Costa Rica resulting in a depletion of 18O/16O and 2H/H ratios. A parsimonious four-variable regression model (r2 = 0.52) was able to predict daily δ18O in precipitation. Air mass back trajectories indicated a combination of Caribbean Sea and Pacific Ocean sources, which is clearly depicted in groundwater isoscape. Aquifers relying on Pacific-originated recharge exhibited a more depleted pattern, whereas recharge areas relying on Caribbean parental moisture showed an enrichment trend. These results can be used to enhance modelling efforts in Central America where scarcity of long-term data limits water resources management plans.