Editors’ Vox is a blog from AGU’s Publications Department.
Ensuring the sustainability of water resources and ecosystems in a changing world requires a thorough understanding of how water moves through Earth’s Critical Zone, a dynamic interface where air, water, soil, plants, and rocks interact. Researchers can track and model this movement of water using naturally occurring markers or “tracers.”
A recent article in Reviews of Geophysics explores the latest advancements in tracer-aided mixing models and how they can help us to better understand the Critical Zone. Here, we asked the authors to give an overview of the Critical Zone, how tracer-aided mixing modeling works, and future directions for research.
What is the Critical Zone (CZ)?
The Critical Zone is Earth’s “living skin”—the dynamic layer where the atmosphere, hydrosphere, biosphere, and lithosphere interact. It stretches from the top of the vegetation canopy and, in cold regions, from the surface of snowpacks and glaciers, down through soils and into the deeper aquifers. It encompasses lakes, streams, and wetlands at the surface, and extends beyond the soil layer to underlying groundwater aquifers. It is where rainfall, snowmelt and glacier melt become soil moisture, where plants take up water and return it to the atmosphere, where aquifers get recharged, and where streamflow is generated. In short, the Critical Zone is where most processes that sustain terrestrial life and freshwater resources unfold.
Why is it important to understand how water moves through the Critical Zone?
Virtually every freshwater resource we rely on (e.g., drinking water, irrigation) passes through the Critical Zone.
Virtually every freshwater resource we rely on (e.g., drinking water, irrigation) passes through the Critical Zone at some point. Global warming, land-use changes, and intensifying water demand emerging from rapid urbanization and changes in agriculture are reshaping how water is stored and released within the Critical Zone, often in ways we cannot yet predict. Understanding how much water is stored within the Critical Zone, how this water is both recharged from rainfall and snowmelt and eventually discharged into streams, and the timescale of these dynamic processes is essential for protecting ecosystems, safeguarding water supplies, and adapting to a changing climate.
How would you explain a tracer-aided mixing model to a non-specialist?
Imagine mixing a glass of orange juice with a glass of apple juice, and trying afterwards to work out how much of each went into the glass. If the juices had distinctive “fingerprints” (imagine its color, sugar content, or a specific chemical) and these fingerprints primarily changed because of the mixing of these two juices, you can then measure the fingerprint in the final mixture and back-calculate the proportion of its distinct sources.
Tracer-aided mixing models work in a similar way but can track the entire water cycle. Different water sources (e.g., rainfall, snowmelt, glacier melt, soil water, groundwater) can have distinct “fingerprints” in a naturally occurring tracer, such as stable isotopes of water or specific dissolved elements. By measuring these fingerprints in the streamwater or groundwater and in its potential sources for example, hydrologists can estimate how much each source contributed to the streamwater or groundwater.
What are some of the most significant and exciting recent advances in tracer-aided mixing models?
Classical mixing models relied on demanding assumptions: that all water sources can be identified and sampled, and that their signatures were distinct and constant in time. Much of the recent progress has been about relaxing these assumptions.
Bayesian approaches now estimate full probability distributions and provide a more realistic picture of uncertainty. Methods like Convex Hull End-Member Mixing Analysis (CHEMMA) use machine learning to infer the distinct sources directly from data, while ensemble hydrograph separation exploits tracer fluctuations over time, thereby making un-mixing feasible even when multiple sources have overlapping signatures. Perhaps the most conceptually novel advance is end-member splitting, which flips the question from “where does streamflow come from?” to “where does precipitation go?”
Alongside these modeling advances, there have been immense advances in how tracers are measured. Portable laser and mass spectrometers now enable high-frequency, in-situ tracer measurements which allows us to capture critical hydrological events such as storms and snowmelt in near-real time.
What are stable water isotope tracers and what are their advantages?
Stable water isotopes are naturally occurring non-radioactive atoms of hydrogen and oxygen that make up a water molecule but have slightly different molecular masses. The two stable isotopes widely used in hydrology are 2H (deuterium) and 18O (oxygen-18). Because these isotopes are part of the water molecule itself, they directly travel with the water molecule. Their key advantages are: (1) they are conservative, meaning they do not react chemically as water moves through soils and aquifers, and (2) they carry distinct signatures resulting from climatic variables such as air temperature.
These properties make stable water isotopes the most versatile and widely used tracer in Critical Zone hydrology.
Consequently, in the European Alps, winter precipitation has a different isotopic signature than summer precipitation because winters are cooler than summers. Other hydrological processes such as evaporation and sublimation leave a recognizable fingerprint on the remaining water, thereby allowing us to estimate how much evaporation or sublimation occurred. Stable water isotopes can be measured in essentially every water compartment, from atmospheric vapor and precipitation to snowpack, plant xylem, soil water, streams, and groundwater. Together, these properties make stable water isotopes the most versatile and widely used tracer in Critical Zone hydrology.
What are the current limitations of tracer-aided mixing models?
Despite their power, mixing models still face many constraints. End-member signatures vary in space and time, are sometimes too similar to distinguish, and some sources may be overlooked entirely. Non-conservative tracers such as nitrate or sulfate can react with their environment along their journey, thereby biasing results if these reactions are not explicitly accounted for.
Sampling is another major bottleneck. Capturing the spatial heterogeneity of soils, snowpacks, and groundwater requires a lot of measurements that are often logistically or financially prohibitive, especially in remote regions. Many of the newer, more powerful tracers such as noble gases or stable isotopes of trace elements, can only be analyzed by a handful of specialized laboratories. As a result, global coverage remains highly uneven, with key regions such as the Arctic and the global South still under-sampled.
What are some of the major unsolved questions and where is more research needed?
There are several fronts where more research is needed. Source signatures are not static, and methods that explicitly capture their variability in time are still underdeveloped. Embedding tracers within global Earth System Models would, in theory, enable more accurate assessment of hydrological partitioning e.g., how rainfall, snowmelt, and glacier melt are split between sublimation, evapotranspiration, groundwater, and streamflow. These will directly inform more robust climate projections, but this remains technically demanding.
Expanding data coverage in under-sampled regions is critical, and citizen science and low-cost sensors may help. Machine learning is a promising approach for uncovering non-linear relationships and gap-filling sparse datasets, but requires training data that often do not yet exist. Greater interdisciplinary integration, e.g., combining tracers with remote sensing, ecological indicators, and biogeochemical data, could yield a more holistic view of the Critical Zone. Finally, the field would benefit from shared protocols and open data practices to enhance progress.
—Andrea L. Popp ([email protected]; 
0000-0003-3911-8105), Swedish Meteorological and Hydrological Institute, Sweden; Harsh Beria ([email protected]; 0000-0003-2597-9449), ETH Zurich, Switzerland
Editor’s Note: It is the policy of AGU Publications to invite the authors of articles published in Reviews of Geophysics to write a summary for Eos Editors’ Vox.