Effectively quantifying hot moments of nitrous oxide (N2O) emissions from agricultural soils is critical for managing this potent greenhouse gas. However, we are challenged by a lack of standard approaches for identifying hot moments, including (1) determining thresholds above which emissions are considered hot moments, and (2) considering seasonal variation in the magnitude and frequency distribution of net N2O fluxes. We used one year of hourly N2O flux measurements from 16 autochambers that varied in flux magnitude and frequency distribution in a conventionally tilled maize field in central Illinois, USA to compare three approaches to identify hot moment thresholds: 4x the standard deviation (SD) above the mean, 1.5x the interquartile range (IQR), and isolation forest (IF) identification of anomalous values. We also compared these approaches on seasonally subdivided data (early, late, non-growing seasons) vs. the whole year. Our analyses of the datasets revealed that 1.5x IQR method best identified N2O hot moments. In contrast, the 4 SD method yielded hot moment threshold values too high, and the IF method yielded threshold values too low, leading to missed N2O hot moments or low net N2O fluxes mischaracterized as hot moments, respectively. Furthermore, seasonally subdividing the dataset facilitated identification of smaller hot moments in the late and non-growing seasons when N2O hot moments were generally smaller, but it also increased hot moment threshold values in the early growing season when N2O hot moments were larger. Consequently, we recommend using the 1.5x IQR method on whole year datasets to identify N2O hot moments.

Installation of subsurface drainage systems has profoundly altered the nitrogen cycle in agricultural regions across the globe, facilitating substantial loss of nitrate (NO3-) to surface water systems. Lack of understanding of the sources and processes controlling NO3- loss from tile-drained agroecosystems hinders the development of management strategies aimed at reducing this loss. The natural abundance nitrogen and oxygen isotopes of NO3- provide a valuable tool for differentiating nitrogen sources and tracking the biogeochemical transformations acting on NO3-. This study combined multi-years of tile drainage measurements with NO3- isotopic analysis to examine NO3- source and transport mechanisms in a tile-drained corn-soybean field. The tile drainage NO3- isotope data were supplemented by characterization of the nitrogen isotopic composition of potential NO3- sources (fertilizer, soil nitrogen, and crop biomass) in the field and the oxygen isotopic composition of NO3- produced by nitrification in soil incubations. The results show that NO3- isotopes in tile drainage were highly responsive to tile discharge variation and fertilizer input. After accounting for isotopic fractionations during nitrification and denitrification, the isotopic signature of tile drainage NO3- was temporally stable and similar to those of fertilizer and soybean residue during unfertilized periods. This temporal invariance in NO3- isotopic signature indicates a nitrogen legacy effect, possibly resulting from N recycling at the soil microsite scale and a large water storage for NO3- mixing. Collectively, these results demonstrate how combining field NO3- isotope data with knowledge of isotopic fractionations can reveal mechanisms controlling NO3- cycling and transport under complex field conditions.

Recent theoretical advances related to time-variant water age in hydrologic systems have opened the door to a new method that probes water mixing and selection behaviors using StorAge Selection (SAS) functions. In this study, SAS functions were applied to investigate storage, water mixing behaviors, and nitrate (NO3-) export regimes in a tile-drained corn-soybean rotation field in the Midwestern United States. The natural abundance stable nitrogen and oxygen isotopes of tile drainage NO3- were also measured to provide constraints on biogeochemical NO3- transformations. The SAS functions calibrated using chloride measurements at tile drain outlets revealed a strong young water preference during tile discharge generation. The use of a time-variant SAS function for tile discharge generated unique water age dynamics that reveals an inverse storage effect driven by activation of preferential flow paths and mechanically explains the observed variations in NO3- isotopes. Combining the water age estimates with NO3- isotope fingerprinting delineated NO3- export dynamics at the tile-drain scale, where a lack of strong contrast in NO3- concentration across the soil profile results in chemostatic NO3- export regimes. For the first time, NO3- isotopes were embedded into a water age-based transport model to model reactive NO3- transport under transient conditions. Results from this modeling study provided a proof-of-concept for the potential of coupled water age modeling and NO3- isotope analysis in elucidating complex mechanisms that control the coupled water and NO3- transport. Further integration of water age theory and NO3- isotope biogeochemistry is expected to significantly improve reactive NO3- transport modeling.

Stabilization of microbial-derived products such as extracellular enzymes (EE) has gained attention as a possibly important mechanism leading to the persistence of soil organic carbon (SOC). While the controls on EE activities and their stabilization in the surface soil are reasonably well-understood, how these activities change with soil depth and possibly diverge from those at the soil surface due to distinct physical, chemical, and biotic conditions remains unclear. We assessed EE activity to a depth of 1 m (10 cm increments) in 19 soil profiles across the Critical Zone Observatory Network, which represents a wide range of climates, soil orders, and vegetation types. Activities of four carbon (C)-acquiring enzymes (α-glucosidase, β-glucosidase, β-xylosidase, and cellobiohydrolase), two nitrogen (N)-acquiring enzymes (N-acetylglucosaminidase and leucine aminopeptidase), and one phosphorus (P)-acquiring enzyme (acid phosphatase) were measured fluorometrically along with SOC, total N, Olsen P, pH, clay concentration, and phospholipid fatty acids, which we used to characterize the microbial community composition and biomass (MB). For all EEs, activities per gram soil correlated positively with MB and SOC; all of which decreased logarithmically with depth (p < 0.05). Across all sites, over half of the potential soil EE activities per gram soil consistently occurred below 20 cm for all measured EEs. Activities per unit MB or SOC were substantially higher at depth (soils below 20 cm accounted for 80% of whole-profile EE activity), suggesting an accumulation of stabilized (i.e., mineral sorbed) EEs in subsoil horizons. The pronounced enzyme stabilization in subsurface horizons was corroborated by mixed-effects models that showed a significant, positive relationship between clay concentration and MB-normalized EE activities in the subsoil. Furthermore, the negative relationships between soil C, N, and P and C-, N-, and P-acquiring EEs found in the surface soil decoupled at 20 cm, which could have also been caused by EE stabilization. This suggesting that EEs do not reflect soil nutrient availabilities at depth. Taken together, our results suggest that deeper soil horizons hold a significant reservoir of EEs, and that the controls of subsoil EEs differ from their surface soil counterparts.