Water balance affects foliar and soil nutrients differently.

Water balance influences soil development, and consequently plant communities, by driving weathering of soil minerals and leaching of plant nutrients from the soil. Along gradients in water balance, soils exhibit process domains where chemical properties are relatively stable punctuated by pedogenic thresholds where soil chemical properties change rapidly with little additional change in water balance. We ask if plant macronutrient concentrations in leaves also exhibit non-linear trends along water balance gradients, and if so, how these non-linearities relate to those in soils. We analyze foliar nutrient concentrations and foliar N:P ratios from eight species that span a range of growth forms along three water balance gradients (three of the species are found on multiple gradients). The gradients are located on basaltic substrate of different ages and have previously been characterized by studies on soil development. We find that maximum concentrations of foliar macronutrients occur at an intermediate water balance. As with soil nutrients, time mediates the effect of water balance on foliar nutrients, such that plants on older soils attain maximum nutrient concentrations at a lower water balance. On both a young, 20 ky and an old, 4100 ky water balance gradient, foliar nutrients reach peak concentrations at a water balance greater than the threshold for depletion of rock-derived nutrients in surface soils. Our findings suggest that plant acquisition of essential nutrients is imperfectly predicted by overall soil nutrient availability because the regulation of internal nutrient pools by plants makes nutrient pools within leaves partially independent of soil nutrient availability.

Carbonate clumped isotope analysis (Δ47 ) of 21 carbonate standards determined via gas-source isotope-ratio mass spectrometry on four instrumental configurations using carbonate-based standardization and multiyear data sets.

RATIONALE: Clumped isotope geochemistry examines the pairing or clumping of heavy isotopes in molecules and provides information about the thermodynamic and kinetic controls on their formation. The first clumped isotope measurements of carbonate minerals were first published 15 years ago, and since then, interlaboratory offsets have been observed, and laboratory and community practices for measurement, data analysis, and instrumentation have evolved. Here we briefly review historical and recent developments for measurements, share Tripati Lab practices for four different instrument configurations, test a recently published proposal for carbonate-based standardization on multiple instruments using multi-year data sets, and report values for 21 different carbonate standards that allow for recalculations of previously published data sets. METHODS: We examine data from 4628 standard measurements on Thermo MAT 253 and Nu Perspective IS mass spectrometers, using a common acid bath (90°C) and small-sample (70°C) individual reaction vessels. Each configuration was investigated by treating some standards as anchors (working standards) and the remainder as unknowns (consistency standards). RESULTS: We show that different acid digestion systems and mass spectrometer models yield indistinguishable results when instrument drift is well characterized. For linearity correction, mixed gas-and-carbonate standardization or carbonate-only standardization yields similar results. No difference is observed in the use of three or eight working standards for the construction of transfer functions. CONCLUSIONS: We show that all configurations yield similar results if instrument drift is robustly characterized and validate a recent proposal for carbonate-based standardization using large multiyear data sets. Δ47 values are reported for 21 carbonate standards on both the absolute reference frame (ARF; also refered to as the Carbon Dioxide Equilibrated Scale or CDES) and the new InterCarb-Carbon Dioxide Equilibrium Scale (I-CDES) reference frame, facilitating intercomparison of data from a diversity of labs and instrument configurations and restandardization of a broad range of sample sets between 2006, when the first carbonate measurements were published, and the present.

Quantitative Analysis of Pedogenic Thresholds and Domains in Volcanic Soils.

Pedogenic thresholds describe where soil properties or processes change in an abrupt/nonlinear fashion in response to small changes in environmental forcing. Contrastingly, soil process domains refer to the space between thresholds where soil properties are either unchanged, or change gradually, across a broad range of environmental forcing. Here, we test quantitatively for the presence of thresholds in patterns of soil properties across a climatic gradient on soils developed from ~20 ky old basaltic substrate on the Island of Hawai'i. From multiple soil properties, we quantitatively identified a threshold at ~750 mm/y of water balance (precipitation minus potential evapotranspiration), delineating the upper water balance boundary of soil fertility in these soils. From the threshold in the ratio of exchangeable Ca to total Ca we identified the lower water balance boundary of soil fertility in these soils at -1000 mm/y, however this threshold was qualitatively described as it lies near the limit of the climate gradient data where the statistical approach can not be applied. These two results represent the first time that pedogenic thresholds have been identified using statistically rigorous methods and the limitations of said methods, respectively. Comparing the 20 ky soils to soils that developed on basaltic substrates of 1.2 ky, 7.5 ky, 150 ky, and 4100 ky in a time-climate matrix, we found that our quantitative analysis supports previous qualitatively identified thresholds in the soils developed from older substrates. We also identified the 20 ky as the transition from kinetic to supply limitation for plant nutrients in soil in this system.