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Differentiating the contributions of photosynthesis and respiration to the global carbon cycle is critical for improving predictive climate models. Carbonic anhydrase (CA) activity in leaves is responsible for the largest biosphere-atmosphere trace gas fluxes of carbonyl sulfide (COS) and the oxygen-18 isotopologue of carbon dioxide (CO18O) that both reflect gross photosynthetic rates. However, CA activity also occurs in soils and will be a source of uncertainty in the use of COS and CO18O as carbon cycle tracers until process-based constraints are improved. In this study, we measured COS and CO18O exchange rates and estimated the corresponding CA activity in soils from a range of biomes and land use types. Soil CA activity was not uniform for COS and CO2, and patterns of divergence were related to microbial community composition and CA gene expression patterns. In some cases, the same microbial taxa and CA classes catalyzed both COS and CO2 reactions in soil, but in other cases the specificity towards the two substrates differed markedly. CA activity for COS was related to fungal taxa and β-D-CA expression, whereas CA activity for CO2 was related to algal and bacterial taxa and α-CA expression. This study integrates gas exchange measurements, enzyme activity models, and characterization of soil taxonomic and genetic diversity to build connections between CA activity and the soil microbiome. Importantly, our results identify kinetic parameters to represent soil CA activity during application of COS and CO18O as carbon cycle tracers.

Current understanding of phosphorus (P) cycling in soils can be enhanced by integrating previously discrete findings concerning P speciation, exchange kinetics, and the underlying biological and geochemical processes. Here, we combine sequential extraction with P K-edge X-ray absorption spectroscopy and isotopic methods (33P and 18O in phosphate) to characterize P cycling on a climatic gradient in Hawaii. We link P pools to P species and estimate the turnover times for commonly considered P pools. Dissolved P turned over in seconds, resin-extractable P in minutes, NaOH-extractable inorganic P in weeks to months, and HCl-extractable P in years to millennia. Furthermore, we show that in arid-zone soils, some primary mineral P remains even after 150 ky of soil development, whereas in humid-zone soils of the same age, all P in all pools has been biologically cycled. The integrative information we provide makes possible a more dynamic, process-oriented conceptual model of P cycling in soils.

The supply of nitrogen (N) constrains primary productivity in many ecosystems, raising the question "what controls the availability and cycling of N"? As a step toward answering this question, we evaluated N cycling processes and aspects of their regulation on a climate gradient on Kohala Volcano, Hawaii, USA. The gradient extends from sites receiving 3,000 mm/yr, and the pedology and dynamics of rock-derived nutrients in soils on the gradient are well understood. In particular, there is a soil process domain at intermediate rainfall within which ongoing weathering and biological uplift have enriched total and available pools of rock-derived nutrients substantially; sites at higher rainfall than this domain are acid and infertile as a consequence of depletion of rock-derived nutrients, while sites at lower rainfall are unproductive and subject to wind erosion. We found elevated rates of potential net N mineralization in the domain where rock-derived nutrients are enriched. Higher-rainfall sites have low rates of potential net N mineralization and high rates of microbial N immobilization, despite relatively high rates of gross N mineralization. Lower-rainfall sites have moderately low potential net N mineralization, relatively low rates of gross N mineralization, and rates of microbial N immobilization sufficient to sequester almost all the mineral N produced. Bulk soil δ15 N also varied along the gradient, from +4‰ at high rainfall sites to +14‰ at low rainfall sites, indicating differences in the sources and dynamics of soil N. Our analysis shows that there is a strong association between N cycling and soil process domains that are defined using soil characteristics independent of N along this gradient, and that short-term controls of N cycling can be understood in terms of the supply of and demand for N.

The oxygen isotope ratio of phosphates is a powerful tool to study phosphorus in the soil‐plant system. In the past two decades, the scientific community has made substantial progress in characterizing biogeochemical processes that lead to an alteration of oxygen isotope ratios in phosphates and in evaluating oxygen isotope ratios of phosphates in plants and soils under various environmental conditions around the globe. However, there are still uncertainties with respect to their interpretation in environmental systems. These uncertainties include the comprehensive analysis of isotope endmembers, artifacts during the chemical extractions and the phosphate purification protocols, overlapping isotope values from various processes and sources, gaps of knowledge about isotope effects of metabolic pathways, and the possibly erroneous assumption that insights from experiments under controlled laboratory conditions can be directly translated into the complex soil‐plant system. This paper provides a critical discussion of these uncertainties addressing recommendations and needs for future research and gives an outlook on recent technological advances, such as triple oxygen isotope analysis or the use of high‐resolution mass spectrometry. We conclude by suggesting that a concerted and systematic effort by scientists from a wide range of disciplines will be necessary to remove the uncertainties in the interpretation of oxygen isotope ratios in phosphates as an environmental tracer. [ABSTRACT FROM AUTHOR]

Recent studies from the Hawaiian Islands showed that pedogenic thresholds demarcate domains in which rock-derived nutrient dynamics remain similar across wide variations in rainfall. These thresholds appear related to certain aspects of N cycling, but the degree to which they correspond to patterns of biological N fixation (BNF)—the dominant input of N into less-managed ecosystems—remains unclear. We measured aboveground plant biomass, foliar nutrient concentrations, and foliar δ15N along a climate gradient on ~ 150,000-year-old basaltic substrate to characterize foliar N sources and spatially relate them to soil nutrients. Patterns in legume δ15N correspond to known pedogenic thresholds along the rainfall gradient, with low δ15N values (~ 0 to − 2‰) occurring in the dry, biologically inactive domain and the wet, highly weathered domain. Elevated δ15N in the middle, fertile domain suggests a greater reliance of legumes on soil N where it has accumulated over time. Non-legume face N deficiencies throughout most of the gradient while legumes maintain low C:N ratios via symbiotic BNF. However, legume abundance declines outside the fertile domain, limiting ecosystem N inputs. Breakpoints in legume δ15N data suggest that P (and potentially other nutrients) limits BNF and, by extension, legume abundance in wet region. Nutrients may also constrain legume abundance in the dry domain, but pedogenic effects could not be isolated from climatic constraints at the dry sites. We conclude that pedogenic thresholds defined by climate can be informative of foliar δ15N patterns in cases where legumes are not directly constrained by climate, land use, or other external factors. [ABSTRACT FROM AUTHOR]

Differentiating the contributions of photosynthesis and respiration to the global carbon cycle is critical for improving predictive climate models. Carbonic anhydrase (CA) activity in leaves is responsible for the largest biosphere-atmosphere trace gas fluxes of carbonyl sulfide (COS) and the oxygen-18 isotopologue of carbon dioxide (CO18O) that both reflect gross photosynthetic rates. However, CA activity also occurs in soils and will be a source of uncertainty in the use of COS and CO18O as carbon cycle tracers until process-based constraints are improved. In this study, we measured COS and CO18O exchange rates and estimated the corresponding CA activity in soils from a range of biomes and land use types. Soil CA activity was not uniform for COS and CO2, and patterns of divergence were related to microbial community composition and CA gene expression patterns. In some cases, the same microbial taxa and CA classes catalyzed both COS and CO2 reactions in soil, but in other cases the specificity towards the two substrates differed markedly. CA activity for COS was related to fungal taxa and β-D-CA expression, whereas CA activity for CO2 was related to algal and bacterial taxa and α-CA expression. This study integrates gas exchange measurements, enzyme activity models, and characterization of soil taxonomic and genetic diversity to build connections between CA activity and the soil microbiome. Importantly, our results identify kinetic parameters to represent soil CA activity during application of COS and CO18O as carbon cycle tracers. [ABSTRACT FROM AUTHOR]