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Anoxic microsites, zones of oxygen depletion in otherwise well-aerated soils, serve as prominent controls on several biogeochemical cycles (e.g., carbon, nitrogen, iron). However, relatively little is known about the spatiotemporal distribution of anoxic microsites and thus little is known about their biogeochemical influence. Here, we use time-integrative measures of past anoxia (i.e., electrochemical measurements and quantification of anaerobic functional genes) to determine how the spatial distribution of anoxic microsites varies between aggregate interiors and bulk soils in soils of two distinct textures across multiple depths in a California grassland. We found greater evidence of anoxia in topsoils vs. subsoils and finer vs. coarse-textured soils. Counter to many traditional depictions of soil aggregates, we observed that aggregate interiors showed equal or less evidence of anoxic microsites than bulk soils. Across the entire dataset, our combined proxies for anoxic microsite prevalence were strongly and positively correlated with organic C concentration (R2 = 0.80), highlighting the importance of soil organic C availability and microbial oxygen demand in creating anoxic microsites. Our results contribute to a growing body of evidence that soil oxygen demand (i.e., microbial respiration) can play a more prominent role in anoxic microsite formation than soil oxygen supply, provoking questions about the suitability of using aggregate size and moisture as lone proxies for soil oxygen availability.

Redox reactions underlie several biogeochemical processes and are typically spatiotemporally heterogeneous in soils and sediments. However, redox heterogeneity has yet to be incorporated into mainstream conceptualizations and modeling of soil biogeochemistry. Anoxic microsites, a defining feature of soil redox heterogeneity, are non-majority oxygen depleted zones in otherwise oxic environments. Neglecting to account for anoxic microsites can generate major uncertainties in quantitative assessments of greenhouse gas emissions, C sequestration, as well as nutrient and contaminant cycling at the ecosystem to global scales. However, only a few studies have observed/characterized anoxic microsites in undisturbed soils, primarily, because soil is opaque and microsites require µm-cm scale resolution over cm-m scales. Consequently, our current understanding of microsite characteristics does not support model parameterization. To resolve this knowledge gap, we demonstrate through this proof-of-concept study that X-ray fluorescence (XRF) 2D mapping can reliably detect, quantify, and provide basic redox characterization of anoxic microsites using solid phase “forensic” evidence. First, we tested and developed a systematic data processing approach to eliminate false positive redox microsites, i.e., artefacts, detected from synchrotron-based multiple-energy XRF 2D mapping of Fe (as a proxy of redox-sensitive elements) in Fe-“rich” sediment cores with artificially injected microsites. Then, spatial distribution of FeII and FeIII species from full, natural soil core slices (over cm-m lengths/widths) were mapped at 1–100 µm resolution. These investigations revealed direct evidence of anoxic microsites in predominantly oxic soils such as from an oak savanna and toeslope soil of a mountainous watershed, where anaerobicity would typically not be expected. We also revealed preferential spatial distribution of redox microsites inside aggregates from oak savanna soils. We anticipate that this approach will advance our understanding of soil biogeochemistry and help resolve “anomalous” occurrences of reduced products in nominally oxic soils.

Shrub species are expanding across the Arctic in response to climate change and biotic interactions. Changes in belowground carbon (C) and nitrogen (N) storage are of global importance because Arctic soils store approximately half of global soil C. We collected 10 (60 cm) soil cores each from graminoid- and shrub-dominated soils in western Greenland and determined soil texture, pH, C and N pools, and C:N ratios by depth for the mineral soil. To investigate the relative chemical stability of soil C between vegetation types, we employed a novel sequential extraction method for measuring organo-mineral C pools of increasing bond strength. We found that (i) mineral soil C and N storage was significantly greater under graminoids than shrubs (29.0 ± 1.8 versus 22.5 ± 3.0 kg·C·m−2 and 1.9 ± .12 versus 1.4 ± 1.9 kg·N·m−2), (ii) chemical mechanisms of C storage in the organo-mineral soil fraction did not differ between graminoid and shrub soils, and (iii) weak adsorption to mineral surfaces accounted for 40%–60% of C storage in organo-mineral fractions — a pool that is relatively sensitive to environmental disturbance. Differences in these C pools suggest that rates of C accumulation and retention differ by vegetation type, which could have implications for predicting future soil C pool storage.