skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: X-ray chemical imaging for assessing redox microsites within soils and sediments
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 FeIIand FeIIIspecies 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.  more » « less
Award ID(s):
1952802
PAR ID:
10541440
Author(s) / Creator(s):
; ; ; ; ; ; ;
Publisher / Repository:
Frontiers
Date Published:
Journal Name:
Frontiers in Environmental Chemistry
Volume:
5
ISSN:
2673-4486
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; (, Biogeosciences)
    null (Ed.)
    Abstract. The strong phosphorus (P) sorption capacity of iron (Fe)and aluminum (Al) minerals in highly weathered, acidic soils of humidtropical forests is generally assumed to be an important driver of Plimitation to plants and microbial activity in these ecosystems. Humidtropical forest soils often experience fluctuating redox conditions thatreduce Fe and raise pH. It is commonly thought that Fe reduction generallydecreases the capacity and strength of P sorption. Here we examined theeffects of 14 d oxic and anoxic incubations on soil P sorption dynamics inhumid tropical forest soils from Puerto Rico. Contrary to the conventionalbelief, soil P sorption capacity did not decrease under anoxic conditions,suggesting that soil minerals remain strong P sinks even under reducingconditions. Sorption of P occurred very rapidly in these soils, with atleast 60 % of the added P disappearing from the solution within 6 h.Estimated P sorption capacities were much higher, often by an order ofmagnitude, than the soil total P contents. However, the strength of Psorption under reducing conditions was weaker, as indicated by the increasedsolubility of sorbed P in NaHCO3 solution. Our results show that highlyweathered soil minerals can retain P even under anoxic conditions, where itmight otherwise be susceptible to leaching. Anoxic events can alsopotentially increase P bioavailability by decreasing the strength, ratherthan the capacity, of P sorption. These results improve our understanding ofthe redox effects on biogeochemical cycling in tropical forests. 
    more » « less
  2. ; ; ; (, Proceedings of the National Academy of Sciences)
    This study investigates mechanisms that generate regularly spaced iron-rich bands in upland soils. These striking features appear in soils worldwide, but beyond a generalized association with changing redox, their genesis is yet to be explained. Upland soils exhibit significant redox fluctuations driven by rainfall, groundwater changes, or irrigation. Pattern formation in such systems provides an opportunity to investigate the temporal aspects of spatial self-organization, which have been heretofore understudied. By comparing multiple alternative mechanisms, we found that regular iron banding in upland soils is explained by coupling two sets of scale-dependent feedbacks, the general principle of Turing morphogenesis. First, clay dispersion and coagulation in iron redox fluctuations amplify soil Fe(III) aggregation and crystal growth to a level that negatively affects root growth. Second, the activation of this negative root response to highly crystalline Fe(III) leads to the formation of rhythmic iron bands. In forming iron bands, environmental variability plays a critical role. It creates alternating anoxic and oxic conditions for required pattern-forming processes to occur in distinctly separated times and determines durations of anoxic and oxic episodes, thereby controlling relative rates of processes accompanying oxidation and reduction reactions. As Turing morphogenesis requires ratios of certain process rates to be within a specific range, environmental variability thus modifies the likelihood that pattern formation will occur. Projected changes of climatic regime could significantly alter many spatially self-organized systems, as well as the ecological functioning associated with the striking patterns they present. This temporal dimension of pattern formation merits close attention in the future. 
    more » « less
  3. ; ; ; ; (, Ecology)
    Abstract Humid tropical forests are among the most productive ecosystems globally, yet they often occur on soils with high phosphorus (P) sorption capacity, lowering P availability to biota. Short‐term anoxic events are thought to release sorbed P and enhance its acquisition by soil microbes. However, the actual effects of anoxic conditions on microbial P acquisition in humid tropical forest soils are surprisingly poorly studied. We used laboratory incubations of bulk soils, NanoSIMS analysis of single microbial cells, and landscape‐scale measurements in the Luquillo Experimental Forest (LEF), Puerto Rico to test the hypothesis that anoxic conditions increase microbial P acquisition in humid tropical forests. In laboratory and field experiments, we found that microbial P uptake generally decreased under anoxic conditions, leading to high microbial carbon (C) to P ratios in anoxic soils. The decreased P acquisition under anoxic conditions was correlated with lower microbial C use efficiency (CUE), an index of microbial energy transfer in ecosystems. Phosphorus amendments to anoxic soils led to increased microbial P uptake and higher CUE suggesting that microbes were less able to access and utilize P under natural low redox conditions. Under oxic conditions, microbial C:P ratios and CUE did not respond to changes in substrate stoichiometry. These results challenge the existing paradigm by showing that anoxic conditions can decrease microbial P uptake and ultimately constrain microbial CUE. Our findings indicate that soil redox conditions tightly couple soil P and C cycles and advance our understanding of controls on P cycling in humid tropical forest ecosystems. 
    more » « less
  4. ; ; ; ; ; ; ; ; ; (, Palaeogeography, Palaeoclimatology, Palaeoecology)
    It is clear from modern analogue studies that O2-deficient conditions favor preservation of organic matter (OM) in fine-grained sedimentary rocks (black shales). It is also clear that appreciable productivity and OM flux to the sediment are required to establish and maintain these conditions. However, debates regarding redox controls on OM accumulation in black shales have mainly focused on oxic versus anoxic conditions, and the implications of different anoxic redox states remain unexplored. Here, we present detailed multi-proxy sedimentary geochemical studies of major Paleozoic and Mesozoic North American black shale units to elucidate their depositional redox conditions. This is the first broad-scale study to use a consistent geochemical methodology and to incorporate data from Fe-speciation – presently the only redox proxy able to clearly distinguish anoxic depositional conditions as ferruginous (H2S-limited) or euxinic (H2S-replete, Fe-limited). These data are coupled with total organic carbon (TOC), programmed pyrolysis, and redox-sensitive trace element proxies, with almost all measurements analyzed using the same geochemical methodology. Consistent with expectations based on previous geochemical and paleontological/ichnological studies, these analyses demonstrate that the study units were almost exclusively deposited under anoxic bottom waters. These analyses also demonstrate that there is wide variance in the prevalence of euxinic versus ferruginous conditions, with many North American black shale units deposited under predominantly ferruginous or oscillatory conditions. TOC is significantly higher under euxinic bottom waters in analyses of both preserved (present day) TOC and reconstructed initial TOC values, although sediments deposited under both redox states do have economically viable TOC content. While this correlation does not reveal the mechanism behind higher organic enrichment in euxinic environments, which may be different in different basins, it does open new research avenues regarding resource exploration and the biogeochemistry of ancient reducing environments. 
    more » « less
  5. ; ; (, Biogeochemistry)
    Abstract Soil microbial communities play a pivotal role in controlling soil carbon cycling and its climate feedback. Accurately predicting microbial respiration in soils has been challenged by the intricate resource heterogeneity of soil systems. This makes it difficult to formulate mathematical expressions for carbon fluxes at the soil bulk scale which are fundamental for soil carbon models. Recent advances in characterizing and modeling soil heterogeneity are promising. Yet they have been independent of soil structure characterizations, hence increasing the number of empirical parameters needed to model microbial processes. Soil structure, intended as the aggregate and pore size distributions, is, in fact, a key contributor to soil organization and heterogeneity and is related to the presence of microsites and associated environmental conditions in which microbial communities are active. In this study, we present a theoretical framework that accounts for the effects of microsites heterogeneity on microbial activity by explicitly linking heterogeneity to the distribution of aggregate sizes and their resources. From the soil aggregate size distribution, we derive a mathematical expression for heterotrophic respiration that accounts for soil biogeochemical heterogeneity through measurable biophysical parameters. The expression readily illustrates how various soil heterogeneity scenarios impact respiration rates. In particular, we compare heterogeneous with homogeneous scenarios for the same total carbon substrate and microbial biomass and identify the conditions under which respiration in heterogeneous soils (soils having non-uniform distribution of carbon substrate and microbial biomass carbon across different aggregate size classes) differs from homogeneous soils (soils having uniform distribution of carbon substrate and microbial biomass carbon across different aggregate size classes). The proposed framework may allow a simplified representation of dynamic microbial processes in soil carbon models across different land uses and land covers, key factors affecting soil structure. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email