skip to main content


Title: What do relationships between extractable metals and soil organic carbon concentrations mean?
Abstract

Aluminum (Al)‐bearing and iron (Fe)‐bearing minerals, especially short‐range‐ordered (SRO) phases, are thought to protect soil organic C (SOC). However, it remains methodologically challenging to assess the influence of Al vs. Fe minerals or metal complexes. Whereas SRO Al and Fe phases share some properties, Al dissolved by oxalate (Alox) often correlates stronger with SOC than Fe dissolved by oxalate (Feox) or citrate–dithionite (Fecd). To further evaluate these relationships, we analyzed a large North American soil dataset from the National Ecological Observatory Network. A strong relationship between Aloxand SOC (and weaker Feox‐SOC relationship) persisted even after excluding soils rich in SRO minerals (Andisols and Spodosols). Al dissolved by oxalate was strongly correlated with citrate–dithionite‐extractable Al (Alcd; slope = 0.92,R2 = .69), and discrepancies could be explained (R2 = .87) by greater dissolution of Al‐substituted Fe phases by citrate–dithionite and greater dissolution of aluminosilicates by oxalate. Aluminum dissolved by oxalate and Alcdwere both strong SOC predictors despite their differing relationships with silicon (Si). Al dissolved by oxalate and Sioxstrongly covaried (R2 = .79), but Alcdwas inconsistently related to Sicd(R2 = .18). Similar relationships of Aloxand Alcdwith SOC, despite differences in minerals extracted by oxalate and citrate–dithionite, suggest that Al‐OC complexes (as opposed to aluminosilicate or iron‐bearing minerals) were the best SOC predictor. This raises important questions: do Al‐OC complexes indicate protection from decomposition or simply reflect greater intensity of mineral weathering by organic acids; and, if the latter, then perhaps SOC input is driving Aloxand SOC correlations rather than Al phase composition or abundance.

 
more » « less
Award ID(s):
1802745
NSF-PAR ID:
10366856
Author(s) / Creator(s):
 ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Soil Science Society of America Journal
Volume:
86
Issue:
2
ISSN:
0361-5995
Page Range / eLocation ID:
p. 195-208
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Previous studies found conflicting results on the importance of temperature and precipitation versus geochemical variables for predicting soil organic carbon (SOC) concentrations and trends with depth, and most utilized linear statistical models. To reconcile the controversy, we used data from 2574 mineral horizons from 675 pits from National Ecological Observatory Network sites across North America, typically collected to 1 m depth. Climate was a fundamental predictor of SOC and played similarly important roles as some geochemical predictors. Yet, this only emerged in the generalized additive mixed model and random forest model and was obscured in the linear mixed model. Relationships between water availability and SOC were strongest in very dry ecosystems and SOC increased most strongly at mean annual temperature < 0°C. In all models, depth, oxalate‐extractable Al (Alox), pH, and exchangeable calcium plus exchangeable magnesium were important while silt + clay, oxalate‐extractable Fe (Feox), and vegetation type were weaker predictors. Climate and pH were independently related to SOC and also interacted with geochemical composition: Feoxand Aloxrelated more strongly to SOC in wet or cold climates. Most predictors had nonlinear threshold relationships with SOC, and a saturating response to increasing reactive metals indicates soils where SOC might be limited by C inputs. We observed a mostly constant relative importance of geochemical and climate predictors of SOC with increasing depth, challenging previous statements. Overall, our findings challenge the notion that climate is redundant after accounting for geochemistry and demonstrate that considering their nonlinearities and interactions improves spatial predictions of SOC.

     
    more » « less
  2. Iron (Fe) is ubiquitous in nature and found as Fe II or Fe III in minerals or as dissolved ions Fe 2+ or Fe 3+ in aqueous systems. The interactions of soluble Fe have important implications for fresh water and marine biogeochemical cycles, which have impacts on global terrestrial and atmospheric environments. Upon dissolution of Fe III into natural aquatic systems, organic carboxylic acids efficiently chelate Fe III to form [Fe III –carboxylate] 2+ complexes that undergo a wide range of photochemistry-induced radical reactions. The chemical composition and photochemical transformations of these mixtures are largely unknown, making it challenging to estimate their environmental impact. To investigate the photochemical process of Fe III –carboxylates at the molecular level, we conduct a comprehensive experimental study employing UV-visible spectroscopy, liquid chromatography coupled to photodiode array and high-resolution mass spectrometry detection, and oil immersion flow microscopy. In this study, aqueous solutions of Fe III –citrate were photolyzed under 365 nm light in an experimental setup with an apparent quantum yield of ( φ ) ∼0.02, followed by chemical analyses of reacted mixtures withdrawn at increment time intervals of the experiment. The apparent photochemical reaction kinetics of Fe 3+ –citrates (aq) were expressed as two generalized consecutive reactions of with the experimental rate constants of j 1 ∼ 0.12 min −1 and j 2 ∼ 0.05 min −1 , respectively. Molecular characterization results indicate that R and I consist of both water-soluble organic and Fe–organic species, while P compounds are a mixture of water-soluble and colloidal materials. The latter were identified as Fe–carbonaceous colloids formed at long photolysis times. The carbonaceous content of these colloids was identified as unsaturated organic species with low oxygen content and carbon with a reduced oxidation state, indicative of their plausible radical recombination mechanism under oxygen-deprived conditions typical for the extensively photolyzed mixtures. Based on the molecular characterization results, we discuss the comprehensive reaction mechanism of Fe III –citrate photochemistry and report on the formation of previously unexplored colloidal reaction products, which may contribute to atmospheric and terrestrial light-absorbing materials in aquatic environments. 
    more » « less
  3. Abstract

    The 2018, subaerial eruption of Kīlauea volcano, Hawaii, resulted in a 5‐km‐long stretch of coastline that actively drained lava into the ocean. Nutrients were added to the surrounding ocean through the dissolution of basaltic rock and thermal upwelling of deep water, thereby fueling a large phytoplankton bloom. Lava‐impacted, surface seawater had high suspended particle loads, and concentrations of chlorophyll, silicic acid, phosphate (Pi), nitrate, and iron that were elevated up to 12, 36, 5, 960, and 1,400 times, respectively, above the background oligotrophic levels. Widespread precipitation of iron oxyhydroxides (Feox) led to extensive scavenging of the dissolved Pipool, similar to what occurs along mid‐ocean ridge hydrothermal systems. This scavenging transformed a “fertilization” event into a Pisink near the coast of the ocean entry; however, nutrient data from outside the bloom suggest that Picould also desorb from the Feoxas it is dispersed into the open ocean. From lava quench experiments, we estimate that the hydration state of the Feoxprecipitate (H2O/Fe) was 5.2–5.7, and that the equilibrium partition coefficient of Piinto Feox(solid/liquid) was 106. In addition,33Piradiotracer incubations were used to differentiate between biotic and abiotic uptake of Piat Kīlauea's ocean entry. These findings are important for understanding modern‐day volcanic fertilization events, modeling nutrient dynamics during major events in Earth history (such as oxygenation of the atmosphere and the formation of large igneous provinces), and predicting the marine response to greater continental weathering in a warming climate.

     
    more » « less
  4. Abstract

    The transition between blueschist and eclogite plays an important role in subduction zones via dehydration and densification processes in descending oceanic slabs. There are a number of previous petrological studies describing potential mineral reactions taking place at the transition. An experimental determination of such reactions could help constrain the pressure–temperature conditions of the transition as well as the processes of dehydration. However, previous experimental contributions have focused on the stability of spontaneously formed hydrous minerals in basaltic compositions rather than on reactions among already formed blueschist facies minerals. Therefore, this study conducted three groups of experiments to explore the metamorphic reactions among blueschist facies minerals at conditions corresponding to warm subduction, where faster reaction rates are possible on the time scale of laboratory experiments. The first group of experiments was to establish experimental reversals of the reaction glaucophane+paragonite to jadeite+pyrope+quartz+H2O over the range of 2.2–3.5 GPa and 650–820°C. This reaction has long been treated as key to the blueschist–eclogite transition. However, only the growth of glaucophane+paragonite was observed at the intersectional stability field of both paragonite and jadeite+quartz, confirming thermodynamic calculations that the reaction is not stable in the system Na2O–MgO–Al2O3–SiO2–H2O. The second set of experiments involved unreversed experiments using glaucophane+zoisite ±quartz in low‐Fe and Ca‐rich systems and were run at 1.8–2.4 GPa and 600–780°C. These produced omphacite+paragonite/kyanite+H2O accompanied by compositional shifts in the sodium amphibole, glaucophane, towards sodium–calcium amphiboles such as winchite (☐(CaNa)(Mg4Al)Si8O22(OH)2) and barroisite (☐(CaNa)(Mg3Al2)(AlSi7)O22(OH)2). This suggests that a two‐step dehydration occurs, first involving the breakdown of glaucophane+zoisite towards a paragonite‐bearing assemblage, then the breakdown of paragonite to release H2O. It also indicates that sodium–calcium amphibole can coexist with eclogite phases, thereby extending the thermal stability of amphibole to greater subduction zone depths. The third set of experiments was an experimental investigation at 2.0–2.4 GPa and 630–850°C involving a high‐Fe (Fe#=Fetotal/(Fetotal+Mg)≈0.36) natural glaucophane, synthetic paragonite and their eclogite‐forming reaction products. The results indicated that garnet and omphacite grew over most of these pressure–temperature conditions, which demonstrates the importance of Fe‐rich glaucophane in forming the key eclogite assemblage of garnet+omphacite, even under warm subduction zone conditions. Based on the experiments of this study, reaction between glaucophane+zoisite is instrumental in controlling dehydration processes at the blueschist–eclogite transition during warm subduction.

     
    more » « less
  5. Abstract

    We present ab initio (LDA + Usc) studies of high‐temperature and high‐pressure elastic properties of pure as well as iron‐bearing (ferrous, Fe2+, and ferric, Fe3+) and aluminum‐bearing MgSiO3postperovskite, the likely dominant phase in the deep lower mantle of the Earth. Thermal effects are addressed within the quasiharmonic approximation by combining vibrational density of states and static elastic coefficients. Aggregate elastic moduli and sound velocities for the Mg end members are successfully compared with scarce experimental data available. Effects of iron (Fe) and aluminum (Al) substitutions on elastic properties and their pressure and temperature dependence have been thoroughly investigated. At the observed perovskite to postperovskite transition (P = 125 GPa andT = 2,500 K), compressional and shear velocities increase by 0–1% and 1.5–3.75%, respectively. This observation is consistent with some seismic studies of the Ddiscontinuity beneath the Caribbean, which suggests that our robust estimates of elastic properties of the postperovskite phase will be very helpful to understand lateral velocity variations in the deep lower mantle region and to constrain its composition and thermal structure.

     
    more » « less