Spatial associations and chemical composition of organic carbon

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Spatial associations and chemical composition of organic carbon sequestered in Fe, Ca, and organic carbon ternary systems Tyler Sowers, Dinesh Adhikari, Jian Wang, Yu Yang, and Donald L. Sparks Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.8b01158 • Publication Date (Web): 17 May 2018 Downloaded from http://pubs.acs.org on May 17, 2018

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Spatial associations and chemical composition of organic carbon sequestered in Fe, Ca, and

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organic carbon ternary systems

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Tyler D. Sowersa*, Dinesh Adhikarib, Jian Wangc, Yu Yangb, and Donald L. Sparksa

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a

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Delaware, Newark, Delaware, 19716, USA.

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b

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89557 USA.

Department of Plant and Soil Sciences, Delaware Environmental Institute, University of

Department of Civil and Environmental Engineering, University of Nevada, Reno, Nevada,

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c

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Canada

Canadian Light Source Inc., University of Saskatchewan, Saskatoon, Saskatchewan S7N 2V3,

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*Corresponding author - Delaware Environmental Institute, ISE Lab, 221 Academy Street,

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Room 465, University of Delaware, Newark, DE 19716; (252)-241-3374; [email protected]

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Abstract Figure

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Abstract

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Organo-mineral associations of organic carbon (OC) with iron (Fe) oxides play a major

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role in environmental OC sequestration, a process crucial to mitigating climate change. Calcium

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has been found to have high co-association with OC in soils containing high Fe content, increase

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OC sorption extent to poorly-crystalline Fe oxides, and has long been suspected to form bridging

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complexes with Fe and OC. Due to the growing realization that Ca may be an important

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component of C cycling, we launched a scanning transmission X-ray microscopy (STXM)

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investigation, paired with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, in

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order to spatially resolve Fe, Ca, and OC relationships and probe the effect of Ca on sorbed OC

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speciation. We performed STXM-NEXAFS analysis on 2-line ferrihydrite reacted with leaf

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litter-extractable dissolved OC and citric acid in the absence and presence of Ca. Organic carbon

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was found to highly associate with Ca (R2 = 0.91). Carboxylic acid moieties were dominantly

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sequestered; however, Ca facilitated the additional sequestration of aromatic and phenolic

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moieties. Also, C NEXAFS revealed polyvalent metal ion complexation. Our results provide

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evidence for the presence of Fe-Ca-OC ternary complexation, which has the potential to

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significantly impact how organo-mineral associations are modeled.

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Introduction Soils house the largest terrestrial surface reservoir of organic carbon (OC).1-5 Preservation

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of OC in soil systems not only enhances soil productivity, but stabilizes OC that could otherwise

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be transferred to the atmosphere as a greenhouse gas.2, 5-8 Due to the importance of OC

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preservation, considerable research probing the sequestration of OC in environmental soil

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systems has been performed in order to elucidate primary drivers and mechanisms of OC

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stability.9-12 Along with physical and freeze/thaw processes, organo-mineral associations have

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been found to be increasingly important in environmental OC sequestration.3, 13, 14 Metal oxides

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with high affinity for OC are of particular importance.

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Iron (Fe) oxides are environmentally ubiquitous in soils and possess a high sorption

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capacity for OC.10, 15-17 Poorly crystalline Fe oxide phases, such as 2-line ferrihydrite, with high

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surface area and reactivity are important drivers of OC cycling in environmental systems;16-18

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therefore, recent research involving soil organo-mineral associations has focused primarily on

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ferrihydrite and goethite (a common, but less reactive Fe oxide phase).9, 13, 14, 19-23 Research

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investigating OC sequestration to Fe oxides has identified Fe-OC adsorption and coprecipitation

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reactions as important pathways for OC sequestration (up to 200 and 230 mg OC sequestered g-1

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ferrihydrite, respectively).9, 24 Recently, powerful spectroscopy analyses have been applied to

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these systems to further explore spatial information and mechanisms of OC sequestration by

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soils and Fe oxides.25-30

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Many advanced spectroscopic techniques have been utilized in the attempt to elucidate

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OC sequestration processes; however, attenuated total reflectance-Fourier transform infrared

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spectroscopy (ATR-FTIR) and scanning transmission X-ray microscopy (STXM) paired with

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near-edge X-ray absorption spectroscopy (NEXAFS) are among the most effective. ATR-FTIR

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investigations of OC associations with Fe oxides have attributed OC sequestration to primarily

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inner-sphere ligand exchange mechanisms.19, 23, 30 STXM-NEXAFS is an increasingly popular

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technique by which OC distribution, associations with other elements, and speciation may

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readily be determined.5, 28, 29 Although this is a powerful technique that can provide both spatial

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and chemical information, limited research has been performed on OC associations with soils

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and Fe oxides.9, 25, 27-29 Chen et al. and Henneberry et al. found that carboxylic acid moieties were

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the dominant OC moiety sequestered by ferrihydrite adsorption complexes and coprecipitates

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through inner-sphere ligand exchange processes using a combination of STXM-NEXAFS and

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ATR-FTIR.9, 27 Using STXM-NEXAFS mapping, Wan et al. and Chen et al. found that soils

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containing high concentration of Fe oxides had high spatial elemental associations between C

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and Fe.25, 29 However, an unexplained high correlation between C and calcium (Ca), in the

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absence of carbonate minerals, was also observed in select soil samples.

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Calcium has long been proposed to form bridging complexes with soil OC and metal

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oxides;20, 21 however, little research exists exploring the effect of Ca on OC sequestration. Recent

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work by our group has shown that leaf-litter extractable dissolved OC sorption to 2-line

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ferrihydrite in the presence of 10 mM Ca resulted in a 20% increase in OC sorbed

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concentration.24 Similarly, batch sorption experiments have found that fulvic acid and humic acid

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sorption to iron oxide and clay minerals increased in the presence of Ca and was suspected to be

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due to ternary complex formation.20, 21, 31 Calcium has the potential to significantly impact OC

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sequestration to Fe oxides, but is in need of further advanced spectroscopic investigation.

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Therefore, we hypothesize that OC sequestration to 2-line ferrihydrite in the presence of Ca may

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promote the formation of Fe-Ca-OC ternary complexes that may be spatially resolved

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performing STXM-NEXAFS analysis. In order to address our hypothesis, we (1) determined

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spatially correlated Fe, Ca, and C relationships in samples containing ferrihydrite and natural

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dissolved organic matter (DOM) or citric acid in the presence or absence of Ca using STXM

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elemental composite maps, (2) compared C 1s NEXAFS spectra at localized clusters identified

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via principal component analysis (PCA) for complexes synthesized in the presence or absence of

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Ca, and (3) probed changes in sorbed C speciation and sorption mechanism in the presence or

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absence of Ca using C 1s NEXAFS and ATR-FTIR spectroscopy.

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Methods

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Adsorption Complex Synthesis

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Prior to STXM-NEXAFS analysis, natural DOM and citric acid were complexed to

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synthetic 2-line ferrihydrite in the absence or presence of Ca. Water-extractable DOM was made

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using methods previously discussed in Chen et al. and Sowers et al.9, 24 Leaf litter was collected

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from the organic horizon of a forest Ultisol located at the Stroud Water Research Center in

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Avondale, Pennsylvania. Collected leaf litter was then shaken (200 rpm) for 90 hours with

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deionized (DI) water (1:2 leaf litter: DI water; mass basis). The extraction was sieved (0.1 mm)

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and centrifuged (20,000 g) twice in 30 minute cycles. The collected supernatant was then filtered

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through sequentially through 0.8, 0.45, and 0.2 µm pore size polyethersulfone filters.

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The newly created DOM stock was characterized for elemental composition

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(approximately 2000 mg L-1 C; SI Table S1 & S2) and was reacted with 2-line ferrihydrite such

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that initial molar C/Fe equaled 4.7. Synthetic 2-line ferrihydrite was synthesized according to

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well-known methodology described in Schwertmann et al.17 For the Ca receiving samples, CaCl2

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(Fischer) and DOM were added concomitantly such that initial Ca concentration equaled 30 mM

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Ca. An initial molar C/Fe ratio and Ca concentration of 4.7 C/Fe and 30 mM Ca, respectively,

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were chosen based off prior experiments by the authors.24 High C/Fe molar ratios have been

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found to potentially disguise C spectroscopic features, particularly in infrared (IR) spectroscopy;9

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therefore, 2.5 and 4.7 molar C/Fe was used for all spectroscopic experiments to limit this sorbed

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concentration effect. 30 mM Ca was used for all Ca-receiving samples as this was found in the

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authors’ past work to be the maximum Ca concentration that synergistically affects OC

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sequestration to synthetic 2-line ferrihydrite.24 All reactions were set to pH 6.25 ± 0.10 using

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dilute NaOH and mixed (dark) via rotary shaker at approximately 50 rpm for 24 hours. pH 6.25

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was chosen as it was the lowest pH value we expected to observe ternary complexation, while

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also maintaining environmental applicability to an acidic soil system. Upon sorption reaction

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completion, samples were centrifuged, decanted, washed twice with DI water, and the solids

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stored moist in a freezer at -4°C until further spectroscopic analysis. The previously outlined

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procedure was repeated for the citric acid system, except citric acid was used in place of natural

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DOM.

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Scanning Transmission X-ray Microscopy STXM-NEXAFS data was collected at beamline 10ID-1 at the Canadian Light Source

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(Saskatoon, Saskatchewan) for all DOM-bearing and citric acid-bearing sample synthesized

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earlier at initial C/Fe molar ratios of 4.7. A subsample of ferrihydrite wet-paste was suspended in

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DI water such that approximately 0.5 mg of sample was suspended with 1 mL DI water.9, 25

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Approximately 3 µL of the well-mixed suspension was applied to a Si3N4 window such that the

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window was covered with suspension. Prior to analysis, the sample was allowed to air-dry for

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approximately 30 minutes and then placed on the STXM sample holder. The STXM chamber

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was pumped to rough vacuum and then backfilled with 1/6 atmosphere He for the measurements.

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A maximum spatial resolution of approximately 30 nm was achieved using a Fresnel zone plate.

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Dwell time equaled 1 ms with a pixel size of approximately 40 nm for all measurements taken.

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C 1s, Ca 2p, and Fe 2p data was obtained by raster scanning from 280 to 735 eV at

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specific regions of interest identified at low magnification (up to approximately 2500 µm2) at the

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C K-edge (288 eV). Image stacks were generated for each element across the aforementioned eV

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range and averages of these stacks at specific eV ranges were then used when processing

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collected STXM-NEXAFS data.

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Processing of STXM-NEXAFS Data All data stacks were aligned using Stack Analyze (Stony Brook, V2.7) and processed

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using the aXis2000 software package.32, 33 PCA and cluster analysis was performed using PCA

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GUI 1.1.1 software.34 After alignment and identifying I0 (incident flux), aXis2000 was used to

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convert aligned and stacked image data to optical density using the following equation: OD =

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ln(I0/I), where I is equal to the flux transmitted through the sample. Generated images up to ± 0.5

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eV of the resonance energy for each element were averaged for chemical mapping. The averaged

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images at each element’s resonance energies were subtracted with averaged images at the

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elements’ specific pre-edge range (SI Table S3) in order to obtain chemical maps.

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Optical density is correlated to element thickness (Lambert-Beer’s law) and was

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calculated for all elements analyzed (SI Table S3 and S4). Thickness estimates were made using

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methods described in Wan et al.29 and Chen et al.25 For C, the product of RE*µ*f *ρ was used to

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calculate the conversion factor for optical density to C thickness (SI Table S4). RE is a

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dimensionless resonance enhancement factor, µ (cm2 g-1) is the mass absorption coefficient

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above the C absorption edge minus the mass absorption coefficient below the C edge, f (g g-1) is

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the fraction of C in the solid phase (mass basis), and ρ (g cm-3) is the density of the solid phase

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(SI Table S4).29 f and ρ were calculated using values published in Stevenson et al.35 Scaling

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factors for Ca and Fe were taken from Chen et al.25 and used for optical density to thickness

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conversions in our study. Optical density correlations between elements were obtained by

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aligning optical density maps for each element (images averaged from the edge energy stack

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range minus corresponding images averaged from the pre-edge energy stack range, SI Table S3)

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and then comparing the maps on a per pixel basis.

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PCA and cluster analysis were performed to identify regions of statistically unique

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spectra. Three to four components were typically used when searching for significant

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components and then lowered if significant features between two components were congruent.

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An eigenimage scaling factor of 0.3 was used for all cluster analyses and singular value

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decomposition was performed when analyzing cluster spectra.

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ATR-FTIR Freeze-dried DOM and ferrihydrite samples were analyzed using a Bruker ATR-FTIR.

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Spectra were scanned from 4000 to 600 cm-1 at a spectra resolution of 2 cm-1. 2-line ferrihydrite

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spectra was subtracted from all OC-bearing ferrihydrite samples to remove contributions from

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ferrihydrite and focus on the chemical composition of the bound OC. Automatic baseline

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correction and normalization was applied to all spectra. All samples were dried and analyzed

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soon after to avoid the effects of moisture uptake on sample spectra. The OPUS Version 7.2

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spectroscopy software suite (Bruker) was used to process all collected spectra.

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Results and Discussion

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Elemental Mapping of Fe, Ca, and C All ferrihydrite samples reacted with either DOM or citric acid in the presence or absence

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of Ca were analyzed for spatial Fe, Ca, and C distribution using STXM mapping (Figure 1). For

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all STXM color-coded composite RGB maps, the presence of red, green, and blue are

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represented by C, Ca, and Fe, respectively. The intensity of the color correlates to optical density

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and represents the relative concentration of each respective element per unit area.29 Co-

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associations between C, Ca, and Fe may be identified by observing the colors produced by

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mixtures of red, green, and blue (RGB) and looking at the relative contributions of RGB values

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at regions of interest (SI Figure S1) For Figures 1A, 1C, and 1D, cyan-blue regions represent

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areas of poor transmission and were identified as too thick (optical density > 2.25);29 therefore,

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these regions were excluded from all further analyses. For Figure 1A (ferrihydrite-DOM, no Ca

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addition), the purple region represents a strong co-association of C and Fe. Similar C and Fe co-

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association was seen by Chen et al.9 for ferrihydrite-OC adsorption complexes synthesized in

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similar experimental conditions. A drastic difference in element co-association may be observed

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when ferrihydrite was reacted with DOM in the presence of Ca (Figure 1B). The purple regions

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observed in Figure 1A are mostly absent and predominately replaced by a pervasive network of

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white, grey and yellow, with hot spots of pink. The presence of white and grey regions represent

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areas at which Fe, Ca, and C are well associated, suggesting potential ternary relationships or

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homogenous distribution of C and Ca sorption sites. Yellow regions are found throughout the

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sample and indicate co-association of C and Ca. A high correlation between C and Ca has also

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been found for natural samples in similar STXM studies and will be discussed further.25, 28, 29 No

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separate C phases were observed in the DOM system, contrasting what was observed in

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Henneberry et al.27 in Fe-OM coprecipitate systems but similar to Chen et al.9

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Differences in RGB maps for citric acid reacted samples were much less marked, as

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shown in Fig. 1C and 1D. These particles possess a strong intensity of purple except the particle

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in the middle of Fig. 1C, suggesting a strong association of Fe and C. Unlike Figure 1B, no

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white, grey or, yellow regions were observed in Figure 1D; therefore, Figure 1D lacks the

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suggested Fe-Ca-C ternary associations observed in Figure 1B. Although the RGB elemental

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distribution maps allow for a qualitative analysis of Fe, Ca, C co-association, a more quantitative

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approach to identifying correlations between elements of interest may be performed by

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comparing elemental optical density.

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Optical Density Correlation Between Elements

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Spatial correlations of Fe, Ca, and C are presented in elemental optical density correlation

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plots (Figure 2). The Fe/C optical density plot for the DOM-bearing ferrihydrite sample shown in

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Figure 2A showed a strong C/Fe correlation (0.9464) and C thickness ranging up to 135 nm.

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The high correlation is congruent with C/Fe relationship Chen et al.25 observed for DOM-

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ferrihydrite adsorption complexes. Compared to C STXM analysis of soils, the observed

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maximum C thickness of our samples was approximately 100 nm less; however, this disparity is

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suspected to be due to soil C microaggregate formation.5, 29 Average C thickness was

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approximately 65 nm which is comparable to the 68 nm C thickness observed in Ultisols taken

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from oxic environments.25 DOM sorption to ferrihydrite in the presence of 30 mM Ca resulted in

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a significant decrease in C/Fe correlation (R2 = 0.6242, Figure 1B) with a concurrent strong

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correlation between C and Ca (R2 = 0.9144, Figure 1C), implying that different associations

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between Fe-C and Fe-Ca-C may exist. Ca/Fe was also found to have a strong positive correlation

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of 0.7373 (SI Figure S2A). Although the C/Fe correlation is lower in the system containing Ca,

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the optical density relationship for C/Fe, C/Ca, and Ca/Fe are positively correlated, indicating a

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high ternary association between Fe, Ca, and C. The 0.9144 correlation coefficient between C

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and Ca in Figure 1C demonstrates the potential importance of Ca content when modeling C

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cycling in environmental systems. The strong relationship between C and Ca has been observed

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in other STXM studies of natural soil samples. Phaeozem29 (naturally high in Ca) and Ultisol25

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(pasture soil receiving Ca from liming amendments) soils were found to have C/Ca optical

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density correlations of 0.767 and 0.870, respectively. Ca in both soils was also found to be well

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correlated to Fe (R2 > 0.75). With this in mind, STXM investigation of natural soils yielded

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similar results to what was seen in our ferrihydrite, Ca, and natural DOM systems; therefore, our

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results may be applicable to soil systems containing Fe oxides and Ca when investigating soil C

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cycling. Another interesting phenomenon is the decrease in C/Fe correlation by approximately a

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third when Ca and DOM were concurrently added to a ferrihydrite suspension. High correlation

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between C and Ca relative to the significant decrease in C/Fe correlation suggests that C is more

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closely associated with Ca in ternary systems containing Fe, Ca, and C, potentially signifying

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that Ca is important to the complexation of C to Fe as a bridging element.

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Calcium had a large effect on the optical density correlation plots in the DOM system;

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however, the effect of Ca on the citric acid system was observed to be less significant. The C/Fe

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optical density plot for citric acid-bearing ferrihydrite (Figure 2D) was found to have a low

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correlation between C and Fe. The poor correlation between C and Fe in this system is most

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likely attributable to poor transmission due to sample thickness throughout a large portion of

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citric acid-ferrihydrite STXM map. Sample thickness was not a major issue for the citric acid-

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bearing ferrihydrite sample reacted in the presence of Ca (Figure 2E, F). A strong correlation

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coefficient of 0.7636 was found between C and Fe, suggesting a strong relationship between C

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and Fe. This is expected to be the case as citric acid is a tricarboxylic acid that is known to form

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inner sphere complexes with iron oxides.13, 19 Unlike the DOM system in Figure 2C, Figure 2F

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shows a much lower correlation between C and Ca in the citric acid system. From this

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observation, it may be suggested that citric acid is less associated with Ca than natural DOM.

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This may be due to the heterogeneity of OC functional moieties in the DOM solution versus the

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singular carboxylic species present in citric acid (tricarboxylic acid). Interestingly, Ca is highly

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associated with Fe in the citric acid system (SI Figure S1B) compared to the DOM system. C/Ca

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and Ca/Fe correlations in the citric acid system, in conjunction with the analysis of Figure 1D,

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are likely best explained by both Ca and C being sorbed separately to the ferrihydrite surface

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such that Ca and C are not highly associated.

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Identifying the Speciation and Spatial Heterogeneity of C in Fh-Ca-OC Complexes

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C K-edge STXM-NEXAFS of DOM. STXM-NEXAFS analysis was used to spatially investigate

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the chemical speciation of sequestered OC to ferrihydrite in the absence and presence of Ca

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(Figure 3 and 4, respectively). Optical density of the averaged stack images (Figures 3A and 4A)

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increase with the intensity of white and decreases with the degree of black. The pre-edge

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averaged image was subtracted from the averaged stack image on the C K-edge in order to focus

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on areas representing sequestered C and to identify areas affected by sample thickness (Figure

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3B and 4B). Principal component analysis (PCA) was used to identify unique clusters of pixels

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within each STXM stack that represent regions of statistically different C 1s NEXAFS spectra

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(Figure 3C and 4C).34 The red cluster in Figure 3C is a region identified as having poor sample

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transmission and was excluded from the analysis; however, all regions in Figure 4C were found

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to be of appropriate thickness. Corresponding C 1s NEXAFS for the whole sample, all clusters

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of interest identified through PCA, and a DOM standard were collected (Figures 3D and 4D).

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Resonance energies taken from the C 1s NEXAFS data may be used to identify functional

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groups present in the sample (Table 1) which was then used to characterize OC species present

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for all samples tested.25, 27-29, 36, 37

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For the DOM-bearing ferrihydrite sample reacted in the absence of Ca, three unique

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clusters were observed from the PCA (Figure 3C and 3D). Cluster 1 (yellow) was found to be the

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most predominant within the DOM-ferrihydrite adsorption complex and corresponded well to the

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spectra of the whole sample. Both of the spectra are dominated by a peak at 288.5 eV

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representing carboxylic C.5, 28, 29 Compared to the DOM standard, the carboxylic peak for the

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whole sample and cluster 1 spectra is diminished and significantly broader. This feature is

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indicative of carboxylate complexation to Fe oxide, likely through ligand exchange processes.25,

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37

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aromatic and phenolic C functional moieties. These features are severely diminished compared

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to the DOM standard, suggesting that aromatic and phenolic groups in the DOM are not

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preferentially sequestered to ferrihydrite.26, 29 Cluster 2 (green) and 3 (purple) were found at the

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edge of the particle and were found to have sharper peaks at 288.5 eV than those observed for

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the whole sample and Cluster 1. The strong, thin peak at resonance energy 288.5 eV suggests

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that carboxylic C is still the most predominant resonance feature but is largely representative of

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the DOM standard and thus may not be as strongly complexed to ferrihydrite compared to the

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Cluster 1 region.5, 25 For Cluster 2 and 3, the phenolic peak at approximately 286.8 eV was

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heightened, indicating that there may be localized areas on ferrihydrite that preferentially

Slight features at 285.6 eV and 286.7 eV were also observed, representing the presence of

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sequester phenolic C from DOM. Aromatic groups for both Cluster 2 and 3 were found to be

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comparable to the whole sample spectra and Cluster 1.

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Carbon 1s NEXAFS spectra collected for ferrihydrite-Ca-DOM (Figure 4D) were found

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to have predominant dissimilarities to the spectra from the ferrihydrite-DOM system (Figure

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3D). Compared to Figure 3D, the most predominant feature change promoted by the presence of

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Ca was the extreme diminishment of the carboxylic C peak at 288.5 eV (~30% decrease in

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relative peak area compared to the DOM standard) and the emergence of a shoulder at 287.3-

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287.6 eV. This feature was observed for all cluster spectra shown in Figure 4D. Plaschke et al.37

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and Armbruster et al.36 saw congruent features in C 1s NEXAFS spectra of humic sorption to

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various polyvalent metal ions. Polyvalent metal ion complexation with humic acid resulted in a

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decrease in the carboxylic C resonance intensity with concomitant emergence of a shoulder

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approximately 1 eV below the carboxylic peak.36, 37 The sharp decrease in our sample spectra in

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Figure 4D with the emergence of the aforementioned shoulder strongly suggests that Ca is may

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be interacting with DOM carboxylic C groups. The absence of shoulder formation at 287.3-287.6

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eV and the high intensity carboxylic C resonance energy at 288.5 eV in Figure 3D suggests that

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the ferrihydrite-Ca-DOM system is uniquely binding carboxylic C compared to the relatively

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simpler spectra observed for the ferrihydrite-DOM system; therefore, the feature changes at

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288.5 eV and 287.3-287.6 eV are suggestive that the presence of Ca affects the binding of DOM

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to ferrihydrite. We expect this feature would be promoted further for ferrihydrite-Ca-DOM

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samples synthesized at increasing pH, which will be analyzed further in future research.

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Resonance energies representative of aromatic C (285.3-285.6 eV) in the ferrihydrite-Ca-

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DOM system (Figure 4D) are also found to significantly differ from the ferrihydrite-DOM

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system (Figure 3D). All clusters in Figure 4D show a higher intensity, developed aromatic peak

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at 285.6 eV compared to Figure 3D. Chen et al.9 inferred that increases in aromatic C peak

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intensity is associated with increased aromatic C complexation to ferrihydrite complexes;

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therefore, the spectra suggest that the Ca-containing system may be facilitating increased

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association of aromatic C to ferrihydrite. Phenolic groups were also identified in the sample

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spectra at 286.7-286.9 eV; however, there were no noticeable differences between Figure 3D and

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4D.

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Although all ferrihydrite-Ca-DOM C 1s NEXAFS spectra in Figure 4D were found to

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have similar peak locations/features, Cluster 2Ca (green) was found to possess the most

350

distinguishable features. This region represents a large continuous region on the ferrihydrite

351

particle shown in Figure 4C. A clear shoulder can be observed at approximately 287.3 eV, along

352

with the diminishment of the carboxylic C peak at 288.5 eV. Also, a distinct, relatively high

353

intensity aromatic peak at 285.6 eV was observed. In conjunction with this unique spectra, the

354

Cluster 2Ca region was also observed in Figure 1B. High intensity optical density contributions

355

from C (red), Ca (green), and Fe (blue) were observed in almost equal proportions from the same

356

region represented by Cluster 2Ca in Figure 4C, resulting in this region appearing white. Due to

357

the presence of unique C NEXAFS features that differ greatly from the system receiving no Ca

358

inputs and the high degree of association between Fe, Ca, and C observed in Figure 1B, Cluster

359

2Ca is expected to be a region of Fe-Ca-C ternary complexation, potentially through Ca-bridging

360

structures.

361 362

C K-edge STXM-NEXAFS Analysis of Citric Acid. PCA revealed only one unique cluster shown

363

in yellow for the ferrihydrite-citric acid (SI Figure S3A) and red for the ferrihydrite-Ca-citric

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364

acid. The contrasting color (red and yellow, respectively) represent regions that were identified

365

as too thick for further analysis. Ferrihydrite-citric acid and ferrihydrite-Ca-citric acid spectra (SI

366

359 Figure S3C) were found to have similar features. Both spectra were dominated by a broad

367

carboxylic C peak at 288.5 eV with no other significant features. The broad carboxylic C peak

368

for both samples suggest that both citric acid-treated samples are complexing strongly to

369

ferrihydrite, similar to the feature seen for the ferrihydrite-DOM spectra (SI Figure S3C). No

370

major differences in the C 1s NEXAFS spectra were observed when citric acid was reacted with

371

ferrihydrite in the presence of Ca; therefore, we expect that Ca has little to no effect on the

372

complexation of OC derived from citric acid.

373 374

ATR-FTIR. In conjunction with C 1s NEXAFS, ATR-FTIR data was collected for ferrihydrite

375

samples reacted with DOM or citric acid in the absence or presence of Ca in order to probe C

376

speciation and mechanism of sorption (Figure 5). In addition to the molar C/Fe ratio used for

377

STXM samples (4.7 C/Fe), a lower molar ratio of 2.5 C/Fe was also tested in order to probe

378

features that otherwise would be undistinguishable.9 An absorbance band at 1585 cm-1 was

379

observed for the DOM stock and for 2.5 C/Fe DOM_ 30 mM Ca, with every other sample,

380

except, having a band at approximately 1570 cm-1. Absorbance band formation from 1585 to

381

1570 cm-1 is associated with the presence of asymmetric carboxyl C groups (SI Table S6). All

382

bands, excluding 2.5 C/Fe DOM_ 30 mM Ca, were found to shift from 1585 to 1570 cm-1 and

383

have decreased intensity compared to the DOM standard. The shift and depression of the

384

asymmetric carboxyl C band suggests that asymmetric carboxyl C may be strongly bound to

385

ferrihydrite.9, 19, 23 In conjunction with the asymmetric carboxyl C band, a symmetric carboxyl

386

band may be found from 1400 to 1380 cm-1 for all samples. The DOM standard has a high

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387

intensity absorbance band at 1400 cm-1, but all other C-reacted ferrihydrite samples were found

388

to shift to 1384 or 1380 cm-1. Shifting of the symmetric carboxyl C group from 1400 to 1384 cm-

389

1

390

processes,9, 19, 30 suggesting that ligand exchange of OC to ferrihydrite through symmetric

391

carboxyl C groups is a predominant mechanism of sorption for both citric acid and DOM

392

samples.

is a well-documented characteristic of OC sorption to ferrihydrite through ligand exchange

393

Interestingly, the 2.5 C/Fe DOM_ 30 mM Ca was found to have different absorbance

394

band features compared to all other samples. The asymmetric carboxyl C band was significantly

395

decreased similar to other samples but did not shift from 1585 to 1570 cm-1. The decreased

396

intensity of this peak compared to the DOM stock suggests that asymmetric carboxyl C is

397

associating with ferrihydrite in sample 2.5 C/Fe DOM_ 30 mM Ca; however, the lack of a shift

398

suggests that asymmetric carboxyl C is binding weakly to ferrihydrite in this system.10, 23 Also,

399

the symmetric carboxyl C peak was found to shift to 1380 cm-1 rather than 1384 cm-1 and had a

400

higher peak intensity compared to sample 2.5 C/Fe DOM_No Ca. The increased shift and

401

intensity of the symmetric carboxyl C band for 2.5 C/Fe DOM_30 mM Ca compared to 2.5 C/Fe

402

DOM_No Ca suggests that Ca is playing a role in the binding of symmetric carboxyl C, likely

403

through ligand exchange processes.23, 30 Changes in aromatic and phenolic absorbance bands

404

were indistinguishable from the collected ATR-FTIR spectra, likely due to the strong absorbance

405

bands of carboxyl C. Polysaccharide peaks (SI Table S6) were also observed in spectra for the

406

DOM systems, indicating the presence of sequestered DOM polysaccharide functional groups,23,

407

38

but to a lesser degree compared to carboxyl C functional groups.

408 409

Ca L-edge STXM-NEXAFS Analysis

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410

Ca 2p NEXAFS spectra were collected for both ferrihydrite-Ca-DOM and ferrihydrite-Ca-citric

411

acid samples. For both, PCA revealed only one unique spectra (SI Figure S4). Four Ca

412

reference spectra were used: Ca-bearing ferrihydrite, sorbed Ca to extracellular polymeric

413

substance (EPS), CaCl2, and calcite.25, 39 For both DOM and citric samples, four total peaks were

414

observed. L3 2P3/2 and L2 2P1/2 peaks were observed at 349.2 and 352.6 eV, respectively. These

415

two major peaks are characteristic of Ca spin-orbital partners found in Ca L-edge NEXAFS.40 A

416

smaller peak precedes each previously mentioned larger peak at 348.2 and 351.4, respectively,

417

and gives an indication of the crystallinity of present Ca structures.41

418

When comparing both ferrihydrite-Ca-DOM (Fh_Ca_DOM) and ferrihydrite-Ca-citric

419

acid (Fh_Ca_Citric Acid) Ca 2p NEXAFS spectra to reference spectra (SI Figure S4), both

420

samples corresponded poorly to calcite and CaCl2 and well to the Ca-bearing ferrihydrite

421

(Fh_Ca) and Ca-containing organic compound (Sorbed Ca_EPS). The calcite spectra poorly

422

agrees with our samples and CaCl2 was found to have higher intensity peaks at the two small L3

423

2P3/2 and L2 2P1/2 with all four peaks shifted to a slightly lower eV (349.2 and 352.4 eV for the

424

two major peaks at (ii) and (iv); 348 and 351.3 eV for two smaller peaks at (i) and (iii) (SI Figure

425

S4)) characteristic of Ca L-edge NEXAFS for CaCl2.42 Therefore, we conclude that present Ca

426

species are not present in the form of calcite nor CaCl2. The Sorbed Ca_EPS and Fh _Ca

427

reference standards were found to correspond well to our samples, mostly due to similar nature

428

of the low intensity L3 2P3/2 and L2 2P1/2 peaks at 348.2 and 351.4 eV, respectively. This

429

suggests that Ca incorporated into ferrihydrite-Ca-OC samples are of poorly crystalline or

430

amorphous nature.41 Fh_Ca was observed to have higher peak intensity at the L3 2P3/2 (349.2 eV)

431

and L2 2P1/2 (352.6 eV) peaks compared to the sample spectra, especially for the Fh_Ca_DOM

432

sample, suggesting that the concurrent presence of ferrihydrite and DOM may have a unique

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433

impact on the coordination of Ca; however, the role of Ca as a bridging cation needs to further

434

explored in future spectroscopic analysis.

435 436 437

Evidence for Fe-Ca-OC Ternary Complex Formation Through a combination of spatial associations and C speciation spectra obtained

438

primarily via STXM-NEXAFS, we have investigated potential ternary interactions of Fe, Ca, and

439

OC in systems containing ferrihydrite, Ca, and either DOM or citric acid. Batch sorption data

440

from our past work (SI Figure S5 and S6)24 were paired with ATR-IR and STXM-NEXAFS

441

analysis in order to extensively probe the occurrence and chemical speciation of Fe-Ca-OC

442

ternary complexes. Evenly-proportioned mixtures of C, Ca, and Fe in color-coded RGB maps,

443

high correlation (R2 = 0.91) between C and Ca in optical density correlation plots, and the

444

polyvalent metal ion complexation C 1s NEXAFS feature (decrease of the carboxyl C peak at

445

288.5 eV paired with the emergence of a shoulder at 287.5 eV) all provide significant evidence

446

that Fe-Ca-OC complexes are forming in systems containing ferrihydrite, Ca, and natural DOM,

447

likely through cation-bridging of carboxylic C to the ferrihydrite surface. Also, Ca has recently

448

been shown by the authors to synergistically influence OC sequestration to ferrihydrite,

449

providing further evidence of Fe-Ca-OC ternary complex formation24. Additionally, for the

450

DOM system, the optical density correlation of the C/Fe plot was found to decrease from R2 =

451

0.95 to R2 =0.62 when Ca was added, along with high C/Ca and Ca/Fe correlation (R2 = 0.91 and

452

0.74, respectively). This indicates that Ca is well associated to both C and Fe whereas C is

453

significantly more associated with Ca than Fe; therefore, we suggest that Ca is significantly

454

involved in the complexation of C to Fe, most likely through Ca-bridging structures. ATR-IR

455

data supports this conclusion, as features indicative of ligand exchange of symmetric carboxyl C

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456

were observed and enhanced with the addition of Ca. These findings relate well to the work of

457

others that have observed high correlation of C, Ca, and Fe in iron oxide and soil systems.9, 20, 25,

458

29

459

for DOM were observed for the citric acid systems. This is likely due to the chemical

460

heterogeneity of natural DOM; however, this needs to be further explored using other model OC

461

compounds.

462

Citric acid and Fe were found to well-related; however, none of the ternary features observed

Overall, the proposed occurrence of Fe-Ca-OC ternary complexes has the potential to

463

significantly impact how organo-mineral associations are modeled in current environmental C

464

cycling models and the development of potential C sequestration management strategies in soil

465

systems containing Fe oxides. We expect this phenomenon, measured currently at slightly acidic

466

pH conditions, to occur to a greater extent in basic, calcareous soils, which will be examined in

467

the future. Also, we have observed in past research that increasing Ca concentration from 1 mM

468

Ca up to 30 mM Ca resulted in increased OC sorption for samples equilibrated at initial molar

469

C/Fe ratios of 4.7 and 12.5 (SI Figure S6).24 Therefore, we expect that ternary complexation may

470

be occurring in a wide range of systems, which warrants further spectroscopic investigation.

471

Additional work needs to be performed to understand the stability of proposed Fe-Ca-OC ternary

472

complexes with changing environmental conditions (redox, temperature, etc.). Increased

473

spectroscopic work is also needed to elucidate the proposed Ca-bridging mechanism of Fe-Ca-

474

OC ternary complexes, which may be accomplished using chemically similar polyvalent cations

475

of greater atomic mass (e.g., strontium).

476 477

Acknowledgements

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478

This publication was made possible by the National Science Foundation EPSCoR Grant No. IIA-

479

1301765, the State of Delaware, the Delaware Environmental Institute, and the Donald L. and

480

Joy G. Sparks Graduate Fellowship. The authors thank the UD Soil Testing Lab, UD Advanced

481

Materials Characterization Lab, Stroud Water Research Center, Canadian Light Source, and the

482

UD Environmental Soil Chemistry group for their support. The Canadian Light Source is funded

483

by the Canada Foundation for Innovation, the Natural Sciences and Engineering Research

484

Council of Canada, the National Research Council Canada, the Canadian Institutes of Health

485

Research, the Government of Saskatchewan, Western Economic Diversification Canada, and the

486

University of Saskatchewan.

487 488 489 490 491 492 493 494 495 496 497 498 499 500

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Figures.

1 µm

C

B

A

D

2 µm

C Ca Fe

1 µm 1 µm

502 503

Figure 1: Color-coded composite RGB optical density maps created from STXM-NEXAFS data.

504

Red, green, and blue represent carbon, calcium, and iron, respectively. RGB maps are shown for

505

ferrihydrite-DOM (A), ferrihydrite-Ca-DOM (B), ferrihydrite-citric acid (C), and ferrihydrite-

506

Ca-citric acid samples (D). Cyan regions in Figure 1A and Figure 1D were identified as regions

507

too thick for transmission.

508

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Page 24 of 34

DOM

Citric Acid

A

D

B

E

C

F

No Calcium

Calcium

509

Figure 2: Elemental optical density correlation plots between C, Ca, and Fe for DOM-bearing

510

(A-C) and citric acid-bearing (D-F) ferrihydrite. Linear correlation coefficients are provided for

511

each plot. Thickness values for each element are also provided (calculated using SI Table S3).

512

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0.54

A

D

1 µm

0

B

C

513 514

Figure 3: C K-edge STXM average stack optical density map for ferrihydrite-DOM of the C K-

515

edge (287.7-288.8 eV) and the C K-edge minus C pre-edge (287.7-288.8 eV minus 280-282 eV)

516

difference map are shown in A and B, respectively. PCA of the C K-edge stack is shown in C

517

and respective C 1s STXM-NEXAFS spectra for the whole sample and each of the 3 clusters

518

identified through PCA are shown in D. A standard of the DOM stock is also included.9 Peak

519

assignments are located in Table 1.

520

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0.48

A

D

2 µm

0

B

C

521 522

Figure 4: C K-edge STXM average stack optical density map for ferrihydrite-Ca-DOM of the C

523

K-edge (287.7-288.8 eV) and the C K-edge minus C pre-edge (287.7-288.8 eV minus 280-282

524

eV) difference map are shown in A and B, respectively. PCA of the C K-edge stack is shown in

525

C and respective C 1s STXM-NEXAFS spectra for the whole sample and each of the 3 clusters

526

identified through PCA are shown in D. A standard of the DOM stock is also included.9 Peak

527

assignments are located in Table 1.

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528 529

Figure 5: ATR-FTIR spectra for ferrihydrite samples reacted with either DOM or citric acid in

530

the absence or presence of Ca. A molar C/Fe ratio of 2.5 or 4.7 was used for DOM samples in

531

order to reveal spectra features that may be difficult to distinguish at high molar C/Fe ratios.9 A

532

reference standard for the stock DOM used for DOM reactions is also included.

533 534

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535

Page 28 of 34

Table 1: C 1s NEXAFS peak energies with C functional group interpretation Peak Number

Peak Energies (eV)

C Functional Groups

Transition

References

i, ii

285.2-285.6

Aromatic (Caromatic=Caromatic)

1s-π*

Henneberry et al., 2009; Solomon et al., 2012; Chen et al., 2014

iii

286.7-286.9

Phenolic Caromatic-OH

1s-π*

Wan et al., 2007; Solomon et al., 2012; Chen et al., 2014

iv

287.5

Aliphatic (C-H)

1s-3p/σ*

Wan et al., 2007; Solomon et al., 2013

Boxed Region

287.2-287.6

Polyvalent metal ion complexation to COOH

NA

Plaschke et al., 2005; Armbruster et al., 2009

v

288.5

Carboxylic Acid (COOH)

1s-π*

Wan et al., 2007; Solomon et al., 2012; Chen et al., 2014

536 537 538 539 540 541 542 543 544 545 546 547 548 549

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