Fe(II)âInduced Mineral Transformation of Ferrihydrite-Organic Matter

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Fe(II)–Induced Mineral Transformation of FerrihydriteOrganic Matter Adsorption and Coprecipitation Complexes in the Absence and Presence of As(III) Chunmei Chen, and Donald L. Sparks ACS Earth Space Chem., Just Accepted Manuscript • DOI: 10.1021/ acsearthspacechem.8b00041 • Publication Date (Web): 13 Sep 2018 Downloaded from http://pubs.acs.org on September 14, 2018

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ACS Earth and Space Chemistry

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Fe(II)–Induced Mineral Transformation of Ferrihydrite-Organic Matter Adsorption and

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Coprecipitation Complexes in the Absence and Presence of As(III)

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Chunmei Chen* and Donald L. Sparks

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Department of Plant and Soil Sciences

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Delaware Environmental Institute

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University of Delaware, Newark, DE, USA 19711

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Corresponding Author

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*Phone: (302)8318345. Fax: (302)8310605. E-mail: [email protected]

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1 ACS Paragon Plus Environment

ACS Earth and Space Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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Abstract The poorly crystalline ferrihydrite (Fh) is often associated with organic matter (OM) and

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metal(loid)s like arsenic (As). The transformation of Fh to more stable and hence less reactive

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phases is catalyzed by surface reaction with Fe(II). However, little is known regarding the impact

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of various specific OM types and the co-existence of OM and As on the secondary

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mineralization of Fh. Accordingly, we explored the extent and the resulting secondary minerals

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of Fe(II)-induced transformation of (As(III)-adsorbed) OM-Fh adsorption and coprecipitation

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complexes, which were synthesized using two types of OM (DOM extracted from the O horizon

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of an Ultisol and polygalacturonic acid (PGA) as a proxy for polysaccharides. Regardless of OM

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type, increased contents of the coprecipitated or adsorbed OM led to a decrease in Fh

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transformation in both the absence and presence of As(III). Adsorbed As(III) caused a decrease

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in Fh conversion for both pure Fh and OM-Fh complexes. We observed only small differences in

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Fe(II)-induced transformation of OM-Fh coprecipitates vs. adsorptive complexes. However,

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without adsorbed As(III), OM types strongly influenced the secondary mineral products: DOM

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impeded goethite (Gt) and stimulated lepidocrocite (Lp) formation, while only Gt was formed for

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PGA. When As(III) and OM coexists, As (III) favored Lp over Gt formation for both DOM- and

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PGA-Fh complexes. These findings provide evidence that the mineral evolution of Fh largely

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depends on the potential additive/competing influence of coexisting constituents.

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Keywords: EXAFS; iron oxides; crystallization; dissolved organic matter; polysaccharides; arsenic

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Introduction Fe(III) (oxyhydr)oxides (hereafter termed Fe oxides) are ubiquitous in soils and

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sediments and can be strong sorbents for soil nutrients, contaminants and organic matter (OM).1-6

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Fe oxides are present in the environment as a wide range of minerals with different

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characteristics such as stability, specific surface area, and reactivity.1, 7-8 Fe oxides can undergo

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reductive dissolution in anoxic environments, releasing Fe(II)3, 9, 10. The adsorption of Fe(II) onto

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Fe(III) oxides induces electron transfer from Fe(II) to the host Fe oxides with accompanying

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recrystallization of the Fe oxides to thermodynamically more stable forms.11-16 This

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transformation process has wider implications than just the cycling of Fe alone, as the varying

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properties of Fe phases, such as surface area and crystallinity and their interaction with Fe(II),

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can affect the cycling of metal(loid)s and OM that are either adsorbed to or coprecipitated with

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Fe oxides17-19. Mineralogical changes are particularly dramatic when the initial Fe(III) oxide

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phase is ferrihydrite (Fh), a poorly-crystalline/amorphous Fe mineral, which readily undergoes

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Fe(II)-catalyzed crystallization to lepidocrocite (Lp), goethite (Gt) and magnetite11, 12-16.

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The rate and extent of Fe(II)-catalyzed Fh transformation, as well as the mineralogy and

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physicochemical properties of the products, may be affected by the presence of surface-

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associated or structurally incorporated elements. In nature, Fe oxides like Fh are often associated

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with OM20-22, via adsorption and/or coprecipitation23-26. OM was shown to hinder Fe(II)-induced

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Fh transformation by surface-site blockage and/or organic Fe(II) complexation.19, 27, 28 With

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respect to OM adsorption on pre-existing Fe oxides, OM coprecipitation with Fh results in

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smaller crystal sizes and greater structural disorder19, 28-30, and may subsequently affect the

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reactivity and stability of Fh. Chen et al. showed that Fh coprecipitated with OM extracted from

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forest litter samples, displayed a linear decrease in mineral transformation rates with increasing



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OM contents following reaction with Fe(II), and favored Lp formation over Gt and magnetite.19

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Recently, it was observed that, at similar OM loadings, coprecipitated Fh was more reactive

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towards microbial reduction than Fh with adsorbed OM.31-32 However, the impact of adsorbed vs.

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copecipitated OM on abiotic Fh transformation induced by Fe(II) has not been directly compared.

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In addition, OM composition in natural environments is very complex, comprising a collection

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of simple and macromolecular organic groups33-35. However, the impact of varying specific

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organic compounds on Fh transformation and the nature of the resulting products is rarely

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investigated36, 37.

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OM-rich soil and sediments tend to show high affinities for trace metal(loid)s like arsenic

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(As).38-41 As(V) has a strong affinity for both Al and Fe oxides, while As(III) adsorption is

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largely limited to Fe oxides.42-45 The As content of naturally occurring iron oxides shows great

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variation ranging from an As/Fe molar ratio of 2.4 × 10−6 to 0.146-49, with As speciation primarily

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As(III) in some cases49. Although low As(V) concentrations (As/Fe 1.1), a complete suppression of Fh transformation was

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observed following 7 days of reaction (Figure 1; SI Figure S6 and S7). The impaired Fh

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transformation by OM, which is consistent with previous studies19, 27, 28, 60, could be attributable

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to the decreased Fe(II) adsorption (SI Table S3), the surface blockage as indicated by surface

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area measurement (SI Table S1), and organic complexation of Fe(II). This could reduce the

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direct contact between Fe(II) and the mineral surface, and hence inhibit/slowdown mineral

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transformation19, 28. Previous studies have also demonstrated that OM can retard transformation

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of Fh to more crystalline minerals by blocking dissolution sites or hindering nucleation of more

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stable minerals even in the absence of Fe(II).61, 62

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Apart from the amount of Fh-associated OM, we demonstrated for the first time that the

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type of OM is a another key factor in determining the products of the Fe(II)-catalyzed Fh

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transformation in the absence of As(III). Although the extent of Fh preservation was greater for

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DOM than for PGA at a C/Fe ratio of ~0.85, a similar degree of Fh preservation between PGA

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and DOM was observed at all the other C/Fe ratios (SI Figure S11). The reaction products of

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Fe(II)-catalyzed transformation of Fh are primarily a function of Fe(II)/Fh ratio, pH and ligand

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type. The Fe(II) concentration (~0.5 mmol/g Fh) used in this study was below the threshold


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required for magnetite precipitation (~1.0 mmol Fe(II)/g Fh) at circumneutral pH 11. Consistent

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with previous studies11, 16, 19, FeSO4 (~0.5 mmol/g Fh) favored the conversion of pure Fh to Gt at

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pH 7 (buffered with PIPES). In contrast to only Gt formation for pure Fh, DOM resulted in more

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Lp formation with less Gt (Figure 1a; SI Figure S6), as observed previously19. However,

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interestingly, only Gt formation was observed for PGA (Figure 1b; SI Figure S7). These results

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indicate a strong role of OM composition in Fh transformation products. Lp is

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thermodynamically unstable with respect to Gt, and thus Lp may serve as a precursor to Gt

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formation.1 Transformation of Lp to Gt was noticed in our previous study of reaction of pure Fh

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with Fe(II)19. However, mineral-associated DOM stabilized Lp from further transformation19. In

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contrast, only Gt formation with PGA may suggest that unlike DOM, polysaccharides may be

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unable to hinder the transformation of Lp to Gt. However, future studies on temporal mineral

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evolution are needed to unravel if Lp is formed as an intermediate product, or if Fh is directly

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converted to Gt during reaction of PGA-Fh with Fe(II). The amount of Fe(II) removed from

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solution following 1 hour of reaction is nearly equivalent for DOM- and PGA-Fh complexes (SI

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Table S3). This implies that the difference in the transformation products between DOM and

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PGA is unlikely due to Fe(II) sorption, although it is currently unknown if the amount of electron

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transfer from adsorbed Fe(II) to bulk Fe(III) differed between PGA- and DOM-Fh complexes. It

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was suggested that the effectiveness in suppressing crystallization depends on how strongly the

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organic compounds sorb onto Fe oxides36, 37. Although the solid-phase C content in all samples

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before and after reaction with Fe(II) indicates no significant loss of solid-phase OM (SI Table

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S2), DOM appeared to bind more strongly with Fe oxides than PGA (SI Figure S10). Thus, the

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displacement of DOM on oxides by the Fe(II) ions may be more difficult than that for PGA.

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Therefore, DOM could more effectively stabilize meta-stable oxides like Lp from



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recrystallization than extracellular organic compounds from plant root exudates or microbial EPS.

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In addition, DOM contains aromatic and phenolic C in addition to carboxyl groups, while PGA

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only has carboxylic C (SI Figure S1). The aromatic and phenolic C may hinder the nucleation of

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more stable minerals like Gt. Considering the common associations of OM and oxides in nature6,

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, the influence of varying OM types on mineral evolution needs to be fully explored. The FTIR spectra of the adsorbed and coprecipitated OM were similar for both PGA and

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DOM (SI Figure S2). In addition, we observed no difference in the extent or products of Fh

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transformation between coprecipitates and adsorption complexes at the lowest and highest OM

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contents for both DOM and PGA (Figure 1 and SI Figure S11). With intermediate OM contents

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(C/Fe=0.52-0.88), the coprecipitated OM resulted in slightly more Fh transformation (5-10% of

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total Fe) to Gt than the adsorbed OM for both DOM and PGA. This might be due to the smaller

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particle size and lower crystallinity of the coprecipitated Fh, based on Mössbauer analysis from

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previous studies19, 29. Overall, the reactivity of OM-Fh adsorption and coprecipitation complexes

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did not display large differences in the reactivity towards Fe(II). Similarly, a previous study,

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which compared microbial Fe(III) reduction of DOM-Fh complexes, showed Fe(III) reduction

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rates was only slightly higher for DOM-Fh coprepitates (0.038-0.058 mmol h-1) compared to the

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adsorption complexes (0.02-0.05 mmol h-1).32 In addition, it was previously reported that the

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differences in the degradability of the adsorbed and coprecipitated DOM and lignin were small 63.

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Collectively, we may not expect dramatic differences in the stability, transformation and

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composition of both organic and mineral components of OM-Fh complexes formed via

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coprecipitation vs. adsorption in natural environments.

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Fe(II)-induced transformation of As(III)-bearing (OM-)Fh


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Following reaction with Fe(II), the oxidation state of the adsorbed As(III) remained

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unchanged based on As K-edge XANES analysis (SI Section 8). Similar to As(III)-free systems,

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the extent of Fh preservation also increased with increasing OM contents when As(III) was

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adsorbed. Adsorbed As(III) resulted in a decrease in Fh conversion and hence the preservation of

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Fh, compared to the corresponding As-free treatment for both pure- and OM-Fh (Figure 2 and SI

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Figure S11), as determined by EXAFS LCF. Previous studies have found that adsorbed As(V)

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can inhibit Fe(II)-catalyzed Fh transformation.18, 51 We showed here that this is true for As(III)

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with an As(III)/Fe ratio of 0.03, and the co-existence of As(III) and OM resulted in less Fh

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transformation than OM-free and As-bearing systems following short-term (≤ 7 days) exposure

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to Fe(II). Such inhibition of phase transformation has been reasoned to result from As covalently

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bonded to the surface of Fh64, which can reduce the extent of electron exchange between Fe(II)

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and Fe(III) required for Fe(II)-catalyzed transformation 51, 65. Arsenic is also believed to retard

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Fh transformation in a similar way as hydroxyl-carboxylic acids 66. Cornell and Schwertmann

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suggested that the anion linkage of two or more units of Fh forms a network of particles resistant

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to dissolution 37.

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Adsorbed As(III) also alters the secondary products of Fh transformation—for both pure-

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and OM-Fh (Figure 2). Unlike pure Fh, reaction of As(III)-bearing Fh with Fe(II) produced

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primarily Lp with much less Gt following 7 days of reaction (Figure 2; SI Figure S5b). The

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preferential formation of Lp during abiotic As(V)-bearing Fh transformation has also been noted

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previously 18, 51. A previous study showed that Lp could be slowly converted to Gt in the absence

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of other constituents at the longer reaction time scale (e.g. months), however no transformation

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of Lp was observed in the presence of DOM even following 3-month reaction with Fe(II).19

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Therefore similar to what was observed for DOM, As could inhibit or at least slow down the



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transformation of the relatively unstable Fe oxides like Lp to more stable Gt, possibly by

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blocking dissolution sites or by preventing polymerization of thermodynamically stable Fe(III)

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minerals 67, 68.

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An interesting and important finding is that adsorbed As(III) minimizes the impact of

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OM types on the secondary products of Fe(II)-catalyzed OM-Fh complex transformation with an

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As/Fe ratio of 0.03 (Figure 2). The co-existence of DOM and As(III) on Fh increased Lp

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formation by inhibiting Gt formation, relative to As-free DOM-Fh complexes (Figure 2; SI

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Figure S8). This favored Lp over Gt formation by adsorbed As(III), was much more dramatic

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for PGA-Fh complexes, compared to DOM-Fh complexes (Figure 2; SI Figure S9).

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Consequently, in the presence of adsorbed As(III), nearly identical secondary products were

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observed between DOM- and PGA-Fh complexes (Figure 2). While As(III) (As/Fe = 0.03) and

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OM (C/Fe = 0.3-0.6) co-occur in the systems with ~0.5 mmol FeSO4/g Fh and pH 7, Lp

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formation was much more pronounced relative to Gt, regardless of OM types. Therefore, with

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adsorbed As(III), the concentrations of Fh-associated OM and As(III) are critical in determining

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the mineral evolution. Owing to the significant co-occurrence of As and OM in contaminated

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sites, the observed less-crystalline (and hence more reactive) Fe oxides including Fh and Lp in

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the presence of As and OM, has to be considered when evaluating the reactivity of Fe minerals

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and the subsequent impact on the fate of OM and metal(oids) associated with these minerals in

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the environment.

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Environmental Implications In soils and sediments, where Fe oxides are impure, alteration of mineral transformation by impurities may influence the dynamics of OM, metals and nutrients associated with Fe oxides.


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Here, we note that the adsorbed or coprecipitated OM and the adsorbed As(III) decreased the

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extent of Fh transformation. These findings may provide an explanation for the preservation of

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Fh-like phases in natural environments 49, 69, 70. Transformation of Fh to presumably less-reactive

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Gt is expect to preferentially occur in environments lacking of DOM and As(III) (i.e.

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uncontaminated subsurface environments). In addition, the decreased Fh transformation, as well

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as the favored Lp over Gt formation in the presence of DOM and As(III), has important

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implications for predicting the fate of Fe minerals and their associated species such as As and

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OM. The persistence of Fh/Lp in OM-rich and As-contaminated fields may provide reactive

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surface area for OM, metals or nutrients, as well as electron transfer reactions. For example,

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rapid reductive dissolution of these presumably more bioavailable oxides such as Fh and Lp,

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may consequently drive OM 71, 72 and As mobilization 73, 74 to the aqueous phase under anoxic

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conditions.

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Supporting Information

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Additional details on Fe EXAFS analysis, XRD data, FTIR measurements, and As XANES

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analysis.

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Acknowledgements This research is a part of the Christina River Basin Critical Zone Observatory (CRB-CZO)

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project that was supported by the National Science Foundation (EAR 0724971). XAS analysis

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was carried out at the Stanford Synchrotron Radiation Lightsource, a Directorate of SLAC

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National Accelerator Laboratory and an Office of Science User Facility operated for the U.S.

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Department of Energy Office of Science by Stanford University. We are also grateful to the



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Shanghai Synchrotron Radiation Facility for use of the synchrotron radiation facilities at

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beamline 14W.

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Figure 1 Secondary minerals formed following 7 days of reaction of 1 mM Fe(II) with

511

ferrihydrite (C/Fe = 0) as well as (a) DOM- and (b) PGA-ferrihydrite adsorption vs.

512

coprecipitation complexes, as a function of C/Fe molar ratios. Mineral percentages were obtained

513

via linear combination fitting of k3-weighted Fe EXAFS spectra with reference minerals. The k3-

514

weighted EXAFS spectra and linear combination fits are shown in Supporting Information (SI

515

Figure S13 and S14).

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Figure 2 Secondary minerals formed following 7 days of reaction of 1 mM Fe(II) with As(III)-

538

bearing ferrihydrite, as well as As(III)-bearing (a) DOM- and (b) PGA-ferrihydrite adsorption vs.

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coprecipitation complexes, as a function of C/Fe molar ratios. Mineral percentages were obtained

540

via linear combination fitting of k3-weighted Fe EXAFS spectra with reference minerals. The k3-

541

weighted EXAFS spectra and linear combination fits are shown in Supporting Information (SI

542

Figure S15 and S16).

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Fe(II)âInduced Mineral Transformation of Ferrihydrite-Organic Matter

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