Sea Level Rise Induced Arsenic Release from Historically

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Sea level rise induced arsenic release from historically contaminated coastal soils Joshua J. LeMonte, Jason W. Stuckey, Joshua Z. Sanchez, Ryan V Tappero, Jörg Rinklebe, and Donald L. Sparks Environ. Sci. Technol., Just Accepted Manuscript • Publication Date (Web): 04 May 2017 Downloaded from http://pubs.acs.org on May 5, 2017

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Environmental Science & Technology

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Sea level rise induced arsenic release from historically contaminated coastal soils

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Joshua J. LeMontea,b, Jason W. Stuckeya, Joshua Z. Sancheza, Ryan Tapperoc, Jörg

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Rinklebed, and Donald L. Sparksa*

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a

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of Delaware, Newark, Delaware, 19711, USA.

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b

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Center, Vicksburg, MS, 39180, USA

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

Currently: U.S. Army Corps of Engineers, Engineer Research & Development

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c

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11973, USA

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d

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Architecture and Civil Engineering, University of Wuppertal, Wuppertal, 42285,

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Germany

Photon Sciences Division, Brookhaven National Laboratory, Bldg 743, Upton, NY,

Institute of Foundation Engineering, Water- and Waste-Management, School of

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

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Street, Suite 250, University of Delaware, Newark, DE 19716; (302) 831-3436;

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[email protected]

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ACS Paragon Plus Environment


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Abstract Climate change-induced perturbations in the hydrologic regime are expected to

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impact biogeochemical processes, including contaminant mobility and cycling.

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Elevated levels of geogenic and anthropogenic arsenic are found along many coasts

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around the world, most notably in south and southeast Asia, but also in the United

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States, particularly along the Mid-Atlantic coast. The mechanism by and the extent to

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which arsenic may be released in contaminated coastal soils due to sea level rise are

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unknown. Here we show a series of data from a coastal arsenic-contaminated soil

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exposed to sea and river waters in biogeochemical microcosm reactors across field-

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validated redox conditions. We find that reducing conditions lead to arsenic release

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from historically contaminated coastal soils through reductive dissolution of arsenic-

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bearing mineral oxides in both sea and river water inundations, with less arsenic

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release from sea water scenarios than river water due to inhibition of oxide

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dissolution. For the first time, we systematically display gradation of solid phase soil-

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arsenic speciation across defined redox windows from reducing to oxidizing

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conditions in natural waters by combining biogeochemical microcosm experiments

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and X-ray absorption spectroscopy. Our results demonstrate the threat of sea level rise

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stands to impact arsenic release from contaminated coastal soils by changing redox

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conditions.

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Keywords: sea level rise, arsenic, geochemistry, soil chemistry, XANES, redox

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Introduction Earth’s climate is changing and as a result, frequency and intensity of storm

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surges are increasing and sea levels are rising.1 It is estimated that the global mean sea

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level will rise by 0.8 m over the next century and impact the 25% of the world’s

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population inhabiting coastal zones.2,3 Increased storm surges and flooding have

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garnered the bulk of research and media attention associated with sea level rise (SLR)

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due to the physical and economic threats posed to coastal regions. However, chemical

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and mineralogical changes in the subsurface that result from saltwater inundation and

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prolonged flooding, and the concomitant impacts on contaminant fate and transport,

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remain poorly understood.3–5

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Climate change induced shifts in the hydrologic regime are expected to impact

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biogeochemical processes including contaminant mobility and cycling.6 These

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changes will alter soil redox conditions and introduce salinity and reducing zones in

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areas that have long remained oxic or less brackish and thus threaten to release redox

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sensitive toxic elements such as arsenic (As) to groundwater. Elevated levels of As,

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from both geogenic and anthropogenic sources, are found along the world’s coastlines.

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In south and southeast Asia, tens of millions of people have been chronically poisoned

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by As-contaminated groundwater.7 Within the United States, As has been detected in

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nearly 20% of public groundwater supplies, and elevated levels of As are present at

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more than a third of the U.S. EPA’s superfund sites on the National Priorities List.8

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Parts of the world are experiencing faster rates of SLR than the global average.9,10 The

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Atlantic coastlines are particularly susceptible to near-future SLR, including the Mid-

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Atlantic coast of the U.S. where SLR rates are higher than elsewhere in the world due

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to the combination of SLR and coastal subsidence.9,11 It has been recommended that

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states in this region prepare for SLR of at least 1 m by 2100.12 Situated in the center of

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the Mid-Atlantic, Delaware is expecting at least 1 m of SLR, likely impacting many

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coastal As-contaminated sites, making it an ideal study location.

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The fate and transport of As in soils and sediments is intimately tied to

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environmental conditions (e.g., Eh, pH, ionic competition) as well as the

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biogeochemical redox cycling of other soil constituents such as Fe, Al, and Mn

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(oxyhydr)oxides (referred to as “oxides” hereafter), S, and C.6,7,13 Anaerobic

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conditions lead to reduction of surface bound AsV to the more weakly sorbed AsIII, and

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thus increase As mobility.14 Reducing conditions also promote reductive dissolution of

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As-bearing Fe oxides and favor dissimilatory metal reducing bacteria. Dissimilatory

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reduction of Fe oxides is the suspected primary driver of As release under reducing

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conditions in soils and sediments. Additionally, reduction of arsenate to arsenite by

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As-respiring bacteria can be a driver of As release and be uncoupled from

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dissimilatory Fe reduction.15 In high SO42- systems As release may be inhibited via

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ligand complexation or energetic favorability of dissimilatory SO42- reduction in lieu

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of dissimilatory reduction of Fe oxides.16,17

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Whereas much research has been conducted on As cycling, the stability of As

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in historically contaminated soils is uncertain.18 Furthermore, the extent to which SLR

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will impact mobilization of existing contaminants in coastal soils is unknown. To fill

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this knowledge gap, here we systematically evaluate the effects of inundation with

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seawater and river water on As mobilization and speciation across pre-defined Eh

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zones using a historically As contaminated soil from the densely populated Delaware

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coastline. For the first time, measurements of As release to solution were coupled with

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solid phase speciation under preset redox conditions, while simultaneously monitoring

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factors controlling As cycling and redox chemistry (e.g. pH, Fe, DOC, S).

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Experimental

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Soil Sampling and Characterization

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A series of experiments were conducted using automated biogeochemical

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microcosm reactors (MC hereafter) to elucidate soil-As dynamics when inundated

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with sea and river water across pre-defined redox windows. The soil used was

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collected from a historically As-contaminated industrial site in Wilmington, Delaware,

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USA, projected to be inundated by 1 m of SLR by 2100. The city of Wilmington, DE

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has a long history of industrial activities including leather tanning, chemical

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production, and ore processing.19 Each of these industries has contributed to the

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widespread As contamination currently found along the banks of the tidally influenced

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Christina River that flows through Wilmington. The soil was sampled from along the

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banks of a tidal basin constructed as part of a remediation effort for an adjacent U.S.

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EPA superfund site.

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The soil was sampled from 0-20 cm from 10 random locations at the site and

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combined into one composite sample.20 The composited sample was homogenized,

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air-dried, ground to pass through a 2 mm sieve, and stored at 4°C in the dark until

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experiments were conducted. Soil pHwater, texture, and organic matter were measured

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using standard methods.21 Particle size was determined by laser diffraction (Beckman

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Coulter LS 13 320). Total metal content of the homogenized soil samples was

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determined by microwave-acid digestion (US EPA 1995 Method 3051), followed by

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analysis via inductively coupled plasma atomic emission spectrometry (ICP-AES,

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Thermo Elemental Intrepid II XSP Duo View).22 Total (“free”) iron oxide content was

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determined using the citrate-bicarbonate-dithionite method.23 Poorly crystalline

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(“active”) iron oxide content was determined using the acid ammonium oxalate in

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darkness method.23

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Microcosm Studies

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An advanced automated biogeochemical microcosm (MC) system was used to

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simulate oxidizing and reducing conditions. This system has been used successfully by

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others; a detailed description can be found therein.24–26

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At the initiation of each MC trial, an additional 10 g of “fresh” (moist) soil

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collected from the respective field location was added to each MC as a microbial

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inoculant. Additionally, 10 g of dried and ground reed (Phragmites australis) collected

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at the site was used as a slow-release C source for microorganisms. Two 10 g doses of

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glucose were also added to each MC to prime the system for reaching low redox

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potentials by ensuring a C-limited system did not exist. Minimum Eh levels were

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obtained through microbial reduction and flushing the MC with N2 gas.

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After reaching a stable Eh minimum, the Eh was sequentially raised in 100 +/- 20 mV

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increments by injecting O2 gas into the reactor then regulating at the target Eh using

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O2 (to increase Eh) or N2 (to decrease Eh). Each targeted Eh window was maintained

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for 72 h and then a slurry sample was taken. A total of six distinct Eh levels (-300 to

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+200 mV) were set and sampled for each replicate. The experimental Eh range was

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field-validated through installation and monitoring of multilevel in situ redox sensors

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at the soil sampling site (Paleo Terra, Amsterdam, Netherlands).

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Measurements of Eh, pH, and temperature of the microcosms were logged

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every 10 minutes for the entirety of the incubation. Mean Eh values during the 6 h

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prior to sampling was previously determined to give the best correlation coefficients

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between Eh/pH and metal(loid)s in solution within the MC system and therefore will

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be presented in this study.26 Slurry samples were sealed at sampling and immediately

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centrifuged at 1000 g for 10 min. Once centrifuged, samples were moved into an

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anaerobic glove box and the supernatant was filtered through a 0.45 µm Millipore

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nylon membrane (Whatman, Inc). While under the 95% N2/5% H2 atmosphere,

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aqueous subsamples were prepared for total elemental analyses. Subsamples analyzed

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via ICP mass spectrometry (ICP-MS) for total metal content in solution were acidified

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to 2% trace metal grade HNO3 and diluted to eliminate potential for C-induced As

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signal amplification (Agilent Technologies, 7500cx ICP-MS).27 Total organic carbon

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(TOC) was determined by high temperature catalytic oxidation (Vario TOC cube,

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Elementar Americas, Mt. Laurel, NJ). Iron(II) was determined by the phenanthroline

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method (Hach, Loveland, CO), sulfide was determined by the US EPA methylene blue

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method (Hach), ammonium was determined by the high range salicylate method

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(Hach), and alkalinity was determined by the bromcresol green-methyl red indicator

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method using the Hach digital titrator, all within 2 h of sampling.

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Correlations between solution geochemical data and arsenic release were

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explored using multivariate Partial Least Squares Regression (PLSR).28

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Bulk X-ray Absorption Spectroscopy

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Samples from each defined redox window, from -300 mV to +200 mV in 100

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mV increments, were selected from both the freshwater and seawater trials for As K-

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edge X-ray absorption spectroscopy (XAS) analysis. Following centrifugation and

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decanting, samples were dried under a 95%N2/5%H2 atmosphere and the dried soils

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were mounted onto 1 mm thick aluminum between layers of 25 µm thick Kapton tape.

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Analyses were performed at beamline 4-3 at the Stanford Synchrotron Radiation

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Lightsource (SSRL). Fitting was performed with the refined manual linear

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combination fitting tool available from beamline 10.3.2 at the Advanced Light Source

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(ALS; https://sites.google.com/a/lbl.gov/als-beamline1032). Fitting was evaluated by

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calculating the normalized sum of squares (NSS) residual of the fit involving inclusion

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of the ith component [NSS = Σ(y – yfit)2)/Σ(y2)]. Inclusion of each component was

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required to 1) improve the NSS by at least 10% and 2) represent at least 5% of the

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measured signal.

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Bulk S K-edge XANES analyses were performed on a subset of the same soils

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analyzed for As XANES. Analyses were conducted at beamlines 14-3 at SSRL and

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SXS at the Brazilian Synchrotron Light Laboratory. Least squares fitting of

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normalized XANES fluorescence spectra was performed over a range of 2465–2490

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eV using the LINEST function in Microsoft Excel, with details explained

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previously.7,29

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Micro X-ray Fluorescence (µXRF) Mapping and µXANES Spectroscopy

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Samples from the most extreme redox windows (-300 mV and +200 mV) were

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selected from both the freshwater and seawater trials. These samples were dried under

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95%N2/5%H2 atmosphere and resin-embedded (EPOTEK 301_2FL) at low

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temperature and low O2 (Spectrum Petrographics method X26A). A thin section was

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then prepared and mounted onto a quartz slide. Samples were transported to the

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beamline under inert atmosphere, where they were kept until analysis. To determine

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elemental hot spots and colocation patterns, fine-scale µXRF mapping and µXANES

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spectroscopy were performed at SSRL beamline 2-3 following a previously described

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protocol. The beamline was equipped with KB focusing mirrors providing a spot size

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of 2x2 µm. Elemental maps were generated using a single-element Si drift Vortex

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detector; the sample was continuously rastered across the X-ray beam using a 5 µm

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pixel size and dwell time of 50 ms per pixel. Windowed counts of each element were

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isolated from the full X-ray fluorescence spectra and normalized to the intensity of the

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incident X-ray beam (I0). Energy was selected using a Si (111) double crystal

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monochromator and calibrated by assigning the whiteline position of Na3AsO4

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standard to 11.874 keV.

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Based on µXANES spectra of six As standards, representing the potential

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chemical species within the reacted sediments, a 1.5 mm x 1.5 mm (2.25 mm2) region

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of the thin section was mapped at 11.867, 11.870, 11.873, 11.877, and 11.881 keV

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incident energy. Using the SMAK routine, principal component analysis (PCA) was

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performed on dead time corrected maps to determine optimal locations for µXANES

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spectral analysis.30 Least squares fitting of normalized µXANES spectra was

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optimized at ±20 eV from E0 in Athena.31 Normalized µXANES spectra of the As

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standards corresponding to the five incident energies were used to fit the multiple

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energy µXRF maps in a non-negative linear least squares routine in SMAK.32

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More experimental details can be found in the Supporting Information.

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Results and Discussion

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Arsenic Dynamics in Solution Across Eh Zones

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The reacted soil was a loam with mean particle size of 737.1 µm (s.d. 641.6

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µm) and pH = 5.9. Total As concentration in the soil was 1.3 g kg-1 and the total Fe

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concentration was 9.7 wt %, 75% of which were amorphous hydrous Fe oxides (Table

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1). Arsenic speciation in the soil collected and preserved for XANES analysis was

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primarily AsIII (data not shown).

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Inundation with both waters resulted in decreased Eh and increased pH, as has

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been seen previously (Fig. S1).25,33,34 The river water had an initial pH of 7.2, and an

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EC of 0.7 mmhos cm-1. The seawater had an initial pH of 7.8 and an EC of 45.6

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mmhos cm-1. Arsenic was below detection (< 0.5 µg L-1) in both unreacted waters

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(Table 1). Arsenic concentrations in solution increased as Eh decreased in both the

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river water and seawater trials (Fig. 1). River water inundation resulted in

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approximately twice as much As release than seawater (Fig. 1). Sequential extractions

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revealed that 86% of total As is occluded in hydrous oxides, with the balance of As

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sorbed (13% inner-sphere and 1% outer-sphere). These results suggest that As release

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cannot be explained by sorption processes. Rather, dissolution (ligand, proton, and/or

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reductive) of As-bearing mineral oxides may be driving As release.

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Total SO42- in the seawater system was ten times that of the freshwater system,

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with levels reaching nearly 70 mg L-1 at Eh levels greater than 100 mV. It is expected

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a large amount of seawater SO42- sorbed to the soil, potentially stabilizing As-bearing

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hydrous oxides by forming bidentate binuclear ligand complexes.17 Elevated SO42- in

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solution can competitively inhibit dissimilatory reduction of AsV and FeIII via

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dissimilatory reduction of SO42- at pH > 5.0, represented as:16,35 + → 2 +

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Preferential or concurrent SO42- reduction may preserve occluded AsV and

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result in decreased As release, which is a possible explanation for the decreased As in

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solution in the seawater inundation scenario as compared to the river water. This is a

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thermodynamic possibility if the Gibbs free energy (∆G0) of dissimilatory sulfate or

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Fe reduction are equally favorable, as can be the case depending on which Fe oxide is

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being reduced.36,37 It has been shown that following intrusion by water with high

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salinity, mineralization of organic C can shift rapidly from Fe reduction to SO42-

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reduction.38

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Whereas As cycling can be strongly impacted by S cycling in reduced soils and

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sediments, As was not correlated to sulfide (S2-) or sulfate in solution for either

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inundation scenario (Fig. 1). Additionally, there was no pattern of S2- or SO42- in

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solution across Eh and pH values (Fig. S3). Sulfide was below the method detection

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limit (1 mg L-1) for both waters for the duration of the experiment. It is likely that S2-

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was formed under the reducing conditions through the reduction of SO42-, but likely

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rapidly transitioned to Fe-S, As-S, or Fe-As-S precipitates in the high AsIII and FeII

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solution, resulting in the low S2- in solution throughout the duration of the

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experiment.16 High rates of SO2- reduction, particularly in the seawater treatments may

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have resulted in formation of aqueous As-S complexes (e.g. HAs3S62-).39 Thioarsenic

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species can be found in environmental samples that have high levels of solution As

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and S, but likely were not significant in this system because of the high levels of Fe

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that would sequester As and S by coprecipitation.40

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The difference in As release between treatments could also be partly attributed

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to the higher imposed osmotic stress of increased salinity on the microbial community

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by seawater. Alkalinity and As release were significantly correlated for both river

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water and seawater, though the correlation was stronger with the river water (r2 = 0.82

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and 0.59, respectively). Alkalinity generation was greater in the river water (5000 mg

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L-1 at -225 mV) than the seawater (3500 mg L-1 at -187 mV), indicating decreased

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microbial activity in the seawater, suggesting microbial inhibition.41 Salinity in soil is

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a major source of stress on soil microbial communities, especially in those regions of

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the world undergoing salinization due to climate change.42 Our results suggest that

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introducing salinity to coastal soils through SLR and storm surges may similarly stress

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the microbial communities in the inundated soils and have secondary effects on soil

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chemistry.43 In the case of As mobilization, rapid introduction of increased salinity

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proved beneficial in these soils by inhibiting dissimilatory metal reducing bacteria

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activity. However, a slow shift from fresh water to more saline conditions, as in the

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case of SLR, may allow the microbial community to adjust by accumulating

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osmolytes.42

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To ensure the experiment was not C limited, glucose and P. australis were

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added and thus resulted in high concentrations of solution DOC. Concentrations of

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DOC were similar for both inundation scenarios, ranging from approximately 1600

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mg L-1 at the onset of the experiment (most reducing conditions) to 800 mg L-1 at the

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conclusion of the experiment (most oxidizing conditions). The decrease in DOC in

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solution with increasing Eh levels may be attributed to increased microbial C

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consumption under more oxidizing conditions, or the microbial utilization of DOC

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over the course of the experiment.34,44 The highest concentrations of As were present

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under the same conditions that the highest concentrations of DOC were observed,

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suggesting more available C can stimulate microbially driven reductive release of As

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from As-bearing oxides. In addition to driving microbial reductive release, DOC can

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also act as a carrier for As, thereby increasing As mobility.45 The DOC-As correlation

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was stronger when inundated with river water (r2 = 0.69) than with seawater (r2 =

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0.38).

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Arsenic release increased notably at Eh values below 100 mV, corresponding

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to the value at which reductive dissolution of Fe oxides begins.46 Reductive Fe-oxide

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dissolution also began for both inundation scenarios near the critical redox level of

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100 mV (Fig. S2). Similar to dissolved As, FeII in solution increased under reducing

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conditions, with the lowest levels of FeII present at the highest Eh levels. Both the

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river water and seawater trials reached maximum concentrations of FeII in solution of

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approximately 1000 mg L-1 under the most reducing conditions (below -200 mV), at

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which time As in solution was also at its peak. Though both inundation scenarios

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demonstrated significant correlations between As and Fe(II), a stronger relationship

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was observed in the freshwater (r2 = 0.82 for river water, r2 = 0.38 for seawater; Fig.

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1). Total solution Fe displayed similar behavior (Fig. S2).

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Arsenic release was correlated with a number of other measured factors,

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including pH, total Fe, alkalinity, and DOC (Fig. 1). A two-factor partial least squares

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model comprised of DOC, Eh, Fe(II), pH, total Fe, and Mn explains eighty percent of

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the data variance (SI). Despite the seawater having a higher initial pH prior to

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inundation, when reacted with the soil, the MC pH decreased below the river water

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MC pH, and remained lower throughout the experiment (SI Fig. 1). The seawater

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maximum pH levels were approximately 1 pH unit below the freshwater trials, likely

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due to the “sea salt effect” (where cation exchange processes cause acidification

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following sea salt-rich inundation) and the hydrolysis of exchangeable metal cations

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(e.g., Al) in the soil.47–49 This slight decrease in pH may have contributed to less As in

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solution in the seawater via increased AsV partitioning to the solid phase at lower

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pH.50

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Solid Phase As Speciation Dynamics Across Eh Zones

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Although As speciation in the unreacted soil, collected and preserved for

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XANES analysis, was primarily AsIII (data not shown), the soils were air dried and

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ground prior to experimentation under oxidization-promoting conditions which led to

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As oxidation prior to experimentation. Arsenic speciation in the reacted soils as

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determined by bulk XANES showed As reduction at the lowest reductive potential for

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both inundation scenarios, which corroborates the solution data. Both scenarios

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produced partial reduction of AsV to AsIII, with AsV present under even the most

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anoxic conditions (Fig. 2). In fact, mixed oxidation states were present at all Eh zones.

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Additionally, authigenic As-S complexes formed in both water treatments (Table 2).

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Under the most reducing conditions, As reduction was more pronounced in river water

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as compared to the seawater, with the linear combination fitting (LCF) results showing

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up to 79% AsIII contribution due to the river water treatment and a maximum of 66%

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AsIII ascribed to the seawater treatment (Table 2). As Eh incrementally moved from

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reducing to oxidizing, As was incrementally oxidized and the proportion of AsIII

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decreased by a total of 18% in the river water systems, and 9% in the seawater

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systems. At the most oxic Eh zone, As solid phase speciation was similar (60% AsIII,

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40% AsV) for both waters (+200±20 mV) (Table 2).

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Seawater trials led to more solid phase AsV across the entire Eh range (Fig. 2,

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Table 2). As mentioned earlier, with As in solution, high levels of SO42- can inhibit

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dissolution and/or dissimilatory reduction of hydrous Fe oxides.16,17 Further

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supporting this, solid phase As speciation shows less reduction of As in the high SO42-

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seawater than the river water.

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Arsenic speciation as determined by µXANES showed the same pattern found

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in the bulk XANES analyses, but provides additional insights into the heterogeneity

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that leads to the mixed oxidation state results shown in the bulk XANES data. Multi-

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energy µXRF mapping of the most reduced and oxic samples from each inundation

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scenario suggests very little, if any, As oxidation states that are not some kind of

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As(III)/As(V) mixture. It is possible that this is a limitation of the method, and perhaps

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the use of a nanoprobe beamline would enable detection of distinct oxidation states.

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Tri-color RGB µXRF maps used to determine elemental colocation of As, Fe, and S

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indicate a stronger correlation between As and Fe in the solid phase with seawater

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than river water, suggesting increased As-Fe sorption compounds (Figure 3). These

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maps also show signs of deflocculation in the seawater with visibly smaller particle

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sizes present in the maps, possibly due to the sodicity of the seawater.

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The mean of all 10 points measured by µXANES at each Eh zone was similar

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to that measured by bulk XANES at the same Eh zones, which indicates that the

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microprobe data adequately represent the heterogeneity present in the bulk XANES

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(SI Table 1). There were three to five components of mixed oxidation states at each Eh

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zone as determined by principal component analysis (PCA) (Fig. 3). Similar to the

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bulk XANES, the more oxic Eh zones were mostly AsV. However, some spots (river

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water 184 mV spot A and seawater 183 mV spot A) were comprised of approximately

340

70% AsIII under these oxidizing conditions. This further demonstrates sample

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heterogeneity and possible influence of microsites on overall As release.

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A parallel, but inverse, phenomenon was found in the most reducing zones.

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The solid phase in the river water treatment showed 4 components of mixed oxidation

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state from the PCA, ranging from 69-85% AsIII, coupled with some As-S precipitation

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at -324 mV. The largest contribution from AsV at this Eh zone was 32% (river water 16


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324 mV, spot D). However, for the seawater microcosms at the lowest Eh zone (-254

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mV), three mixed oxidation state PCA components were identified and none of the

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µXANES indicated less than 28% contribution by AsV (seawater -254 mV spot A).

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The maximum contribution of AsV for the reducing seawater microcosms reached up

350

to 59% (seawater -254 mV spot C).

351

These results further demonstrate decreased AsV reduction in the seawater

352

inundations as compared to the river water inundations. Arsenic release under

353

reducing conditions in soil is primarily a microbially mediated process through

354

dissimilatory reductive dissolution of As-bearing Fe oxides such as ferrihydrite,

355

goethite, lepidocrocite, magnetite, or hematite, but can also occur through direct

356

enzymatic reduction of AsV. The energy requisite for reducing these FeIII minerals,

357

their reactivity, surface area, and As sorption capacity are unique for each Fe oxide.51

358

Under certain environmental conditions, concurrent or preferential SO42- reduction is

359

possible when the Gibbs free energy of sulfate reduction is greater than that of more

360

crystalline phases of FeIII. Because reductive dissolution of Fe oxides is a primary

361

driver of As release from soils, it is therefore reasonable to assume AsV reduction and

362

release is limited in the seawater inundations as compared to the river water by

363

reduced microbial activity.

364

Solid Phase S Speciation Dynamics Across Eh Zones

365

Sulfur speciation, as determined by bulk XANES spectroscopy showed

366

considerable variation between the inundation scenarios (Fig. 4). Solid phase sulfur

367

speciation in the river water inundation was primarily comprised of sulfides and

17



368

pyrite, with their respective contributions being inversely related with changes in Eh –

369

organic sulfides increased with increasing Eh whereas pyrite decreased (Fig. 4, Table

370

S1). The pyrite contribution at low Eh suggests the presence of Fe-As-S coprecipitates

371

under reducing conditions and is in agreement with the solid phase As speciation.

372

Sulfate was only present at 184 mV, comprising 12% of the S speciation.

373

The S speciation in soils inundated with seawater was also predominately

374

organic sulfides and pyrite, but the behavior thereof with changing Eh differed from

375

the river water inundations – pyrite and organic sulfide contributions decreased

376

slightly with increasing Eh (Fig. 4, Table S1). Sulfate contribution to S speciation was

377

greater in the seawater than the river water, and increased with increasing Eh,

378

contributing 16% under low Eh and up to 26% at 184 mV. The lower solid-phase

379

sulfate levels under reducing conditions are likely due to dissimilatory sulfate

380

reduction. Although the amount of sulfate reduction is similar in both river and

381

seawater inundations by percent, the amount of total S in the seawater systems is 100

382

times that of the river water. This suggests that the amount of sulfate reduction

383

occurring in the seawater inundation is much greater by mass than in the river water.

384

This corroborates the hypothesis of concurrent or preferential dissimilatory sulfate

385

reduction in the high sulfate seawater systems, potentially resulting in less As release.

386

Implications for Sea Level Rise

387

Climate change induced seawater inundation, short and/or long term flooding,

388

and salinification will alter the biogeochemistry of these sensitive sites. Newly flooded

389

areas will see formerly oxic zones turn more reducing and thereby change the ability

18


Page 18 of 34

Page 19 of 34


390

of the soils and sediments to sequester contaminants. Our findings show that

391

introducing reducing conditions can lead to an increased As release from soils through

392

dissolution of As-bearing mineral oxides in both river water and seawater inundations

393

scenarios. Additionally, short-term inundation with seawater can lead to less As

394

release than inundation with freshwater due to inhibition of oxide dissolution.

395

Accordingly, the threat of SLR stands to impact release of As from contaminated

396

coastal soils primarily by changing the redox conditions and subsurface mineralogy.

397

Future work should include abiotic controls to further understand the mechanisms of

398

As release and the role of microbial communities under different degrees of

399

salinization on the biogeochemical cycling of As. The compounding issues of SLR

400

and its impacts on the cycling of contaminants in coastal soils is of merit for the

401

communities at coastal areas around the world and calls for an appropriate field

402

monitoring and modern lab-based process-orientated research to better understand the

403

underlying biochemical processes and the associated risks for humans and the

404

environment.

405 406

Acknowledgements

407

This work was made possible by a US Department of Defense SMART Fellowship

408

Program awarded to J.J.L., the National Science Foundation EPSCoR Grant No. IIA-

409

1301765, and the state of Delaware. We are appreciative to the Delaware

410

Environmental Institute (DENIN), Caroline Golt for her ICP expertise, DENIN

411

summer scholars Prian Esquivel and Benjamin Wendt for help in collecting and

19



412

preparing samples, and John Cargill and others of the Delaware Department of Natural

413

Resources and Environmental Control for assistance in gaining permissions for field

414

sampling. Thank you to the staff at the Stanford Synchrotron Radiation Lightsource

415

for support. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National

416

Accelerator Laboratory is supported by the US Department of Energy, Office of

417

Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515.

418 419

Supporting Information

420

Details of microcosm experimental methods, bulk X-ray absorption spectroscopy, and

421

figures detailing redox potential, iron, DOC and sulfate in solution, and bulk sulfur

422

XANES results.

423 424

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27



579

TABLES

580

Table 1:

Soil Collection Site

Soil and water characterization

Depth

Texture

(cm) Wilmington, DE, USA

0-20

Loam

EC Water Type

Mean Particle Size (µm)

pH

737

5.9

DOC

Amorphous Hydrous Fe Oxides

Total Fe

Al

As

------------------------- (mg g-1) -------------------------

Ca

97.01

Mg

72.25

Na

As

pH

16.27

Total Fe

13.30

Mn

S

-------------------------- (mg L-1) --------------------------

(mmhos/cm)

581

Page 28 of 34

River

7.2

0.7

4.4

24

9.4

42.4

bd*

0.04

bd

7.8

Sea

7.8

45.6

5.5

369

1091

7153

bd

0.08

bd

789

*bd indicates values that were below the detection limit (0.5 µg L-1 for As and 3 µg L-1 for Mn)

28


Cr

Pb

Mn

S

------------ (mg kg-1) -----------62

360

558

4157

Page 29 of 34

582


Table 2:

Arsenic bulk XANES linear combination fit results..

583 Sea Water Eh6h (mV) 183 169 125 120 10 -25 -94 -127 -187 -188 -240 -254

As As5+ ------------------------(%)-----------------------0 57 43 0 57 43 7 56 37 6 56 38 7 59 34 7 59 34 9 63 28 9 61 30 9 62 29 9 61 30 8 60 32 8 66 26

del-E (eV) 0.4 0.3 -0.13 0.28 -0.11 0.31 -0.25 0.36 -0.43 0.25 0.2 -0.58

River Water As-S As As5+ ------------------------(%)-----------------------0 60 40 0 63 37 8 60 32 8 64 28 10 67 23 11 68 21 12 71 17 11 69 20 11 73 17 11 75 14 10 76 13 10 79 11

del-E (eV) 0.22 -0.81 0.38 -0.56 0.46 -0.62 0.22 -0.69 -0.5 -0.04 -0.2 0.13

As-S*

3+

NSS** 1.06E-03 9.95E-04 1.03E-03 8.80E-04 9.86E-04 8.29E-04 9.24E-04 7.83E-04 9.50E-04 8.01E-04 8.35E-04 8.89E-04

584 585 Eh6h (mV) 185 184 108 81 13 -19 -117 -118 -214 -225 -314 -318 586 587 588 589 590 591

3+

NSS 1.10E-03 1.13E-03 8.49E-04 9.71E-04 8.26E-04 8.86E-04 7.45E-04 8.29E-04 8.02E-04 7.31E-04 8.02E-04 7.12E-04

*The standard used for linear combination fitting that is represented by As-S was realgar (AsS or α-As4S4). **NSS = normalized sum of squares residual of the fit, determined by NSS = Σ(y – yfit)2)/Σ(y2). The standards used for As3+ and As5+ were sodium arsenite and sodium arsenate, respectively. Inclusion of each component was required to 1) improve the NSS by at least 10% and 2) represent at least 5% of the measured signal.

29 ACS Paragon Plus Environment


295x238mm (300 x 300 DPI)


Page 30 of 34

Page 31 of 34


Figure 1. Arsenic in solution as regressed to linked factors. For all bivariate linear regression analyses, n = 20, p value given by analysis of variance 261x187mm (300 x 300 DPI)



Figure 2. A. Arsenic bulk XANES for sea water and river water inundations scenarios across designated Eh windows following 72 h equilibration time at that Eh. The solid lines represent spectra for XANES data and fits obtained by linear combination fitting of the data are dotted lines. B. Weight percent As speciation contribution as determined by linear combination fitting. 262x351mm (300 x 300 DPI)


Page 32 of 34

Page 33 of 34


Figure 3. A. Solid phase As speciation changes via XRF and XANES spectroscopy. River water spectra are expressed in orange and sea water are in purple, with the darker shades indicating lower Eh values. Data are represented by the solid lines and fits obtained by linear combination fitting are dotted lines. B. In the tri-color RBG maps red represents As, blue represents Fe, and green represents S. 195x154mm (300 x 300 DPI)



Figure 4. A. Solid phase S speciation changes via bulk XANES. River water spectra are expressed in orange and sea water are purple, with the darker shades indicating lower Eh values. Data are represented by the solid lines and fits obtained by linear combination fitting are dotted lines. Linear combination fitting was performed using sulfate ester, pyrite, diphenylsulfoxide, and organic sulfides (methionine, cystine, and diphenyldisulfide). B. Weight percent As speciation contribution as determined by linear combination fitting. 193x127mm (300 x 300 DPI)


Page 34 of 34

Sea Level Rise Induced Arsenic Release from Historically

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