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Environmental Processes

Biogeochemical controls on strontium fate at the sediment – water interface of two groundwater-fed wetlands with contrasting hydrologic regimes Antoine Boyer, Mélisa Hatat-Fraile, and Elodie Passeport Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.8b01876 • Publication Date (Web): 22 Jun 2018 Downloaded from http://pubs.acs.org on July 7, 2018

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Biogeochemical controls on strontium fate at the sediment – water

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interface of two groundwater-fed wetlands with contrasting

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hydrologic regimes

4 Antoine Boyer1, Mélisa Hatat-Fraile2, Elodie Passeport1,2*

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6 7 8

Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College Street, Toronto, M5S 3E5, CANADA

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Department of Civil and Mineral Engineering, University of Toronto, 35 St George St., Toronto,

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M5S 1A4, CANADA

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* Corresponding author: Telephone: +1 416-978-5747. Email: [email protected].

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Abstract

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Radioactive strontium (Sr) is a common groundwater contaminant at many nuclear sites. Its

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natural retention in groundwater-fed wetlands is an attractive remediation strategy. However,

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at present, the biogeochemical mechanisms controlling Sr transport at the sediment – water

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interface are poorly understood. In this field study, Sr fate was investigated in two wetlands

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with contrasting vegetation and hydrologic regimes. The marsh was an open-water wetland

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with constant water table and no emergent vegetation. The swamp was vegetated with

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fluctuating water levels and a thick mat of submerged cattail litter in the water column. High-

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resolution porewater Sr concentrations and solid-phase sediment Sr species revealed distinct

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profiles between the two wetlands. The marsh exhibited a strongly reduced environment and

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sharp concentration peaks at the sediment – water interface. In contrast, the smaller

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concentration gradients of the swamp resulted in a reduced flux of Sr to the surface water. The

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organic fraction of the sediment dominated Sr retention compared to the inorganic iron and

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manganese oxides. However, the marsh had a significant fraction of recalcitrant Sr presumably

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due to its incorporation into sulphur and/or carbonate minerals. These results suggest that

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vegetated wetlands with fluctuating hydrologic regimes could act as efficient sinks for Sr

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pollution.

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TOC graphic

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Introduction

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Strontium is a widely distributed alkaline earth metal whose mobility is controlled by

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incorporation into minerals and adsorption onto organic and inorganic compounds. The isotope

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90

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irradiation.5 Due to its high mobility, it quickly enters groundwater resources through

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infiltration of contaminated water6,7 or the leaching of wastes,1,3,8 where nuclear facilities such

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as reactors or waste management areas are present.4 Despite stricter environmental and

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security regulations, the expected increase in the world’s total nuclear electricity production by

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20509 could result in more sites being contaminated with 90Sr. At such sites, many

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groundwater-fed wetlands are present, thus becoming a pathway of 90Sr to surface water. The

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potential to use wetlands as a remediation strategy to retain 90Sr pollution deserves further

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attention. The top 10 cm of wetland sediments, called the benthic boundary, hosts various

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macro-organisms whose exposure to 90Sr amplifies the transfer of the radionuclide through the

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food chain. To protect this key environmental compartment, a better understanding of Sr fate

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at the sediment – water interface is required.

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To date, very limited research has evaluated the fate of Sr in wetlands.10–12 Kröpfelová

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et al.11 and Šíma et al.10 investigated the inlet versus outlet Sr removal efficiency of horizontal

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subsurface flow wetlands receiving municipal wastewater. Limited removal, < 28%, was

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observed for influent Sr concentrations ranging from 234 to 840 μg/L.10 In contrast, through

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laboratory column experiments, Thorpe et al. showed that both oxic and anoxic subsurface

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sand/gravel sediments had a high capacity for Sr adsorption.13 Boyer et al.12 conducted a

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detailed characterization of the Sr adsorption and desorption potentials of various wetland

Sr is a toxic radiochemical with a half-life of 28.8 years1–4 that is only produced by nuclear fuel

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substrates. The authors reported very large Koc adsorption coefficients, ranging from 549 ± 5

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L/kg for leaf litter to 5,960 ± 150 L/kg for moss. Limited desorption was observed, in particular

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for substrates rich in proteins.

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Wetland sediments encompass a wide range of redox and microbial conditions, which are a

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result of large quantities of organic matter and frequent fluctuations of the water level.14

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Although Sr itself is not a redox-sensitive species, remaining at its Sr2+ oxidation state below pH

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13 regardless of the redox potential,15,16 Sr fate can be affected by changes in redox conditions

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due to its complexation with redox-sensitive species. For example, Sr sulfide can form as a

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result of hydrogen sulfide production by sulfate-reducing microorganisms.17,18 However, unlike

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other metals such as copper, arsenic, and iron, Sr sulfide is soluble.10,11 Strontium sulfate, which

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is mostly insoluble, is not expected to form in wetlands since it forms only at high pH and Sr

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concentrations.19

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Iron(III) and manganese(III/IV) oxyhydroxides are well-known sorbents for Sr.6,20,21 However,

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their contribution to removing Sr from sediment porewater is only temporary as Sr can be

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released under anoxic conditions upon reductive dissolution of the oxyhydroxides.22 In addition,

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Frohne et al.23 showed that Sr may not complex with all oxyhydroxides, and other authors have

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suggested that Sr complexes with soil organic matter may have been mistaken as complexes

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with oxyhydroxides.20,24 Indeed, Sr can also adsorb on organic material,12,25 as well as

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carbonates21,26–28 and clay minerals such as montmorillonite, kaolinite, and illite.29–31 While

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Boyer et al.12 highlighted the role of organic matter and specific functional groups in the strong

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retention of Sr, to date, the relative contributions of organic matter and inorganic compounds

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for Sr retention in wetland sediments is still unclear.

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The goal of this study was to compare the speciation of Sr at the sediment – water interface of

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two wetlands with different vegetation and hydrologic regimes. Specifically, the objective was

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to investigate the relative roles of organic and inorganic compounds for Sr fate. The main

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components of the approach were an in situ characterization of steady-state porewater

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biogeochemical signatures and solid-phase sediment chemistry. The implications of the results

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for the management of wetlands receiving Sr-polluted water are discussed.

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Materials and methods

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Site description

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The field study was conducted at the Canadian Nuclear Laboratories (CNL) at Chalk River

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(Ontario, Canada), located about 150 km north-west of Ottawa along the southwestern bank of

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the Ottawa River. Groundwater at the site contains natural Sr. Two groundwater-fed wetlands

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located near the north boundary, a marsh and a swamp, were sampled. The swamp sampling

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location was approximately 130 m upstream of the marsh’s, and both presumably received the

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same input of Sr from the groundwater. The marsh was continuously saturated. Contrarily, the

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water level in the swamp changed significantly during the sampling period, resulting in the

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alternation of flooded vs. partially saturated sediments, as seen in Supporting Information (SI)

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Figure S1. The marsh was an open water wetland with no emergent vegetation but some algae,

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while the swamp was densely vegetated with cattails (Typha latifolia) (SI Figure S2). In the

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swamp, no living plants were present in the immediate vicinity of the porewater and sediment

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sampling locations. However, the swamp surface water had a dense mat of submerged cattail

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litter.

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Field sampling

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The wetland sediment porewater was collected using passive equilibrium samplers called

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peepers, allowing a 1-cm vertical sampling resolution (SI Figure S3). The peepers were covered

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by a 0.22-μm polyvinylidene fluoride membrane (Synder Filtration, Vacaville, USA), previously

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tested to ensure its permeability to Sr (SI Section S2 and Figure S4).

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The peepers were washed with soap and water to remove any machining residues. They were

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then soaked in 5% nitric acid for 2 days and rinsed with deionized (DI) water. The membranes

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were soaked in distilled water for 2 days and DI water for one day, replacing the water every

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day. After cleaning, the peepers were assembled while submerged in DI water. The membrane

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was held in place between the cover and the body of the peeper by multiple nylon screws.

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After assembly, the peepers were placed in a hermetic barrel of DI water where N2 was

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bubbling to keep the water oxygen content below 4%. The peepers were stored and

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transported in the barrel until deployment 5 days after the start of the deoxygenation process.

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A total of four peepers were deployed, two in the swamp, called Swamp-1 and Swamp-2 and

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two in the marsh, called Marsh-1 and Marsh-2 (SI Figure S2). At each location, the two peepers

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were placed about 30 cm away from each other. The peepers were retrieved after 5 weeks in

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the field to allow for equilibrium. Any cells that were not permanently submerged or appeared

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damaged were not sampled. Their submersion was monitored on a weekly visit of the sites. The

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approximate relative depth of the sediment surface, defined as depth zero, for each peeper at

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the time of retrieval was determined by visual observation of residual sediment and

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discoloration on the membrane. At the time of retrieval, the porewater samples from each

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chamber were collected using a syringe (SI Section S1). Peeper retrieval and sample collection

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was completed in less than an hour.

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After the peepers were retrieved, three sediment cores were sampled at each site. The cores

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were sampled less than 20-cm away from their respective peeper locations. The cores were

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sampled and extruded using an Incremental Core Extruding Apparatus from Aquatic Research

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Instruments (Hope, USA). The coring tube was pushed into the sediments manually, sealed and

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the core pulled out. The length of each core was limited by the maximum manual strength that

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could be applied to the coring equipment. On average, the peepers were 63 cm deep in the

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swamp and 61 cm deep in the marsh, but the core depths were 40, 40, and 35 cm in the

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swamp, and 60, 45, and 45 cm in the marsh. The sediment in the swamp was unconsolidated

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and some mixing could have occurred when the core was collected. In the swamp, the depths

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of the sediment cores were shorter than in the marsh due to the difficulty of sampling through

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the consolidation of organic detritus in the swamp sediment. In the marsh, the two 45-cm long

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cores were shorter than the peeper length due to an impenetrable layer of fine sediment,

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which was shallower than in the longer marsh sediment core. The cores were extruded at 5 cm

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intervals, air dried, and stored at room temperature until further analysis.

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Porewater analysis

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All porewater samples were analyzed within one week for dissolved organic carbon (DOC) and

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anions concentrations, and within 2 weeks for metals. Porewater DOC concentrations were

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analysed following EPA procedure 415.1-415.332 with a Fusion UV/Persulfate TOC analyzer

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(Teledyne Tekmar, Mason, USA), and a limit of detection (LOD) of 0.19 mg/L. Anions were

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quantified following EPA method 300.033 with a Dionex ICS-1600 (ThermoFisher Scientific,

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Whaltam, USA) Ion Chromatograph (IC), for nitrate (NO3−), phosphate (PO43−), bromide (Br−),

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sulfate (SO42−), and chloride (Cl−); the LODs were 0.02, 0.19, 0.02, 0.02, 0.02 mg/L, respectively.

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Total iron (Fe), manganese (Mn), calcium (Ca), aluminum (Al), and Sr were analysed following

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EPA method 60034 by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP/OES) with

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a 700-series ICP/OES (Agilent Technologies, Santa Clara, USA), and LODs of 0.07, 0.0008, 0.02,

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0.05, and 0.0006 mg/L, respectively.34

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Sediment analysis

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All 5-cm sediment subsamples were air-dried, ground, and sieved to 2 mm. One gram of sample

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was used for elemental analysis using a LECO SC444 (LECO, Saint Joseph, USA) for total carbon

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(TC), total inorganic carbon (TIC), total organic carbon (TOC), and total nitrogen (TN) analyses.

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The air-dried samples were combusted to CO2 for TC analysis, and were combusted after ashing

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at 475 °C to measure the TIC. The TOC was calculated from the difference between TC and

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TIC.35 The Dumas combustion method was used for TN analysis.36

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Sequential extraction procedures (SEPs) have been widely used to speciate adsorbed metals.37

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To speciate the Sr bound to the wetland sediment, the core samples were sequentially

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extracted using a method adapted from Benitez38 and described in detail in SI Section S3 and

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Table S1. First, the total metals, including total Sr, was determined following a procedure

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adapted from Moldoveanu and Papangelakis.39 Then, four sequential extraction steps were

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completed on a separate sediment sample to quantify Sr in five fractions: F1: exchangeable, F2:

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adsorbed to organic material, F3: adsorbed to Mn oxides and amorphous Fe oxides, F4:

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adsorbed to crystalline Fe oxides, and F5: residual. The residual fraction was obtained by

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subtracting all fractions to the total Sr measured. All extracts’ Sr concentrations were measured

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using the same ICP/OES method as described above for the porewater samples.

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Finally, the particle size distribution was measured on three subsamples from each location

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with a Patrica LA-950 V2 Horiba after rewetting the samples and breaking down the aggregates

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via manual crushing and ultrasonication (SI Section S4).

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Results and discussion

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1. Surface water and porewater

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1.1 Dissolved organic carbon profiles

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The different hydrologic regimes and vegetation caused distinct DOC concentration profiles for

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the swamp and the marsh (Figure 1). The swamp surface water DOC concentrations were 25

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and 26 mg/L for Swamp-1 and Swamp-2, respectively, 1 cm above the sediment surface. The

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swamp porewater DOC concentrations then decreased to 17 and 15 mg/L in Swamp-1 and

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Swamp-2, respectively, at −45 cm. Below −45 cm, a sharp increase in DOC concentrations

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initiated up to 28 mg/L in Swamp-1 and 40 mg/L in Swamp-2. Such an increase in DOC

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porewater concentration in deep horizons of sediments was also observed in other studies.14,40

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For example, Baez-Cazull et al.14 attributed the deep porewater DOC concentration increase, 30

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cm below the sediment surface, to organic acids originating from the partial microbial

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fermentation of organic matter in this zone.

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Swamp-1

Swamp-2

Marsh-1

Marsh-2

b

c

d

e

f

g

h

i

j

Depth [cm]

a

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Figure 1: Porewater concentration gradients for Swamp-1 and 2 (top panels), and Marsh-1 and 2 (bottom panels). The dissolved

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organic carbon (DOC), total iron, total manganese, sulphate, and total strontium concentrations in the two peepers for each

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separate location are plotted using appropriate scales. The straight lines between the data points were drawn to add clarity to the

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figures and do not represent a model. Zero on the vertical axis represents the approximate depth of the sediment surface.

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Similarly, in the present study, the high porewater DOC concentration measured below −45 cm

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was likely a remanence of the emergent vegetation found in the swamp. In contrast, the marsh

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DOC concentration profiles exhibited a sharp DOC concentration peak near the sediment –

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water interface, with maximum porewater DOC concentrations observed at −1 cm. The DOC

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concentration peaks were 52 and 44 mg/L for Marsh-1 and Marsh-2, respectively. This increase

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was followed by a sharp decrease down to −15 cm where DOC concentrations reached 24 and

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23 mg/L for Marsh-1 and Marsh-2, respectively. In the remainder of the marsh vertical profile,

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the DOC concentrations decreased gradually to less than 20 mg/L below −50 cm.

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1.2 Redox geochemistry

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No NO3− was detected in the sediment of both the swamp and the marsh. The reducing

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conditions were therefore anoxic and past the NO3− reducing state. The swamp had lower

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porewater concentrations of total Fe, < 13 mg/L, and total Mn, < 0.7 mg/L, than the marsh with

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up to 52 and 7 mg/L of total Fe and total Mn, respectively (Figure 1). Consistent with these

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ranges, the swamp also had higher SO42− concentrations, up to 2.7 mg/L, than the marsh, < 1.2

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mg/L. These differences between the swamp and the marsh are typical of lower concentrations

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of reduced species in the porewater of environments with fluctuating water tables.41 In both

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the swamp and the marsh, the concentrations of the redox-sensitive species showed a peak

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near or below the sediment – water interface. This peak was sharper in the marsh than in the

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swamp, due to the swamp’s fluctuating water levels that translocated the elements to lower

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depths.41,42

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In Swamp-1, the downward increase in total Fe and Mn concentrations and the decrease in

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SO42− concentrations occurred in parallel from the sediment – water interface down to −20 cm,

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indicating concurrent reduction of SO42−, Fe(III), and Mn(III/IV). A similar pattern was found in

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Swamp-2 except that the increase of total Fe was delayed until −10 cm, suggesting that the

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reduction of Fe(III) occurred after that of SO42−. The reduction of SO42− concurrently or before Fe

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is typically observed in environments with unavailable Fe, significant high concentrations of

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DOC, or high concentrations of SO42−.14 This has been observed by others.14,43,44 The

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concentrations of SO42− in the swamp were not elevated, < 2.7 mg/L, but the DOC

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concentrations, ranging from 25 to 30 mg/L were high.45 It is hypothesized that the reduction of

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SO42− concurrently with or before that of Fe in the top 20 cm of the swamp sediment could

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have been caused by the unavailability of Fe due to its complexation with available DOC.45

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Below −20 cm, the redoxamorphic profile was similar for the two peepers located in the

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swamp: SO42− concentrations increased while total Fe and total Mn concentrations decreased.

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In this −20 to −50 cm interval, SO42− concentrations averaged 1.0 ± 0.3 mg/L. This value is above

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the threshold of 0.5 mg/L defined by Chapelle et al.,46 indicating that the sediments were likely

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still in SO42− reducing conditions and not yet undergoing methanogenesis. The decrease in Fe

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and Mn could indicate that the redox conditions in the wetland are past the reduction of the

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oxyhydroxides, or that Fe and Mn are precipitating with sulfides forming insoluble species.47,48

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The increase in total Fe and total Mn concentrations observed beyond −50 cm in Swamp-1 and

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−45 cm in Swamp-2, could indicate a zone where the reduction of the oxyhydroxides is

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occurring. Alternatively, since these increases correspond in scale and location with the

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increase in DOC concentration for both peepers, the increase in total Fe and Mn concentrations

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could be a result of resuspension of Fe(III) and Mn(III/IV) complexed with organic matter

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colloids smaller than 0.22 µm, the peeper membrane pore size. Similar results were obtained

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by Pullin and Cabaniss,49 who found that Fe(III) could be complexed by fulvic acids in anoxic

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conditions.

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In the marsh, the redoxamorphic conditions were consistent between the duplicate peepers.

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Highly compressed redox gradients were observed at the sediment – water interface. Above

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the sediment – water interface, SO42−, Fe(III), and Mn(III/IV) were reduced concurrently, with

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rapidly changing concentrations of the redox-sensitive species overlapping a narrow vertical

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interval. This reducing zone suggests that the 5 cm in the water column consisted of a floc-like

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ooze layer as described by Kadlec et al.50 The ooze layer consists of a movable layer of loose

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and unconsolidated sediments. The rapid microbial decomposition of algae-derived organic

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matter in this 5-cm deep layer, confirmed by the downward increase in DOC concentration

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could have promoted the observed anoxic conditions that led to the rapid reduction of SO42−,

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Fe(III), and Mn(III/IV). This scenario was also observed by Baez-Cazull et al.,14 who attributed it

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to a microzone of anaerobic conditions driven by dense suspended organic material. In the top

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layer of the marsh sediment, from 0 to −5 cm, the sediments appeared to oxidize, i.e. they

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became less anoxic, as the concentrations of total Fe and total Mn dropped while those of SO42−

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increased, but NO3− concentrations were still below detection. The redox conditions stabilized

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at −10 cm, where SO42− reducing conditions dominated. Similarly, as observed in the swamp,

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the high concentration of DOC from −10 to −20 cm could have reduced the availability of the

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oxyhydroxides contributing to the reduction of SO42− before that of Fe(III) and Mn(III/IV).

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Between −20 and −40 cm, total Fe and total Mn concentrations increased suggesting the

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reduction of Fe(III) and Mn(III/IV). In this depth interval, the SO42− stabilised at 0.60 ± 0.07, close

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to the threshold of 0.5 mg/L defined by Chapelle et al.46

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Altogether, (i) the constant water level of the marsh compared to the fluctuating one in the

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swamp, (ii) the higher porewater concentrations of total Fe and total Mn in the marsh than in

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the swamp, (iii) the porewater Fe, Mn, and SO42− concentration profiles discussed above, and

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(iv) the higher pH of the marsh (6.5 – 6.9) compared to the swamp (5.9 – 6.4) (SI Figure S6) all

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point to the marsh sediments being in a more reduced state than the swamp sediments, and

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potentially in methanogenesis.

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1.3 Total dissolved strontium

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The total dissolved Sr concentrations include the soluble Sr cation Sr2+ and any other Sr

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complexes smaller than 0.22 µm. The porewater Sr concentrations were the highest at the

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bottom of the sediment profiles, due to Sr-containing groundwater input in the two wetlands

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(Figure 1). At the sediment – water interface of both locations, dissolved Sr concentrations

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were low, < 0.06 mg/L except for Swamp-2, suggesting that the wetland sediments were able to

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attenuate Sr and protect the overlaying surface water and benthic zone (0 to −20 cm) from Sr

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contamination. The total porewater Sr concentrations exhibited a gradual downward increase

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in the sediment of both locations, up to maximum concentrations of 0.19 mg/L in the swamp

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and 0.37 mg/L in the marsh at the bottom of the profiles. While they increased significantly by

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122% and 133% in Marsh-1 and Marsh-2, respectively, over the whole 60 cm length of the

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marsh sediment profiles, in the swamp, total Sr concentrations only increased by 47% and 49%

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in Swamp-1 and Swamp-2, respectively. A larger Sr concentration gradient was observed along

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the whole sediment profile of the marsh, and in particular at the sediment – water interface.

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This suggests that a faster upward diffusive transport of Sr to the wetland surface water was

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occurring in the marsh compared to the swamp.

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2. Sediments

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2.1 Total organic carbon and total nitrogen

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In the marsh, the TOC and TN concentrations were lower than in the swamp, consistent with

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the open water of the sampling location in the marsh and the presence of dense vegetation in

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the swamp. The TOC concentrations ranged from 0.5 to 13 % in the marsh and 15 to 24 % in the

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swamp, while those of TN were in the range of 0.2 to 1.2 % in the marsh and 0.7 to 1.7 % in the

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swamp (SI Figure S7).

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Within each location, the three sediment cores showed a consistent general decreasing trend in

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TOC concentrations, in line with the general porewater DOC concentration decrease observed

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at both locations. This results from the decomposition of sediment organic matter throughout

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the profile and an input of fresh organic material at the top of wetland sediments from the

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swamp cattail litter and marsh algae. However, in one of the three cores collected in the

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swamp, core A, an increase in TOC content was observed between −17.5 cm at 16% and −37.5

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cm at 21%, likely due to the localized presence of organic material. There were no significant

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changes in porewater DOC concentrations in any of the two swamp peepers at the

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corresponding depths. It is possible that the peepers did not intersect the local organic material

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found in core A. Alternatively, slower microbial activity, as indicated by the decrease in TN in

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core A, could have limited the breakdown of the sediment TOC into more labile dissolved

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organic molecules.

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The molar TOC/TN ratios were 22 ± 4 and 12 ± 2 for the swamp and the marsh, respectively (SI

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Figure S8). The different ratios are representative of the respective sources of soil nitrogen. For

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both sediments, a portion of the nitrogen was from microbial origin, with an expected TOC/TN

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ratio at approximately 6.51 The low TOC/TN ratio of the marsh can be explained by the low

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TOC/TN ratio of algae, typically between 8 ± 2 52,53 and 12.54 In contrast, the higher TOC/TN

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ratio of the swamp compared to the marsh was due to the contribution of the emergent

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vegetation of the swamp. Indeed, typical TOC/TN ratios of emergent vegetation range from 45

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to 50,54 with values up to 79 ± 14 for Typha species.53 The gradual downward increase in the

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TOC:TN ratio of the swamp sediments (SI Figure S8) could be a result of a decrease in the

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contribution of microbial-derived nitrogen resulting from lower microbial activity.

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2.2 Solid-phase manganese and iron

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The marsh sediments, on average, had higher concentrations of Fe, by 27%, and Mn, by 76%,

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than the swamp sediments (SI Figure S7). This is consistent with the observed swamp and

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marsh porewater Fe and Mn concentrations, which were higher in the marsh than in the

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swamp, by a factor of 4 and 10, respectively. Characteristic of the reduced environment, the

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total Mn concentrations decreased with depth in both the swamp and the marsh: from 0.53 ±

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0.06 to 0.25 ± 0.04 mg/g in the marsh, and 0.27 ± 0.03 to 0.14 ± 0.02 mg/g in the swamp. Unlike

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Mn depletion, Fe depletion did not start at the sediment – water interface. Rather, the

ACS Paragon Plus Environment

Environmental Science & Technology 18

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downward decrease in Fe concentrations started between −12.5 and −22.5 cm in the swamp,

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and between −17.5 and −47.5 cm in the marsh.

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2.3 Cation exchange capacity

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In general, the CEC decreased downward in the marsh and increased downward in the swamp

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(SI Figure S7). The marsh CEC decrease with depth was linearly correlated with the decrease in

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TOC content with an R2 value of 0.87; whereas, the swamp CEC and TOC content did not

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correlate. The particle size distribution analysis revealed that neither the swamp nor the marsh

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had significant clay content (particle size diameter < 2 μm) (SI Figure S5). However, the marsh,

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classified as a silt loam, had finer particles than the swamp, whose texture was sandy loam. At

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both locations, the particle size distribution drifted towards finer particle sizes with increasing

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depth. This suggests that the main contributor to CEC was the organic matter, as also found by

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Helling et al.55 It is likely that the higher CEC observed in the swamp was a result of the higher

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TOC content, between 15 and 25%, than in the marsh where the concentration in TOC was

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