Science of the Total Environment 649 (2019) 264–283

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Iron sulfide formation in young and rapidly-deposited permeable sands

at the land-sea transition zone
Stephan L. Seibert a,⁎, Michael E. Böttcher b, Florian Schubert b, Thomas Pollmann c, Luise Giani c,
Sumiko Tsukamoto d, Manfred Frechen d, Holger Freund e, Hannelore Waska f, Heike Simon f, Tobias Holt a,
Janek Greskowiak a, Gudrun Massmann a
a
Hydrogeology and Landscape Hydrology Group, Institute for Biology and Environmental Sciences, Carl von Ossietzky University of Oldenburg, Ammerländer Heerstraße 114-118, D-26129 Olden-
burg, Germany
b
Geochemistry and Isotope Biogeochemistry Group, Department of Marine Geology, Leibniz Institute for Baltic Sea Research (IOW), D-18119 Warnemünde, Germany
c
Soil Science Group, Institute for Biology and Environmental Sciences, Carl von Ossietzky University of Oldenburg, Ammerländer Heerstraße 114-118, D-26129 Oldenburg, Germany
d
Leibniz Institute for Applied Geophysics (LIAG), S3: Geochronology and Isotope Hydrology, Stilleweg 2, D-30655 Hannover, Germany
e
Geoecology Group, Institute for Chemistry and Biology of the Marine Environment (ICBM), Carl von Ossietzky University of Oldenburg, Schleusenstr. 1, D-26382 Wilhelmshaven, Germany
f
Research Group for Marine Geochemistry (ICBM-MPI Bridging Group), Institute for Chemistry and Biology of the Marine Environment (ICBM), Carl von Ossietzky University of Oldenburg, D-
26129 Oldenburg, Germany

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Biogeochemical cycles in coastal

organic-poor, permeable sands are not
well studied.
• Our multidisciplinary approach covers
aspects of coastal litho- and hydro-
spheres.
• Methods include hydrogeochemical,
sulfur isotope, DOM, and OSL age inves-
tigations.
• SRR are extremely low and organic car-
bon limits iron sulfide formation.
• Biogeochemical cycles are linked to
(seasonal) hydrochemical variations.

a r t i c l e i n f o a b s t r a c t

Article history: Organic-poor, permeable quartz sands are often present at land-sea transition zones in coastal regions. Yet, the
Received 6 June 2018 biogeochemical cycles of carbon, sulfur, and iron are not well studied here. The aim of this work was, therefore,
Received in revised form 20 August 2018 to improve our understanding regarding the chemical processes in these prominent coastal sediments. A 10 m
Accepted 20 August 2018
core was collected at a dune base of the barrier island Spiekeroog, Germany, for this purpose. Additionally,
Available online 23 August 2018
groundwater was sampled from a multi-level well for one year to record seasonal hydrochemical variations.
Editor: José Virgílio Cruz Methods included the analyses of geochemical (total carbon, total inorganic carbon, reactive iron, total sulfur, re-
duced inorganic sulfur) and hydrochemical parameters (field parameters, major ions, DOC, and molecular com-
Keywords: positions of DOM), as well as stable sulfur isotopes (δ34S-sulfate, -sulfide, -total reduced inorganic sulfur).
Pyrite formation Moreover, optically stimulated luminescence (OSL) dating was applied. Results show that the core sediments
Stable sulfur isotopes are very young (b500 a) and were rapidly deposited. They are characterized by remarkably low contents of or-
OSL dating ganic carbon (b0.1% dw.), reactive iron (~10 mmol/kg), and iron sulfides (b3 mmol/kg). Groundwater salinities
Barrier island were low in the top core sediments and increased at depth during most times of the year. However, the sampling
Spiekeroog Island
site is subject to (seasonally) varying salinities, which could be linked to the biogeochemical cycles. For instance,
Subterranean estuary

⁎ Corresponding author.
E-mail address: stephan.seibert@uni-oldenburg.de (S.L. Seibert).

https://doi.org/10.1016/j.scitotenv.2018.08.278
0048-9697/© 2018 Elsevier B.V. All rights reserved.
 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283 265

the infiltration of seawater-derived labile DOM during inundation events drives microbial respiration besides
sedimentary organic matter. Oxygen and nitrate were the dominant electron acceptors for the decomposition
of organic matter in near-surface groundwater, while sulfate reduction was constrained to the lower brackish
sediments. Here, authigenic pyrite formation was inferred based on the detection of dissolved sulfide, intact py-
rite framboids, and matching stable sulfur isotope signatures of dissolved and solid sulfides. We concluded that
the extremely low organic carbon contents limit pyrite formation in the organic-poor, permeable quartz sands.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction the marine environment were previously attributed to a cycling of sul-

The environmental cycles of carbon, sulfur and iron are tightly linked
to each other. Organic matter is constantly produced, degraded, and de-
posited in all marine and terrestrial ecosystems (e.g., Burdige, 2007).
Sulfur in the form of sulfate is a major constituent in seawater
(Howarth, 1984) and present in the atmosphere. Furthermore, iron is
delivered to the sea as nanoparticulate (oxyhdr)oxides (e.g., Moore
and Braucher, 2008; Raiswell et al., 2008; Tagliabue et al., 2009;
Raiswell and Canfield, 2012).
In (marine) sediments, redox conditions rapidly become reducing in
the presence of reactive organic matter (e.g., Canfield et al., 1993a;
Thamdrup et al., 1994; Al-Raei et al., 2009), resulting in the anaerobic
oxidation of organic carbon using mainly sulfate as electron acceptor
(Jørgensen, 1982). The reduction of metal oxides (i.e., iron (oxyhdr)ox-
ides and manganese oxides) is often less relevant for the bulk oxidation
of organic carbon and may proceed via microbes (e.g., Nealson and
Myers, 1990; Lovley, 1991) or coupled to the chemical oxidation of re-
duced sulfide species (e.g., Canfield, 1989; Thamdrup et al., 1994;
Gagnon et al., 1995; Blonder et al., 2017). Methanogenesis classically
presents the terminal stage in the redox sequence (Berner, 1981). How-
ever, zones of iron (oxyhdr)oxide and sulfate reduction and
methanogenesis are often not strictly separated in nature and may over-
lap, depending on iron (oxyhdr)oxide stability, sulfate concentrations,
and substrate levels (e.g., Postma and Jakobsen, 1996; Jakobsen and
Postma, 1999). The role of sulfate as the prominent electron acceptor
in marine sediments was recently corroborated by Hansel et al.
(2015), who suggested that sulfate reduction may precede the
reduction of all types of iron (oxyhdr)oxides, including ferrihydrite,
even at low sulfate concentrations, a finding challenging classical,
thermodynamic-based redox models (e.g., Berner, 1981; Lovley
and Phillips, 1987; Lovley and Goodwin, 1988; Chapelle and Lovley,
1992).
As reaction products of anaerobic organic matter degradation, sul-
fide and ferrous iron are formed that may react to form iron sulfides
like mackinawite, greigite, and finally pyrite (e.g., Berner, 1970;
Luther, 1991; Wilkin and Barnes, 1996; Passier et al., 1997; Rickard
and Luther, 1997; Neretin et al., 2004; Schoonen, 2004; Rickard
and Morse, 2005; Raiswell and Canfield, 2012). The formation/transfor-
mation processes of iron sulfides are inherently coupled to the availabil-
ity of reactive organic matter, sulfate, and iron (oxyhydr)oxides
(e.g., Berner, 1970; Berner and Raiswell, 1984; Lyons and Berner,
1992; Morse et al., 2007), and the application of geochemical indicators
(e.g., C/S ratio, degree of pyritization (DOP), acid volatile sulfide (AVS)/
pyrite ratio) proved useful in investigating the environmental condi-
tions during their formation more closely (Raiswell and Canfield, 2012).
Stable sulfur isotope signatures of dissolved sulfate and sulfide as
well as solid iron sulfides have been widely used as additional tools to
study sulfur sources and biogeochemical processes (e.g., Passier et al.,
1997; Böttcher et al., 2004; Kunzmann et al., 2017). This is applicable
because bacterially mediated sulfate reduction as well as oxidation of
sulfides and disproportionation of sulfur intermediates are associated
with distinct isotope fractionations (Nakai and Jensen, 1964; Canfield
and Thamdrup, 1994; Habicht et al., 1998; Cypionka et al., 1998;
Böttcher et al., 2005). High stable sulfur isotope discrimination between
dissolved sulfate and reduced sulfide of up to about 50‰ observed in
fur species, including re-oxidation of dissolved sulfide and subsequent
disproportionation of sulfur intermediates (Canfield and Thamdrup,
1994; Habicht et al., 1998; Habicht and Canfield, 2001). More recent
studies, however, demonstrated that high isotope discrimination may
also be achieved by dissimilatory sulfate reduction alone (Wortmann
et al., 2001; Rudnicki et al., 2001; Canfield et al., 2010; Sim et al.,
2011) and that the reactivity of the electron donors may be involved
in the developing sulfur isotope discrimination (Kaplan and
Rittenberg, 1964; Sim et al., 2011).
Mineral structures of iron sulfides present a further means to inves-
tigate chemical conditions during formation (e.g., Wilkin et al., 1996;
Böttcher and Lepland, 2000; Merinero et al., 2009; Lin et al., 2016). As
an example, size distribution and variability of pyrite framboids were
successfully used to infer the redox conditions during sediment deposi-
tion or to distinguish between syngenetic and diagenetic pyrite forma-
tion (e.g., Wilkin et al., 1996).
The intense study of isotope biogeochemistry in coastal environ-
ments has substantially improved our understanding of carbon, sulfur,
and iron cycles in the past three decades. Studies were carried out in
fully/brackish marine (e.g., Canfield et al., 1993a; Thamdrup et al.,
1994; Gagnon et al., 1995; Neretin et al., 2004; Neumann et al., 2005),
(semi)euxinic (e.g., Lyons and Berner, 1992; Middelburg, 1991), estua-
rine (e.g., Morse et al., 2007; Morgan et al., 2012; Kraal et al., 2013),
marsh (e.g., Luther and Church, 1988; Dellwig et al., 2002), and fresh-
water environments (e.g., Marnette et al., 1993; Huerta-Diaz et al.,
1998; Canfield et al., 2010). However, very little is known about the cy-
cling of redox sensitive elements, including the formation of iron sul-
fides, in permeable sands with low organic carbon and reactive iron
contents, as only few studies were carried out in such environments
(Böttcher et al., 1998, 2004; Jakobsen and Postma, 1999; Al-Raei et al.,
2009).
The aim of this study was to assess the cycling of carbon, sulfur, and
iron in organic-poor, permeable Holocene sands under the influence of
fresh to brackish groundwater salinities. Investigations were carried out
at the currently developing Ostplate, which forms the eastern part of the
barrier island Spiekeroog, southern North Sea, Germany. Main objec-
tives were to study the geochemical conditions and limiting factors of
pyrite formation in such an environment and to assess the effect of vary-
ing salinity and redox gradients on the biogeochemical cycles. Interpre-
tations are based on a combination of geochemical, hydrochemical,
stable sulfur isotope, and mineral structure investigations, as well as op-
tically stimulated luminescence (OSL) dating.
2. Methodology
2.1. Study site
Core and groundwater sampling were carried out at the Ostplate,
which is the eastern part of the barrier island Spiekeroog, Germany
(Fig. 1a). Spiekeroog Island is located in the southern North Sea in
front of the North German coastline. It has a west-to-east extent of
~9.8 km and a total surface area of ~21.3 km2 (Streif, 1990). To the
east, the tidal inlet Harle separates it from the neighboring island
Wangerooge. The local tidal range of the North Sea is 2.72 m, with a
mean high water of 1.39 m above sea level (masl) and a mean low
266 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283

Fig. 1. a) Location of Spiekeroog Island at the North German coast line. Dotted areas present dune areas N3 masl after Röper et al. (2013), and the thick black lines indicate the positions of
the freshwater lens in the west (Tronicke, 1997) and the near-surface freshwater extent at the Ostplate (Holt et al., 2017), respectively. The red line indicates the cross-section A-A', where
core sampling site and groundwater monitoring wells are located. b) Cross section A-A'. The core sampling site (ground surface elevation = 3.18 masl) at monitoring site DN is indicated,
including the location of the four monitoring wells DN-a, -b, -c, and -d. The elevation profile was obtained from a digital elevation model of the year 2014 (Lower Saxony Water
Management, Coastal Defense and Nature Conservation Agency, NLWKN, 2014). Dotted vertical lines indicate the level of highest high water (hhw, 4.14 masl, Federal Waterways and
Shipping Administration (WSV, 2016)), and blue and red areas conceptualize the assumed extent of the freshwater lens during sampling in April 2016. Question marks indicate that
the exact position of the freshwater saltwater interface is unknown. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this
article.)

water of 1.33 m below sea level (mbsl; annual means from 1995 to
2015, Federal Waterways and Shipping Administration (WSV, 2016)).
While the oldest part of the west of Spiekeroog Island dates from
~1650 and was formed due to the aggregation of aeolian and marine
sands (Sindowski, 1970), the Ostplate developed more recently as a
consequence of land reclamation activities at the mainland. The latter
resulted in a change of currents and the progressive filling and eastward
migration of the former Harle inlet. The filling of the inlet at the Ostplate
proceeded via six distinguishable cycles of sand deposition that oc-
curred after 1650 (cycles 1–4) and before 1600 (cycles 5–6), according
to Sindowski (1968). A prominent dune ridge with secondary dunes
started to form at the Ostplate around 1940. Progressively increasing
in width and height, it allowed for the formation of freshwater lenses
(Röper et al., 2013; Fig. 1a). Holt et al. (2017) further assessed that the
near-surface extent of these freshwater lenses is highly sensitive to sea-
sonal inundation events.
The upper 40 to 60 m of the geologic units in the Spiekeroog area
mainly consist of fine to coarse-grained, permeable quartz sands of Plio-
cene, Pleistocene, and Holocene origin, deposited under changing fluvia-
tile, marine, and aeolian regimes (compare Röper et al., 2013; Seibert
et al., 2018). Minor sediment fractions comprise shell debris, low amounts
of silt and clay, and local embeddings of peat at greater depth. The Holo-
cene base is located at ~14 to 18 mbsl at the study site (LBEG, 2018).
2.2. Core drilling and well construction
Employing dry drilling and using a Nordmeyer DSB-3.4 L well rig, an
undisturbed 10 m sediment core was collected at the Ostplate on 15/03/
2016 during the construction of groundwater monitoring wells at the
northern dune base facing the North Sea (referred to as monitoring
site ‘DN’, Fig. 1b). The core was stored cool and dry in non-transparent
casings until further processing. Three groundwater monitoring wells
(DN-a, -b, and -c) are situated in direct vicinity of the core sampling
site (b2 m distance), and one monitoring well (DN-d) was installed in
the bore of the collected core. All wells have a screen length of 1 m
each and are located at 10.1-9.1 (DN-d), 8.1-7.1 (DN-c), 5.3-4.3 (DN-
b) and 2.0-1.0 (DN-a) m below ground surface (mbgs), respectively
(Fig. 1b).
2.3. Sediment sampling and analysis
Sediment sampling was carried out at the Luminescence Laboratory
of the Leibniz Institute for Applied Geophysics (LIAG) in July 2016 and
included the collection of 8 and 31 subsamples for sediment OSL dating
and geochemical analysis, respectively. Subsamples allotted for OSL dat-
ing were collected from ~0.5 to 7.4 m depth in ~100 cm intervals under
 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283
subdued red light. Additional subsamples for gamma spectrometry
measurements for the determination of the radionuclide concentrations
were collected at each depth. OSL dating could not be carried out for
core sediments at depths N7.4 mbgs, as the high contents of shell debris
impeded the sampling procedure.
For the geochemical analyses, two replicate samples were collected
at sampling intervals of ~30 cm. The first replicates were stored in
60 cm3 centrifuge tubes and subsequently used for the determination
of water content, sedimentary total carbon (TC), total inorganic carbon
(TIC), reactive iron (Fedith, FeHCl), and total sulfur (TS) contents, grain
size distributions, and microscopic analyses of sediment minerals. The
second replicate samples were filled and preserved in 60 cm3 centrifuge
tubes, containing 10 mL of a 20% ZnAc solution, and later used for the
determination of total reduced solid inorganic sulfur (TRIS) contents
and stable sulfur isotope analyses. All samples were immediately stored
in a refrigerator box and frozen within 4 to 6 h after sampling.
The sediment water content of all samples was determined gravi-
metrically by weighing a sediment aliquot before and after freeze-
drying. All samples were sieved afterwards, and only the fraction
b1 mm was processed for geochemical analysis. The fraction N1 mm
consisted of shell fragments only and was used to determine shell con-
tents. TC, TIC, and TS were analyzed using an Eltra CS 580 device, and
total organic carbon (TOC) contents were obtained by subtracting TIC
from TC. Replicate measurements of TC were carried out for 13% (n =
4) of the total sample number, and results were in very good agreement
with each other (average deviation b5%, Fig. A.1.1).
The buffered dithionite (Fedith.) as well as the cold 0.5 M hydro-
chloric acid (FeHCl) extraction methods were used (Raiswell et al.,
1994) to extract the sedimentary reactive iron fraction available for
early diagenetic reaction with dissolved sulfide (e.g., Canfield,
1989). The citrate-dithionite method quantitatively leaches iron
from reactive iron (oxyhydr)oxides (i.e., ferrihydrite, lepidocrocite,
goethite, and hematite) and some iron carbonates (e.g., siderite).
The cold HCl method only extracts iron from poorly-crystalline iron
(oxyhydr)oxides (e.g., ferrihydrite and some lepidocrocite), iron car-
bonates, and some iron silicate phases (Canfield, 1989; Raiswell
et al., 1994). Iron(II) derived from FeS is extracted by both methods.
Iron was determined as Fe2+ after reduction with hydroxylamine
hydrochloride via spectrophotometry, using ferrozine as the
complexing agent following Stookey (1970). Replicate measure-
ments of Fedith. were carried out for all samples and showed a good
overall agreement (Fig. A.2.1).
The AVS (essentially mackinawite, FeS) and chromium reducible
sulfur (CRS; essentially pyrite, FeS2, and elemental sulfur, S0) fractions
in the sediments were determined for selected samples by a two-step
sequential extraction (Fossing and Jørgensen, 1989), using 5 g sediment
aliquots. The AVS fraction was first extracted by the reaction with 1 M
HCl for 1 h under a continuous stream of N2 gas. Potential H2S released
was quantitatively precipitated as ZnS, and concentrations were deter-
mined spectrophotometrically with a Specord 40 spectrophotometer
following the method of Cline (1969). The CRS fraction was extracted
from the remainder of the sample in a second step, using a hot acidic
Cr(II)chloride solution. As for the AVS procedure, emerging H2S was
trapped in ZnAc during the CRS distillation, and concentrations were de-
termined by spectrophotometry using the precipitated ZnS. TRIS (total
reducible inorganic sulfur) is the sum of the AVS and CRS fractions.
AVS was not detected in any sample, and TRIS contents could not be
quantified in sediments at ~2 to 7 mbgs, as no ZnS precipitation was ob-
served. For the δ34S analysis of sedimentary TRIS, the CRS fraction was
directly precipitated as Ag2S in a trap of 0.1 M AgNO3 solution, with sub-
sequent filtration, washing, and drying of the precipitate as described by
Böttcher et al. (2000).
Dry weights of all solid phase contents were corrected for the salt
contribution of pore waters, which remained attached to the sediments
after freeze drying (Appendix A.3). Sedimentary sodium contents
(Seibert et al., 2018) were used for this purpose. Moreover, TS
267
contents were corrected for remaining sulfate from pore waters
(Appendix A.3).
Grain size distributions were determined for five samples collected
at 0.20, 1.80, 4.56, 7.75, and 9.48 mbgs by wet sieving and drying sample
aliquots at 105 °C for 24 h. The mud fraction (b63 μm) of each sediment
sample was obtained during a second round of wet sieving with a sep-
arate sample aliquot, followed by freeze-drying. For the characterization
of the mineralogy, texture, and chemical composition of solid phases in
the separated mud fraction, we applied scanning electron microscopy
coupled with an EDX system (MERLIN VP compact, Carl Zeiss with
AztecEnergy, Oxford Instruments). The mineral powder was first
scanned over night to detect and count iron sulfides, before the jump
mode was used to analyze the texture and major element composition
of the single phases in more detail.
2.4. Groundwater sampling and analysis
Groundwater was sampled by means of a submersible pump
(Eijkelkamp, Tauchpumpe “Gigant”) at all four monitoring wells (DN-
a, -b, -c, -d, Fig. 1b) during six sampling campaigns in April, June, Sep-
tember, and November 2016, as well as in January and March 2017 to
study seasonal variations of the hydrochemistry at the core sampling
site. Field parameters (i.e., electrical conductivity (EC), redox potential,
pH, dissolved oxygen concentrations, and temperature) were deter-
mined in the field, using a Hach HQ 40d multi device with sampling
probes. Sampling included the collection of samples for major ion, dis-
solved organic carbon (DOC), alkalinity, and dissolved sulfide analyses.
A detailed description of the sampling procedures can be viewed in
Seibert et al. (2018), where hydrochemical data obtained from the
fresh upper two wells was partly presented. High sample volumes
(~5 L per well) for the investigation of the stable sulfur isotope signa-
tures of dissolved sulfate (δ34S-SO2− 34
4 ) and dissolved sulfide (δ S-H2S)
were collected once in September 2016. Moreover, samples for the
characterization of dissolved organic matter (DOM) were collected in
September 2016. In addition, DOM samples were collected at the
Ostplate from two monitoring wells of the nearby monitoring site ‘DS’
(fresh to brackish salinities) located at the southern side of the dune
ridge, three monitoring wells of monitoring site ‘B' located at the
beach (brackish to saline salinities), and seawater, respectively, in Sep-
tember 2016 to study DOM compositions as a function of salinity (Ap-
pendix 4).
To quantitatively fix the dissolved sulfide species for the δ34S analy-
sis, groundwater was directly filled in 5 L canisters containing 100 mL of
a 20% ZnAC solution, and the canisters were shaken immediately after-
wards. The precipitated ZnS was filtered off using a water-jet vacuum
pump and 0.45 μm cellulose acetate filters, rinsed with distilled water,
and dried in culture dishes 24 to 48 h after sample collection. The resid-
ual, sulfide-free groundwater samples were stored in a refrigerator and
used to quantitatively precipitate the dissolved sulfate, which was car-
ried out within 2 to 3 weeks after sampling by heating each sample to
~60 °C, decreasing the pH to ~2 to 3 with 37% HCl, and adding sufficient
amounts of a 5% BaCl2 solution. The precipitated BaSO4 was filtered,
rinsed, and dried after 24 to 48 h, as described for the ZnS precipitates.
In July 2017, additional BaSO4 precipitations were carried out for brack-
ish groundwater samples collected in April and November 2016 and
January and March 2017. Those samples had previously been frozen
after sampling and were only defrosted immediately before the BaSO4
precipitation procedure.
Major anions of all groundwater samples were determined by ion
chromatography (883 ICplus), and major cations were determined by
flame atomic absorption spectroscopy (Agilent Technologies 200 Series
AA, 240 AA). Only samples with a charge balance b±5% were accepted
(n = 21). The alkalinity (predominantly bicarbonate) was determined
with a Merck MColortest™ Carbonate Hardness Test (precision
~0.1 mmol/L), and dissolved sulfide concentrations were determined
using a visocolor ECO Test and a PF-12 photometric device. DOC
268 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283
concentrations were measured by high temperature catalytic oxidation
using a Shimadzu TOC-VCPH. A more detailed overview of the
hydrochemical analyses is presented in Seibert et al. (2018). The
hydrochemical composition of each sample was subsequently used to
carry out speciation calculations and determine mineral saturation indi-
ces (e.g., SIcalcite and SIsiderite), employing the geochemical software tool
PHREEQC (Parkhurst and Appelo, 2013).
For the determination of the δ34S signatures of dissolved sulfate, the
precipitated BaSO4 was mixed with V2O5 in Sn cups and combusted in a
Thermo Flash 2000 EA elemental analyzer that was connected to a
Thermo Finnigan MAT 253 gas mass spectrometer via a Thermo Elec-
tron Conflo IV split interface. Sulfur isotope measurements at Leibniz
IOW had a precision of better than ±0.2‰. For δ34S analysis of dissolved
sulfide and TRIS, the precipitated ZnS was converted to Ag2S. Isotope ra-
tios were converted to the V-CDT scale, using international reference
calibration materials and following the procedure given by Mann et al.
(2009).
DOM was pre-concentrated and desalinated according to Dittmar
et al. (2008), by passing the acidified (pH = 2, HCl p.a.) subsamples
over Bond ELUT PPL solid phase extraction cartridges. After washing
with acidified ultrapure water, the DOM extracts were eluted with LC-
MS grade methanol. Samples were 1:1 (v:v) diluted in a methanol-
water matrix to 7 ppm DOC concentrations and measured by
electrospray-ionization Fourier transform ion cyclotron resonance
mass spectrometry (ESI-FT-ICR-MS) on a 15T Bruker solariX instru-
ment. Sample measurement, calibration, and compound classification
(e.g., peptide, polyphenol, or fatty acid compounds) protocols are de-
scribed by Seidel et al. (2014, 2015). For each sample, weighed sums
of the compound classes were calculated to determine site-specific
DOM fingerprints.
2.5. Optically stimulated luminescence (OSL) dating
All sample preparation was carried out under subdued red light.
Oven dried (50 °C) samples were dry-sieved to obtain sand of 150 to
200 μm in diameter. The sand was treated with 10% HCl and diluted so-
dium oxalate solution (Na2C2O4) to destroy carbonates and disperse ag-
gregates. Organic material was removed through wet oxidation using
30% hydrogen peroxide (H2O2). Density separations were carried out
using sodium polytungstate (SPT, Na6[H2W12O40]) to obtain minerals
of different densities, i.e., potassium feldspar (ρ b2.58 g cm−3), plagio-
clase (2.58 g cm−3 b ρ b 2.62 g cm−3), quartz (2.62 g cm−3 b ρ
b 2.7 g cm−3) and heavy minerals (ρ N 2.7 g cm−3). Quartz grains
were selected for luminescence measurement and treated with 40%
hydrofluoric acid (HF) for one hour to etch the α-irradiated outer sur-
face of the grains and to remove remaining feldspar. Subsequently, the
quartz grains were treated with 20% HCl for one hour and dry-sieved
again, using a 150 μm sieve. Ultimately, the quartz grains were depos-
ited on stainless steel discs with a diameter of 6 mm (medium aliquots),
which had been sprayed with silicone oil before deposition to fix the
grains.
OSL measurements were conducted with an automated lumines-
cence reader (Risø TL/OSL DA-20) equipped with blue light stimula-
tion at 470 nm and a 7.5 mm Hoya U-340 detection filter. The single-
aliquot regenerative-dose (SAR) protocol of Murray and Wintle
(2000, 2003) was applied for pretests and determination of the
equivalent dose (De). To minimize the relative contribution of the
medium and slow components of the OSL signal, Early Background
Subtraction (EBG) was applied (Ballarini et al., 2007). OSL signals be-
tween 0 and 0.48 s were calculated and background integration
limits were set from 0.48 to 1.28 s. It was checked that the recycling
ratios and IR/blue OSL depletion ratios of all aliquots were ≤ 10% from
unity according to the range of acceptability suggested by Wintle and
Murray (2006). A one-sided Grubbs test (Grubbs, 1950) was applied
for one time to detect outliers within the measured D e values. D e
values detected as outliers (P b 0.01) were excluded when
calculating the mean De. Before the measurement of De values, pre-
tests were carried out at different preheat temperatures (160 to
260 °C, in 20 °C steps) to find the most appropriate thermal treat-
ment for the OSL measurements (Appendix A.5).
The radionuclide concentrations (K, Th, and U) of 50 g oven-dried
(130 °C) sediment of each subsample allotted for gamma spectrometry
were measured for at least 24 h in plastic containers, using high resolu-
tion gamma spectrometry. The measurements were conducted not ear-
lier than four weeks after filling the containers to allow adjustment of
the radon disequilibrium. The β-dose rate and the γ-dose rate were cal-
culated using the conversion factors of Guérin et al. (2011) and the grain
size dependent β-attenuation of Aitken (1985). By applying the water
content attenuation factor of Aitken (1985), the β- and γ-dose rates
were corrected.
The water content for sample 3596 was set to 3 ± 3 wt%
(Table A.5.1) according to the mean water content of representative
subsamples (n = 9, σ = 1) and a conservative estimate of the range.
Only sample 3596 was taken from depth above the ground water
table (1.22 mbgs in April 2016). All other samples were taken from
depth below the mean groundwater table and were, therefore, con-
sidered to have been constantly water saturated before sampling.
According to water content measurements of artificially water satu-
rated sand samples (n = 10, σ = 1) with representative pore vol-
umes (26 to 38%) and bulk densities (1.3 to 1.5 g cm−3), the water
content for all other samples was set to 19 ± 5 wt%, again applying
a conservative estimate of the range (Table A.5.1). The sediment
dose rate was then obtained by using the corrected β- and γ-dose
rates.
The cosmic dose rate was determined according to Prescott and
Hutton (1994) and Prescott and Stephan (1982). The total dose rate
was calculated by adding the sediment dose rate and the cosmic dose
rate (Table A.5.1). The OSL age of each sample was finally determined
by dividing the mean De by the total dose rate.
3. Results
3.1. Geologic characterization and sediment ages
The upper 1.24 m of the core consisted of aeolian medium to fine-
grained sands with low contents of shell debris (b1% dw., Fig. 2a,
Fig. A.6.1). Sediments at greater depth were of marine origin and
contained higher shell contents. A layer considerably enriched in shell
debris (up to 36% dw.) and consisting of medium to coarse-grained
sands with low contributions of fine sand was found at ~7.00 to
10.00 mbgs, only interrupted by a layer of medium to fine-grained
sands at 7.24 to 7.88 mbgs. Silt and clay fractions were very low (b1%
dw.) in all core sediments (Fig. A.6.1).
OSL ages of the sands ranged between 78 ± 11 and 459 ± 52 a
(Fig. 2b, Table A.5.2), with ages increasing over depth. Sedimentation
rates were calculated based on the obtained ages and the vertical distance
between each sampling point (Fig. 2b). Upper aeolian (b0.51 mbgs) as
well as marine sediments at 1.55 to 2.43 mbgs and 6.38 to 7.35 mbgs
were deposited at lower rates (0.5 to 0.7 cm/a), while lower aeolian sed-
iments at 0.51 to 1.55 mbgs were deposited faster (3.7 cm/a). The highest
sedimentation rate (14.6 cm/a) was estimated for marine sediments at
2.43 and 6.38 mbgs, using the youngest (296 a) and oldest (323
a) sediment ages from this time of rapid deposition.
3.2. Geochemistry
TIC contents were low in the upper 7 m of the core but increased at
greater depths, which is in line with the observed shell contents (Fig. 3a,
c). TOC contents were very low throughout the core (TOCmean ~0.03%
dw.) and showed only little variation, with highest TOC contents
being detected in the aeolian sands and at the core bottom (Fig. 3b). Ex-
tracted reactive iron fractions were low (Fedith. mean: ~10.6 mmol/kg,
 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283 269

Fig. 2. a) Geologic characterization of core sediments. Sample locations for grain size and SEM-EDX analyses are indicated (No. 1 to 5, Appendix A.6). * denotes that medium to coarse-
grained sands at the core bottom contained low fractions of fine sand (compare Fig. A.6.1). b) Sediment ages based on OSL dating (dots) as well as calculated sedimentation rates [cm/
a]. Bars at each dot present the uncertainty associated with the determined ages (Table A.5.2). Sediment ages in depth N 7.4 mbgs could not be determined due to high contents of
shell debris.

FeHCl mean: ~8.5 mmol/kg) and remarkably constant over depth
(Fig. 3d). The offset between both reactive iron fractions was uniform,
neglecting two outliers of FeHCl in the aeolian sands. TRIS was present
at low contents (b0.2 mmol/kg) in the upper sediments and higher con-
tents (up to ~3.0 mmol/kg) at depths N7 mbgs, where groundwater con-
ditions were brackish (Fig. 3e). TS contents were generally higher than
TRIS contents and point towards extremely low TRIS contents in the
sediments from 2 to 7 mbgs, where TRIS could not be detected. Stable
sulfur isotope signatures of TRIS were lower in brackish (b−25‰) com-
pared to the fresh (N − 20‰) sediments (Fig. 3f).
Intact framboidal and euhedral pyrite minerals were only detected
in the silt and clay fraction (b63 μm) of sample 4 and 5, which were col-
lected in the brackish part of the core (Fig. 4). The diameter of the
framboids ranged between ~6 and 14 μm, and the euhedral pyrite had
a width of ~4 μm.
3.3. Hydrochemistry
TDS concentrations indicated fresh groundwater (TDS b1 g/L) in the
upper two monitoring wells (DN-a, -b), while groundwater of the lower

Fig. 3. Depth profiles of a) TIC, b) TOC, c) shell, d) reactive iron (Fedith. and FeHCl), and e) sulfur (TRIS and TS) contents, and f) stable sulfur isotope signatures of TRIS [‰ vs. V-CDT].
Horizontal lines mark the groundwater table (upper solid line) and the approximated transition from fresh to brackish salinities (lower dashed line) in spring 2016, based on
hydrochemical sampling in April 2016. Shell contents presented in c) correspond to the sediment fraction N1 mm (shell fragments) relative to the entire sample weight, while all
other species (a, b, d, and e) were determined for the sediment fraction b1 mm only. ‘bDL’ denotes samples for which TRIS contents could not be determined, as no ZnS precipitation
was observed during the extraction procedure.
270 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283
Fig. 4. Pyrite minerals detected in the brackish sediments using SEM-EDX analysis. a) and b) show framboidal pyrite minerals, found in the sediment fraction b63 μm at 7.75 mbgs. c) and
d) show an euhedral and a framboidal pyrite mineral, respectively, found in the sediment fraction b63 μm at 9.48 mbgs.
two wells (DN-c, -d) was brackish (TDS N1 g/L) in April 2016, approxi-
mately three weeks after core sampling in March 2016 (Fig. 5a). The sa-
linity stratification was steady in spring, summer, and autumn.
However, after storm floods reached monitoring site DN in winter
2016/17, seawater infiltrated and resulted in increased TDS concentra-
tions in the upper two monitoring wells in January 2017 (5 to 12 g/L,
Fig. 5a). TDS levels of groundwater collected during sampling in
March 2017 were lower again (b5 g/L). The pH of all groundwater sam-
ples was slightly alkaline (7.5 to 8.2, Fig. 5b), with only small seasonal
variations. Equilibrium with respect to calcite was noticed for all sam-
ples (Fig. 5c).
Redox potentials decreased over depth and showed seasonal varia-
tions, particularly in the upper two wells (Fig. 5d). DOC was present at
moderate concentrations (~0.1 to 0.7 mmol/L) in all samples (Fig. 5e).
Bicarbonate concentrations increased over depth, except for March
2017 when concentrations in the two bottom wells were lower com-
pared to the previous sampling campaigns (Fig. 5f). Dissolved oxygen
was present in near-surface groundwater, decreased over depth, and
was absent in the lowest well (Fig. 5g). Similar trends were observed
for nitrate, which showed high and seasonally varying concentrations
of up to ~380 μmol/L in near-surface groundwater (Fig. 5h). Dissolved
iron was detected in the lowest well at varying concentrations (b8 to
24 μmol/L, Fig. 5i) and one sample collected at the uppermost well in
March 2017 (~10 μmol/L). Sulfate concentrations correlate with salinity
and were, thus, higher in the brackish compared to the freshwater zone
(Fig. 5j). Infiltrating seawater increased sulfate concentrations in the
former freshwater zone in January and March 2017. Concentrations of
dissolved sulfide were always below the detection limit (b2 μmol/L,
not presented).
Stable sulfur isotope signatures of dissolved sulfate ranged between
+19.5 and +21.7‰ vs. V-CDT in all brackish samples (Fig. 5k). Dis-
solved sulfate in freshwater collected at the upper two wells in Septem-
ber 2016 was relatively depleted in 34S (+2.7 to +9.5‰ vs. V-CDT).
Although dissolved sulfide concentrations were below the detection
limit of the field tests, quantitative precipitation of dissolved sulfides
as ZnS was successful for the two brackish groundwater samples col-
lected in September 2016. The stable sulfur isotope signatures of dis-
solved sulfide in these samples were −28.3 and −14.3‰ vs. V-CDT,
respectively (Fig. 5l).
With regards to DOM compositions, the freshest groundwater sam-
ples were characterized by elevated relative amounts of less-reactive,
aromatic compounds, such as polycyclic aromates and polyphenol com-
pounds (not presented). In contrast, labile DOM compounds, such as
fatty acids (Fig. 6a), peptide compounds (Fig. 6b), and aliphatic,
heteroatom-containing sugars (Fig. 6c), generally increased with in-
creasing electrical conductivities and were at their highest in the seawa-
ter reference sample. Despite this overall trend, it was recognized that
the fresh groundwater samples DN-a and DN-b were relatively enriched
in labile DOM fractions, which especially accounts for sugars.
4. Discussion
4.1. Geomorphologic changes, seasonal variations, and the impact on
groundwater salinities
The upper 7.4 m of the investigated sediments were rapidly depos-
ited, mainly under marine conditions within the previous ~500 years.
Ages of sediments at N7.4 mbgs could not be determined but, based
on the petrography, it is assumed that they are not significantly older
than ~900 a, applying a sedimentation rate of 0.7 cm/a as calculated
for the layer above. Aeolian sands at the top are younger than
~80 years, which is in line with Röper et al. (2013) who reported that
the formation of dunes at the Ostplate started in the 1940's. The esti-
mated sedimentation rates of ~0.5 to 14.6 cm/a at the Ostplate are
very high compared to other marine locations, where sedimentation
rates typically are lower than 1 cm/a (e.g., Silverberg et al., 1986; van
 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283 271

Fig. 5. Results of hydrochemical sampling at monitoring site DN. a) TDS, b) pH, c) SICalcite, d) redox potential, e) DOC, f) bicarbonate, g) dissolved oxygen, h) nitrate, i) dissolved iron,
and j) dissolved sulfate concentrations, and k) δ34S-SO2− 34
4 and l) δ S-H2S signatures [‰ vs. V-CDT] are presented. The groundwater table (full horizontal lines) and the approximated
transition from fresh to brackish groundwater (dashed horizontal lines) are indicated, based on hydrochemical sampling in April 2016. ‘bDL’ denotes the detection limits for nitrate
(16 μmol/L) and dissolved iron (8 μmol/L), respectively.

Weering et al., 1987; Middelburg and de Lange, 1989; Calvert et al.,
1991; Stein et al., 1994).
While the study site remained fully marine until ~80 years ago, sub-
sequent dune growth inhibited the infiltration of seawater during tidal
cycles and most flood events during the year and allowed for the forma-
tion of freshwater lenses (Röper et al., 2013; Holt et al., 2017), resulting
in fresh to brackish groundwater salinities today. However, the study
site is occasionally impacted by storm surges in the winter season, tem-
porarily leading to increased groundwater salinities. During spring until
late autumn, when no storm surges occur at the Ostplate, salinities
quickly return to fresh conditions in the upper sediments due to infil-
trating precipitation and lateral groundwater flow from the freshwater
lens (Holt et al., 2017). Therefore, dune growth accompanied by the for-
mation of freshwater lenses together with the observed seasonal pat-
terns, including storm surges and periods of freshening, result in
highly varying groundwater salinities at the core sampling site (Holt
et al., in preparation). Changing salinities are further linked to the
biogeochemical cycles, either directly (e.g., changes of solute

Fig. 6. Relative concentrations of DOM for a) saturated fatty acids (CHOX), b) peptides, and c) sugars (CHOX) in groundwater samples from the monitoring sites DN (well DN-a, -b, -c, -d),
DS (well DS-b, -c), and B (well B-a, -b, -c), respectively, and a seawater sample collected in September 2016.
272 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283
concentrations, such as dissolved sulfate) or indirectly (e.g., change of
the redox conditions and primary productivity), as stated by Böttcher
and Lepland (2000).
4.2. Characterization of carbon, sulfur, and iron sources
Shell debris, constituting of low Mg-calcite and aragonite (Seibert
et al., 2018), are the main source for the TIC pool, based on correlated
TIC and shell contents (Fig. A.7.1a). The fact that TIC and TOC contents
do not correlate (Fig. A.7.1b) demonstrates the presence of mainly
reworked shell fragments (Böttcher et al., 2004), i.e., organic matter as-
sociated with shell debris was removed before or quickly degraded
upon deposition. The observed TOC contents in the permeable sands
at the Ostplate are extremely low compared to other marine locations
(e.g., Oenema, 1990; Lyons and Berner, 1992; Bottrell et al., 2009;
Sheng et al., 2015) and even among the lowest that were reported for
similar organic-poor, permeable sands (e.g., Böttcher et al., 1998,
2004; Jakobsen and Postma, 1999). Besides sedimentary organic matter
(SOM), (labile) DOM presents a further carbon source in beach sedi-
ments subject to tidally- or storm-driven seawater inundation
(Chipman et al., 2010).
Brackish groundwater samples have a Cl−/SO2− 4 ratio slightly higher
but similar to seawater at Spiekeroog Island (~18 mol*L−1/mol*L−1,
Fig. 7), indicating that dissolved sulfate in brackish samples is of
marine origin. Cl−/SO2− 4 ratios of freshwater samples are lower (~7 to
12 mol ∗ L−1/mol ∗ L−1) and resemble the Cl−/SO2− 4 ratio of local precip-
itation (~12 mol ∗ L−1/mol ∗ L−1). Stable sulfur isotope signatures con-
firm the previous considerations, because dissolved sulfate in all
brackish samples had a δ34S signature close to +21‰ vs. V-CDT,
which is typical for North Sea seawater sulfate (Böttcher et al., 2007),
and the two freshwater samples had δ34S-SO2− 4 values of +9.5
and +2.7‰ vs. V-CDT, respectively, which is similar to the typical
δ34 S-SO 2−
4 signatures in precipitation in North-West Germany
(δ34S-SO2− 4 about +8 ± 2‰ vs. V-CDT; Reckhardt et al., 2017). Stable
sulfur isotope signatures of dissolved sulfate in coastal precipitation,
which are lighter than the typical signature of seawater sulfate, are
an indication for non-marine sulfate sources, predominantly
reflecting emission and deposition of sulfur compounds from (indus-
trial) combustion processes (e.g., Caron et al., 1986; Novák et al.,
2000) or, although presumably of minor importance, sulfur gas
emissions from intertidal sediments (Kristensen et al., 2000).
Fig. 7. Cl−/SO2−
4 ratios of collected groundwater samples. The two vertical grey lines
indicate mean Cl−/SO2− 4 ratios of local seawater and precipitation, respectively,
according to Seibert et al. (2018). Horizontal lines mark the groundwater table (solid
line) and the approximated transition from fresh to brackish salinities (dashed line),
based on hydrochemical sampling in April 2016.
Both analyzed sedimentary reactive iron fractions are coupled to
each other and demonstrate common iron sources. A major portion of
reactive iron in the core sediments can be linked to highly reactive fer-
rihydrite or lepidocrocite, which are extracted with the HCl method
(Raiswell et al., 1994). The offset between the Fedith. and FeHCl fractions
(~2 to 4 mmol/kg) corresponds to a contribution from less reactive iron
(oxyhdr)oxides, e.g., goethite and hematite, which are quantitatively
extracted with the citrate-dithionite method (Canfield, 1989). Two
FeHCl outliers at the core top (Fig. 3d) may indicate a high local contribu-
tion of silicate iron. Furthermore, PHREEQC speciation calculations for
groundwater samples containing dissolved iron indicated that solutions
were close to saturation/supersaturated with respect to siderite
(SIsiderite ~0.1 to 0.5), which shows that iron carbonates possibly present
additional iron sources. In general, reactive iron contents in the perme-
able sands are extremely low and comparable to other (organic-poor)
permeable sands (e.g., Jakobsen and Postma, 1999; Morse, 1999;
Böttcher et al., 2004).
4.3. Degradation of organic matter
Dissolved oxygen and nitrate serve as the most prominent electron
acceptors for the oxidation of organic matter in near-surface groundwa-
ter, as both oxidants were rapidly consumed and absent at depth. Sim-
ilar results for nitrate reduction were obtained by Allen et al. (2014),
who investigated fresh groundwater below a natural dune system in
SW England. Seasonal variations of nitrate concentrations may be ex-
plained by varying nutrient loads linked to the activity of migrating
birds, the oxidation of ammonia liberated during the degradation of or-
ganic matter, or contributions from atmospheric deposition and N2 fix-
ation (Seibert et al., 2018).
Reductive dissolution of iron (oxyhydr)oxides was inferred for the
deepest monitoring well, where dissolved iron was detected. Dissolved
iron observed in the uppermost sampling well in March 2017 was unex-
pected as sampled groundwater contained significant concentrations of
dissolved oxygen and nitrate, and this finding could be explained by the
input of labile marine organic matter during storm events in winter
2016/17 and the presence of reducing microniches. Such redox niches
were, for instance, reported by Jørgensen (1977a) for sulfate reduction
in marine sediments with oxidizing conditions in the surroundings.
Maximum dissolved iron concentrations were up to two orders of mag-
nitude lower compared to other organic-rich locations, where iron sul-
fide formation was observed (e.g., Oenema, 1990; Neumann et al., 2005;
Bottrell et al., 2009; Morgan et al., 2012). The low concentrations of dis-
solved iron in the investigated groundwater may further result from
siderite precipitation (e.g., Magaritz and Luzier, 1985), which is corrob-
orated by PHREEQC speciation calculations for selected groundwater
samples (SIsiderite ~0.1 to 0.5).
Microbial sulfate reduction could not be directly inferred from mea-
sured dissolved sulfide concentrations (b2 μmol/L), whereas an accu-
mulation of dissolved sulfide is often observed for pore waters of iron
sulfide-forming sediments (e.g., Lyons and Berner, 1992; Böttcher
et al., 1998; Morgan et al., 2012). However, the bulk precipitation of
ZnS was successful and calculated Cl−/SO2− 4 ratios of brackish samples
were similar to but slightly higher than the average ratio in seawater
(Fig. 7), which points towards ongoing microbial sulfate reduction
and, consequently, some sulfate consumption. These results are in line
with Magaritz and Luzier (1985) who observed non-conservative be-
havior of sulfate in the seawater-freshwater mixing zone of a coastal
dune aquifer at Coo Bay, Oregon, which was explained by microbial sul-
fate reduction.
Furthermore, a slight increase of δ34S-SO2− 4 values with increasing
−
Cl /SO2− 4 ratios was noticed for most brackish samples (Fig. 8b), and
such an enrichment of 34S in the residual sulfate fraction is typically
found in natural closed-systems under the influence of sulfate reduction
(e.g., Hartmann and Nielsen, 2012). The enrichment of 34S in dissolved
sulfate at the sampling site is, however, very low compared to other
 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283
Fig. 8. a) Cl−/SO2− 34 2−
4 ratios vs. δ S-SO4 signatures of collected groundwater samples. P and S (triangles) mark the composition of precipitation and seawater endmembers, respectively.
The dotted line presents the mixing line between both endmembers. The color scale of the dots indicates the salinity, with EC b1.5 mS/cm corresponding to freshwater. b) Cl−/SO2−
vs. δ34S-SO2−4 signatures of brackish groundwater samples.
terrestrial/marine locations (e.g., Böttcher et al., 1998; Massmann et al.,
2003; Neumann et al., 2005; Bottrell et al., 2009; Antler et al., 2013;
Peketi et al., 2015), indicating extremely low sulfate reduction rates
and essentially open-system conditions (Fig. A.8.1). Pore water sulfate
replenishment at the study site, leading towards essentially open-
system conditions with respect to sulfate, is caused by the seasonal in-
undation events, which further result in a mixing of fresh groundwater
with sulfate-rich and oxygenated seawater.
Sulfate reduction rates (SRR) in the core sediments were estimated
under the assumption that all produced dissolved sulfide reacted to
form pyrite:
SRR ¼ Cpyrite  ρbulk =Δt
with Cpyrite, corresponding to the pyrite content which was formed dur-
ing a certain period of time, Δt, in sediments with the bulk density ρbulk.
Applying the maximum detected pyrite (TRIS) content of ~3 mmol/kg, a
bulk density of 1.42 kg/L, that is typical for dune sands at the Ostplate
(Seibert et al., 2018), and a reaction time of 500 to 900 years for the
oldest sediments, the net SRR corresponds to ~0.01 to 0.02 nmol
∗ cm−3 ∗ d−1. This rate presents a minimum rate, as the majority of dis-
solved sulfide usually undergoes re-oxidation in diffusion-driven ma-
rine sediments (e.g., Thamdrup et al., 1994), and a maximum gross
SRR of ~0.2 to 0.4 nmol ∗ cm−3 ∗ d−1 would be obtained if it is assumed
that ~95% of dissolved sulfide was re-oxidized (Jørgensen, 1982). SRRs
at the study site likely range between the calculated minimum and
maximum rates, as the present system is dominated by advective
groundwater flow, resulting in less re-oxidation compared to
diffusion-driven marine sediments. Our findings are in line with
Jakobsen and Postma (1999) who investigated a similar organic-poor
coastal aquifer (Rømø Island, Denmark) and obtained maximum SRR
of ~0.1 to 14 nmol ∗ cm−3 ∗ d−1, which were directly measured. SRR
in fully (brackish) marine sediments usually are considerably higher
and range between b10 and ~500 nmol ∗ cm−3 ∗ d−1 (e.g., Jørgensen,
1977b; Hines and Lyons, 1982; Canfield et al., 1993b; Kristensen et al.,
2000; Böttcher et al., 2004; Bottrell et al., 2009) but may even reach
values of up to 7000 nmol ∗ cm−3 ∗ d−1 (Habicht and Canfield, 1997).
The very low SRR at the study site are attributed to the low content/re-
activity of the present organic matter, as proposed by Jakobsen and
Postma (1999) for the Rømø aquifer and Kristensen et al. (2000) for in-
tertidal sediments at Konigshafen. Furthermore, the relatively low in-
situ temperatures, averaging ~10 °C, inhibit enhanced microbial activity.
A general increase of SRR with increasing temperatures was reported
for marine studies investigating seasonal SRR in near-surface
273
4 ratios
(intertidal) sediments (e.g., Arnosti et al., 1998; Kristensen et al.,
2000; Böttcher et al., 2004; Westrich and Berner, 1988).
The fact that sulfate reduction was observed in the sediments was
surprising, as reactive iron (oxyhdr)oxides (e.g., ferrihydrite and
lepidocrocite) were present. These are commonly expected to be uti-
lized as electron acceptors prior to the microbial reduction of sulfate
(e.g., Chapelle and Lovley, 1992). Results of this study are, therefore, in-
dicative for the concurrent reduction of iron (oxyhdr)oxides and sulfate,
i.e., the presence of overlapping redox zones, as reported by Postma and
Jakobsen (1996) for the Rømø aquifer, Denmark. Our findings may even
confirm recent incubation experiments with natural sediments by
Hansel et al. (2015), who showed that microbial sulfate reduction is ca-
pable of outcompeting poorly crystalline iron (oxyhydr)oxides as termi-
ð1Þ
nal electron acceptors even at low sulfate levels.
The observed discrimination between δ34S-SO2− 34
4 and δ S-H2S (~35
to 49‰) is typical for sandy marine sediments in the region
(e.g., intertidal sediments in the Spiekeroog Area: ~32 to 42‰,
Böttcher et al., 1998; intertidal sediments at Westerhever: ~33 to
46‰, Böttcher et al., 2004). As experiments from pure cultures sug-
gested a maximum isotope discrimination of ~46‰ during microbial
sulfate reduction (e.g., Chambers and Trudinger, 1979), higher values
were often attributed to recycling of sulfur species, including re-
oxidation of sulfide followed by disproportionation of sulfur intermedi-
ates (e.g., Canfield and Thamdrup, 1994; Böttcher et al., 2005). More re-
cently, however, Canfield et al. (2010) and Sim et al. (2011) could show
that such large isotope fractionation does not necessarily require dis-
proportionation and can be achieved by dissimilatory sulfate reduction
alone. In the absence of dissolved oxidizing agents (i.e., dissolved oxy-
gen and nitrate), the observed isotope discrimination was assigned to
microbial sulfate reduction and low process rates (Habicht and
Canfield, 1997). The overall sulfur isotope discrimination may further
be superimposed by some effect of the disproportionation of sulfur in-
termediates upon re-oxidation with iron (oxyhydr)oxides.
4.4. Pyrite formation/oxidation and limiting factors
Authigenic pyrite formation is inferred for the lower, brackish sedi-
ments, where TRIS contents were elevated and sulfate reduction was
observed. Furthermore, intact framboidal and euhedral pyrites were
present, which confirms the in-situ formation of pyrite (Wilkin et al.,
1996). Further evidence of the in-situ formation of pyrite is the match
between stable sulfur isotope signatures of dissolved sulfide and sedi-
mentary TRIS, demonstrating that locally produced dissolved sulfide is
immobilized due to pyrite precipitation. The important role of pyrite
formation at the anoxic interfaces of fresh and brackish/saline
274 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283
groundwaters was previously noticed by Magaritz and Luzier (1985),
who reported pyrite formation beneath the freshwater-seawater
mixing zone of a similar sandy coastal aquifer. Pyrite contents in the in-
vestigated sediments are among the lowest reported for (organic-poor)
permeable sands (e.g., Morse, 1999; Böttcher et al., 2004; Jakobsen and
Postma, 1999). Iron sulfide contents in anoxic, organic-rich sediments
often are up to three orders of magnitude higher (e.g., Middelburg,
1991; Lyons and Berner, 1992; Neumann et al., 2005).
Very low TRIS contents in the upper, fresh sediments may present an
inert, non-authigenic background pyrite fraction, which was
transported to the site during sediment deposition. This is in line with
the detection of TRIS in the unsaturated zone sediments, where pyrite
formation can be ruled out because of oxic conditions. A further expla-
nation for low TRIS contents in the freshwater zone could be the oxida-
tion of authigenic pyrite as a consequence of salinity/redox changes.
Under fully marine conditions, the site was exclusively influenced by
marine organic matter with a high reactivity (e.g., Cowie et al., 1992;
Aller and Blair, 2004; Fig. 6), which probably resulted in the zone of sul-
fate reduction being located closer to the ground surface. Redox bound-
aries were likely shifted to greater depths upon infiltration of fresh
groundwater with less reactive terrestrial organic matter, potentially
resulting in the oxidation of previously formed pyrite. Pyrite oxidation
could further hold as an explanation for an observed sulfate surplus in
fresh groundwater with a Cl−/SO2− 4 ratio of ~7 mol/L/mol/L, which is
lower than the typical ratios in the precipitation and seawater
endmembers, respectively (Fig. 8a). In addition, the low δ34S-SO2− 4 may have an additional effect on TRIS oxidation and pore water sulfate
value of this sample (+2.7‰ vs. V-CDT) marks that the additional sul-
fate source must be isotopically lighter than dissolved sulfate in both
precipitation and seawater (Fig. 8a). A two-component mixing calcula-
tion was carried out to characterize the additional sulfate source:
CFW  δ34 SFW ¼ Cprecip:  δ34 Sprecip: þ Csource  δ34 Ssource
with C and δ34S being the sulfate concentrations and the stable sulfur
isotope signatures of the fresh groundwater sample (FW), precipitation
(precip.), and the additional sulfate source (source), respectively. Using
the measured sulfate concentration of the fresh groundwater sample
(0.20 mmol/L) and assuming a sulfate contribution from precipitation
(0.12 mmol/L) according to the measured chloride concentration
(1.47 mmol/L) and the average Cl−/SO2− 4 ratio of local precipitation
(~12 mmol/L/mmol/L), an additional sulfate contribution of
~0.08 mmol/L was calculated, which corresponds to ~67% of the esti-
mated sulfate input from precipitation. According to Eq. (2) and using
the measured δ34S-SO2− 4 values of the fresh groundwater sample
Fig. 9. a) C/S plot of sedimentary TOC and TRIS contents. The line indicates C/S ratios of 2.8, corresponding to “normal marine” sediments (Berner and Raiswell, 1983), and b) calculated
Degree of Pyritization (DOP). The groundwater table (full horizontal line) and the approximated transition from fresh to brackish groundwater in April 2016 (dashed horizontal line) are
indicated.
(+2.7‰ vs. V-CDT) and precipitation (+8‰ vs. V-CDT), the stable sul-
fur isotope signature of the additional sulfate source is ~ −6‰ vs. V-
CDT. TRIS in the freshwater zone bears a similar stable isotope signature,
demonstrating that the additional sulfate potentially sources in pyrite
and was released during oxidation with dissolved oxygen or nitrate ac-
cording to the following overall reaction pathways (Appelo and Postma,
2005):
15 7
FeS2 þ O2 þ H2 O→FeðOHÞ3 þ 2SO4 2− þ 4Hþ ð3Þ
4 2
15
5FeS2 þ 15NO3 − þ 5H2 O þ 4Hþ → N2 þ 5FeOOH þ 10SO4 2− þ 9Hþ ð4Þ
2
Up to ~47% of dissolved oxygen or ~32% nitrate, respectively, would
be consumed during the oxidation of pyrite in the freshwater zone with
respect to Eqs. (3) and (4), assuming a pyrite derived sulfate input of
0.08 mmol/L and considering maximum observed dissolved oxygen
and nitrate concentrations of 0.32 mmol/L and 0.38 mmol/L, respec-
tively, in the upper freshwater well. Although the presented concept
of TRIS oxidation as an explanation for additional sulfate in fresh
groundwater appears reasonable and fits the field observations well, it
is understood that previous consideration may suffer from uncer-
tainties. For instance, unknown TRIS reactivity, pore water velocities,
flow fields, or recharge amounts of oxic seawater during storm events
concentrations, respectively.
Regarding limiting factors for pyrite formation, there was no signifi-
cant C/S-correlation between TOC and TRIS contents (Fig. 9a), which is
usually observed for diagenetic pyrite formation under sulfate reducing
conditions (e.g., Lin and Morse, 1991; Lyons and Berner, 1992). Thus,
ð2Þ carbon oxidation must proceed via consumption of more favorable elec-
tron acceptors, such as oxygen and nitrate. Moreover, it is possible that
pyrite formation is not strictly linked to the oxidation of SOM but a dif-
ferent DOM source passing the permeable sands, in which case sedi-
mentary C/S ratios would not be applicable to identify carbon
limitation on pyrite formation. As labile DOM fractions correlate with
salinity, the seasonal inundation events at the core sampling site result
in the infiltration of considerable amounts of seawater and, thus, (la-
bile) DOM. Therefore, it is likely that labile, seawater-derived DOM
drives the redox cycles besides SOM. The availability of dissolved sul-
fate, usually limiting pyrite formation in sediments with fresh to brack-
ish salinities (Berner and Raiswell, 1984), can further be excluded as a
constraint on pyrite formation, since estimated sulfate reduction rates
 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283
were low and no depletion of sulfate was observed. Finally, the Degree
of Pyritization (DOP; Berner, 1970; Raiswell et al., 1988) was calculated
to investigate the effect of iron limitation on pyrite formation:
Fepyrite
DOP ¼
ð5Þ
Fepyrite þ Fereactive
where a value approaching 1 would be obtained if reactive iron is read-
ily transformed to pyrite, which is usually the case under (semi-)euxinic
conditions (e.g., Lyons and Berner, 1992). Assigning Fedith. as Fereactive
and TRIS (FeS2) as Fepyrite, low DOP values were calculated (b0.2,
Fig. 9b). Therefore, the amount of reactive iron (oxyhdr)oxides is not
limiting pyrite formation. We concluded that the low content of reactive
SOM presents the major limiting factor for pyrite formation in the inves-
tigated permeable sands.
5. Conclusions
The aim of this study was to investigate the biogeochemical cycles of
carbon, sulfur, and iron, including the formation of pyrite, in young and
rapidly-deposited, permeable sands at the land-sea transition zone.
Such sediment environments are present in many coastal regions
worldwide, yet, they didn't receive much scientific attention. For this
purpose, a 10 m sediment core was collected at a dune base of the bar-
rier island Spiekeroog, Germany, where groundwater salinities vary
from fresh to brackish. A combination of geochemical, hydrochemical,
and stable sulfur isotope analyses, as well as OSL dating was applied.
The main conclusions of this study are:
• OSL dating allows for the age determination of very young sediments
(b500 years) in high resolution.
• Groundwater salinities strongly affect the cycling of redox sensitive
elements. While authigenic pyrite formation was observed in the
brackish, anoxic sediments, pyrite oxidation was inferred for the
fresh, oxic parts.
• Estimated microbial sulfate reduction rates are extremely low,
resulting in both low dissolved sulfide concentrations and pyrite con-
tents. Comparable rates were only reported for other highly perme-
able, organic-poor sands.
Appendix A
A.1. Total Carbon (TC) measurements
Fig. A.1.1. Replicate measurements of total carbon for selected samples (n = 4). The deviation between the replicate measurements was b5% on average.
275
• Microbial sulfate reduction is observed despite the presence of reac-
tive iron (oxyhydr)oxides. This points towards the concurrent reduc-
tion of sulfate and iron or might even point towards the microbial
consumption of sulfate prior to iron (oxyhdr)oxides.
• The stable sulfur isotope discrimination between dissolved sulfate and
reduced sulfide is typical for sandy sediments that are open systems
with respect to sulfate, such as intertidal sediments in the North Sea
region.
• Low content and reactivity of SOM are identified as the major limiting
factor for pyrite formation in the organic-poor, permeable sands. In
addition, it was ascertained that labile DOM correlates with salinity,
and, as seasonal inundation events occur, labile, seawater-derived
DOM presents a further important source of electron donors in the in-
vestigated sediments.
Acknowledgments
The authors wish to thank the Nationalparkverwaltung
Niedersächsisches Wattenmeer (NLPV), in particular G. Millat and C.
Schulz, for the possibility to conduct studies on the Ostplate. The field
work was further supported by L. Diehl, T. Fresenborg, F. Grünenbaum,
T. Haene, A. Harms, C. H. Lünsdorf, H. Madaj, M. Biel Maeso, and S.
Maiwald. Laboratory work was supported by E. Gründken, C. Lehners,
U. Kücks, S. Plewe, I. Schmiedinger, H. Simon, and I. Ulber. We wish to
thank the members of Section 3 at the Leibniz Institute for Applied Geo-
physics (LIAG) for support during collecting and preparing the core
samples for OSL dating. We are further grateful to the
Microbiogeochemistry Group at the ICBM and Leibniz IOW for the sup-
port during geochemical sample preparation and analyses. We thank S.
Fock, C. Winkelmann, and C. Heithecker of the Nationalparkhaus
Wittbülten, Spiekeroog, for the provision of accommodation and the
support during field work. We highly acknowledge the constructive
comments of Simon Bottrell and one anonymous reviewer, and we ap-
preciate the excellent manuscript handling of the editor J.V. Cruz. We
wish to thank the German Research Foundation for project funding
(DFG project number MA 3274/6-1 and GI 171/25-1). This publication
is dedicated to our very supportive colleague Gerald Millat, who sadly
passed away in 2017.
276 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283

A.2. Fedith. measurements

Fig. A.2.1. Replicate measurements of Fedith.

A.3. Dry weight and TS corrections

The presented geochemical data was corrected for the salt content, which remained attached to the sediments after freeze-drying. For this pur-
pose, sodium contents [g/kg] were used (Seibert et al., 2018) and multiplied by a factor of 3.3, corresponding to the average ratio of Total Dissolved
Solids (TDS, i.e., salt) [mg/L] and Na [mg/L] in seawater at Spiekeroog Island (Fig. A.3.1). In a second step, all determined solid phase contents were
corrected using the following factor:
mdry
f salt ¼

mdry −msalt

where mdry and msalt correspond to the sediment dry weight and the dry weight of salt, respectively. Results show that the remaining amount of salt
(Fig. A.3.1) is very low in comparison to the sediment dry weights, ranging from ~22 to 38 g for all samples.

Fig. A.3.1. Measured sodium contents (Seibert et al., 2018) and estimated salt contents. Salt contents were calculated assuming an average ratio of 3.3 for TDS [mg/L] and Na [mg/L] in
seawater at Spiekeroog Island.
 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283 277

Moreover, measured TS contents were corrected for the contribution of pore water sulfate. Sodium contents (Fig. A.3.1) as well as interpo-
lated Na+/SO2−
4 ratios from groundwater sampling in April 2016 (Fig. A.3.2d) were used for this purpose. The calculated contribution of sulfate
on average corresponds to ~30% of the uncorrected TS content (Fig. A.3.2e).

Fig. A.3.2. a) TDS, b) sodium, and c) sulfate concentrations, and d) Na+/SO2− 4 ratios of groundwater samples collected in April 2016 (dots), and e) TS (full dots) and sulfate contents (open
circles) of the core sediments. Lines in a) to d) present linear interpolations between the sampling points. For the unsaturated zone, hydrochemical analyses of suction cup samples (n = 9)
were used. The suction cups were installed in the unsaturated zone at monitoring site DS in the direct vicinity of the core sampling site at the Ostplate (Fig. A.4.1). Sulfate contents were
obtained by dividing measured sodium contents (Seibert et al., 2018, Fig. A.3.1) by the interpolated pore water Na+/SO2− 4 ratio of the corresponding depth. The groundwater table (full
horizontal lines) and the approximated transition from fresh to brackish groundwater (dashed horizontal lines) are indicated, based on hydrochemical sampling in April 2016.

A.4. Dissolved organic matter (DOM) sampling

Samples for the characterization of DOM were collected at monitoring site DN in September 2016. Furthermore, groundwater samples were ob-
tained from 5 additional wells located at the monitoring site DS and B at the Ostplate, respectively (Fig. A.4.1). Moreover, a seawater sample was col-
lected for DOM analyses.
Two monitoring wells (DS-b, DS-c) are located at monitoring site DS, where the ground surface elevation is ~4.2 masl (Fig. A.4.1). Wells
have a screen length of 1 m and are screened in 4.7 to 5.7 mbgs (DS-b) and 6.7 to 7.7 mbgs (DS-c). Storm events usually do not reach site
DS, and groundwater electrical conductivities (EC) varied from 1.4 to 2.0 mS/cm (DS-b) and 7.6 to 8.5 mS/cm (DS-c), based on bimonthly mon-
itoring in 2016 to 2017.
Three monitoring wells (B-a, B-b, B-c) are located at monitoring site B at the northern beach of the Ostplate (Fig. A.4.1). The ground surface ele-
vation is ~1.8 masl, and, therefore, site B is regularly flooded during storm events. Wells have a screen length of 1 m and are screened in 0.5 to
1.5 mbgs (B-a), 6.6 to 7.6 mbgs (B-b), and 14.0 to 15.0 mbgs (B-c). Groundwater ECs varied from 30.5 to 36.2 mS/cm (B-a), 28.6 to 30.6 mS/cm
(B-b), and 26.2 to 33.7 mS/cm (B-c), based on bimonthly monitoring in 2016 to 2017.
Seawater for DOM analysis was collected at the Ostplate in September 2016 (Fig. A.4.1), and seawater ECs varied from 44.7 to 48.2 mS/cm
for sampling campaigns in 2016 to 2017. A more detailed description of the hydrochemistry is not presented in this study, as groundwater
samples from the monitoring wells at site DS and B only aid to investigate the characteristics and compositions of DOM at the Ostplate as a
function of salinity.
278 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283

Fig. A.4.1. Locations of DOM sampling in September 2016. DN marks the core sampling site, including the groundwater monitoring wells (GMW) DN-a, DN-b, DN-c, and DN-d. DS and B
present additional monitoring sites, with the GMW DS-b, DS-c, and B-a, B-b, and B-c at the southern side of the dune ridge and the northern beach of the Ostplate, respectively. Suction
cups, used for the hydrochemical analysis of soil water, are located at site DS. Furthermore, the seawater sampling location is indicated. Seawater was collected during high tide. Yellow-
hatched areas present dune areas with ground surface elevations N3 masl, according to Röper et al. (2013). (For interpretation of the references to color in this figure legend, the reader is
referred to the web version of this article.)

A.5. Optically stimulated luminescence (OSL) dating

Prior to the De determination, pretests were performed on aliquots of one sample (3594) to find the most appropriate thermal treatment for
OSL measurements (Fig. A.5.1). This included a preheat plateau test, a thermal transfer test (for bleached aliquots), and a dose recovery test at
different preheat temperatures for 10 s and a fixed cut heat temperature of 160 °C. The preheat plateau test (Fig. A.5.1-A) showed a plateau
between 160 and 180 °C, from which the preheat temperature for De measurements should be selected, given the dose recovery ratio at
this temperature is within the acceptable range of ±10% from unity (Wintle and Murray, 2006). At the preheat temperature of 180 °C, the
recycling ratio was close to unity within the acceptable range and no contribution of thermal transferred OSL signals was observed
(Fig. A.5.1-B and -C). For this reason, the De measurements (16 aliquots per sample) and the determination of the dose recovery ratios (6 al-
iquots per sample) were conducted with a preheat temperature of 180 °C, using a cut heat temperature of 160 °C. An example of a typical OSL
decay curve and a dose response curve from an aliquot of sample 3594 is shown in Fig. A.5.2. The final results of OSL dating are presented in
Table A.5.2.
 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283 279

Fig. A.5.1. Pretests results of sample 3594. Equivalent dose (De) measured at preheat temperatures from 160 °C to 260 °C. A) Preheat plateau test, B) thermal transfer test, C) dose recovery
test. Single values are shown as dots and mean values (n = 4) as squares. Standard errors of the means are indicated by bars. During the preheat plateau test, one outlier (1.35 Gy, not
shown) was detected at a preheat temperature of 180 °C and excluded when calculating the mean De (n = 3).

Fig. A.5.2. Example of a typical OSL decay curve and a dose response curve (insert) of one aliquot of sample 3594. The regenerated signals are represented by squares and the
recycling point as a grey dot. Standard errors of the means are indicated by bars. The projection of the natural OSL signal (diamond) onto the dose response curve gave a De
of about 0.19 Gy.
280 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283

Table A.5.1
Results of dose rate determinations.

Sample ID Depth Depth (mean) Grain size Water contenta Element concentration Cosmic dose rate Sediment dose rate Total dose rate

K U Th

[m] [m] [μm] [wt%] [%] [ppm] [ppm] [mGy a−1] [mGy a−1] [mGy a−1]

3596 0.44–0.58 0.51 150–200 3±3 0.39 ± 0.02 0.36 ± 0.02 0.92 ± 0.06 0.20 ± 0.02 0.51 ± 0.06 0.71 ± 0.06
3595 1.46–1.63 1.55 150–200 19 ± 5 0.52 ± 0.03 0.49 ± 0.03 1.20 ± 0.07 0.17 ± 0.02 0.57 ± 0.07 0.74 ± 0.07
3594 2.34–2.52 2.43 150–200 19 ± 5 0.46 ± 0.03 0.30 ± 0.02 0.72 ± 0.05 0.15 ± 0.02 0.47 ± 0.07 0.62 ± 0.07
3593 3.40–3.60 3.50 150–200 19 ± 5 0.45 ± 0.02 0.28 ± 0.02 0.68 ± 0.05 0.13 ± 0.01 0.45 ± 0.07 0.58 ± 0.07
3592 4.33–4.52 4.43 150–200 19 ± 5 0.69 ± 0.04 0.41 ± 0.03 1.12 ± 0.07 0.12 ± 0.01 0.69 ± 0.08 0.81 ± 0.08
3591 5.35–5.53 5.44 150–200 19 ± 5 0.72 ± 0.04 0.29 ± 0.02 0.82 ± 0.05 0.10 ± 0.01 0.68 ± 0.08 0.78 ± 0.08
3590 6.29–6.47 6.38 150–200 19 ± 5 0.75 ± 0.04 0.39 ± 0.03 0.85 ± 0.05 0.09 ± 0.01 0.72 ± 0.08 0.82 ± 0.08
3589 7.30–7.40 7.35 150–200 19 ± 5 0.85 ± 0.04 0.48 ± 0.03 1.27 ± 0.07 0.08 ± 0.01 0.84 ± 0.08 0.93 ± 0.08
a
Water content given in weight percentage of dry sediment.

Table A.5.2
Results of OSL dating. De is the equivalent dose.

Sample ID Depth Depth (mean) Dose recovery ratio Aliquotsa Mean De Ageb

[m] [m] [n] [mGy] [a]

3596 0.44–0.58 0.51 1.00 ± 0.01 15 55 ± 6 78 ± 11

3595 1.46–1.63 1.55 0.97 ± 0.02 15 79 ± 4 106 ± 11
3594 2.34–2.52 2.43 1.01 ± 0.01 16 185 ± 8 300 ± 35
3593 3.40–3.60 3.5 1.00 ± 0.01 16 186 ± 11 319 ± 41
3592 4.33–4.52 4.43 1.02 ± 0.01 15 262 ± 20 323 ± 39
3591 5.35–5.53 5.44 1.03 ± 0.02 15 243 ± 9 310 ± 32
3590 6.29–6.47 6.38 1.05 ± 0.02 15 242 ± 4 296 ± 29
3589 7.30–7.40 7.35 1.02 ± 0.02 16 425 ± 28 459 ± 52
a
Number of accepted aliquots for De determination.
b
OSL age calculated by dividing the mean De by the total dose rate in years (before 2017).

A.6. Grain size distribution

Fig. A.6.1. Grain size distribution of sediment samples collected at five different depths (compare Fig. 2a).
 S.L. Seibert et al. / Science of the Total Environment 649 (2019) 264–283
A.7. Carbon sources
Fig. A.7.1. a) TIC vs. shell contents including a linear regression (line), and b) TIC vs. TOC contents.
A.8. Degradation of organic matter and sulfate reduction
Fig. A.8.1. Cl− vs. SO2−
4 concentrations of collected groundwater samples. The line presents the mixing line between precipitation and seawater endmembers (Seibert et al., 2018). Colors
indicate the electrical conductivity (EC) of each sample.
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