Marine Chemistry 171 (2015) 1020

Contents lists available at ScienceDirect

Marine Chemistry
journal homepage: www.elsevier.com/locate/marchem

Porewater exchange as a driver of carbon dynamics across a

terrestrial-marine transect: Insights from coupled 222Rn and pCO2
observations in the German Wadden Sea
Isaac R. Santos a,b,, Melanie Beck c, Hans-Jrgen Brumsack c, Damien T. Maher b, Thorsten Dittmar d,
Hannelore Waska d, Bernhard Schnetger c
a

National Marine Science Centre, School of Environment, Science and Engineering, Southern Cross University, PO Box 4321, Coffs Harbour, NSW 2450, Australia
Centre for Coastal Biogeochemistry, School of Environment, Science and Engineering, Southern Cross University, PO Box 157, Lismore, NSW 2480, Australia
c
Institute for Chemistry and Biology of the Marine Environment (ICBM), Carl-von-Ossietzky University Oldenburg, D-26111 Oldenburg, Germany
d
Research Group for Marine Geochemistry (ICBM-MPI Bridging Group), Institute for Chemistry and Biology of the Marine Environment (ICBM), University of Oldenburg, Germany
b

a r t i c l e

i n f o

Article history:
Received 12 August 2014
Received in revised form 8 February 2015
Accepted 9 February 2015
Available online 12 February 2015
Keywords:
Subterranean estuaries
Tidal ats
Submarine groundwater discharge
SGD
Sands
Estuary
Radium isotopes
Alkalinity
Nitrogen cycle
Porewater
Spiekeroog Island

a b s t r a c t
We investigate whether radon (222Rn) can be used as a tracer of porewater exchange in the Wadden Sea, and
whether porewater exchange may drive carbon dioxide, dissolved organic carbon (DOC), total dissolved nitrogen
(TDN) and alkalinity dynamics in surface waters. High temporal resolution, automated radon and pCO2 observations were made for about 24 h in ve stations along a coastal transect covering upstream brackish water creeks,
an enclosed shallow harbour receiving freshwater inputs from the catchment (Neuharlingersiel), and the
German Wadden Sea (Spiekeroog Basin). The results revealed clear tidal trends indicative of porewater exchange
in the two Wadden Sea stations. All the investigated waterways were a net source of CO2 to the atmosphere with
average pCO2 ranging from about 3600 atm in upstream creeks to about 600 atm in the Wadden Sea. The input
of upstream creek water could be detected only in the small enclosed harbour, but not in the open Wadden Sea. A
radon mass balance required porewater exchange rates of about 12 cm day1 (equivalent to 1.1% of the tidal
prism volume) in the Wadden Sea. Average alkalinity, TDN, DOC, and pCO2 values in porewater were 4.5, 18.8,
1.3, and 9.7 fold higher than in Wadden Sea surface waters. Those enrichments translated into estimated
porewater-derived uxes of 12161811, 34139, 3471, and 657 mmol m2 day1, respectively, depending
on assumptions about porewater endmember concentrations. The porewater derived free CO2 uxes were comparable to the CO2 outgassing rates estimated for the Wadden Sea (7 to 20 mmol m2 day1). These estimates as
well as signicant correlations between radon and pCO2 suggest that porewater exchange was a major driver of
CO2 outgassing from the Wadden Sea to the atmosphere. Radon can be a useful porewater (or groundwater) tracer in the Wadden Sea in spite of strong winds and well-mixed surface water conditions.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Advective porewater exchange and/or submarine groundwater discharge (SGD) may enhance the transport of carbon, oxygen, nutrients
and trace metals across the sedimentwater interface up to orders of
magnitude faster than molecular diffusion alone(Huettel et al., 2014;
Rocha et al., 2009). Therefore, porewater and groundwater ow should
be considered potential drivers of biogeochemical cycles in coastal waters. The high microbial activity in/on permeable sands, associated with
vigorous input of water and organic matter, create a unique biogeochemical reactor, the signicance of which is now being realised (Erler
et al., 2014; Moore, 2010; Rocha, 2008). In the last few years, porewater
Corresponding author at: Centre for Coastal Biogeochemistry, School of Environment,
Science and Engineering, Southern Cross University, PO Box 157, Lismore, NSW 2480,
Australia.

http://dx.doi.org/10.1016/j.marchem.2015.02.005
0304-4203/ 2015 Elsevier B.V. All rights reserved.

exchange has been demonstrated to increase benthic carbon cycling

(Cook and Roy, 2006; Waska and Kim, 2010), but the inuence of
porewater exchange on CO2 evasion from coastal waters to the atmosphere has not been investigated in detail.
While a number of studies have addressed CO2 outgassing in estuaries and coastal waters, we still lack a comprehensive quantitative understanding about sources of CO2 supersaturation and how specic
processes may inuence CO2 exchange at the waterair interface. Recent reviews of global CO2 uxes revealed that the estuarine CO2 source
is comparable in magnitude to the continental shelf sink (Borges and
Abril, 2011; Cai, 2011). Carbon dioxide supersaturation in estuaries
and some coastal waters is often thought to be driven primarily by the
net balance between photosynthetic CO2 uptake and the subsequent release via organic matter respiration in the water column or surface sediments (Ahad et al., 2008; Chen et al., 2012; Maher and Eyre, 2012).
Little is known about the role of groundwater and porewater in

I.R. Santos et al. / Marine Chemistry 171 (2015) 1020

releasing CO2 to surface waters and subsequent degassing to the atmosphere (Cole et al., 2007). However, several recent studies revealed signicant inputs of dissolved inorganic (DIC) and organic (DOC) carbon
via groundwater and porewater pathways to coastal ecosystems
(Atkins et al., 2013; Cai et al., 2003; Cyronak et al., 2013; Dorsett et al.,
2011; Goni and Gardner, 2003; Kim et al., 2012; Maher et al., 2013;
Santos et al., 2009b; Santos et al., 2012a; Winde et al., 2014).
The Wadden Sea is a relatively well studied intertidal at where
porewater exchange is known to play a major role on regional biogeochemical budgets (Beck and Brumsack, 2012). While current and ripple
interactions (skin circulation) drive porewater exchange in the upper
few centimetres of tidal at sediments at high tide, tidal pumping
(slow body circulation) drives porewater exchange in the upper few
metres of permeable sediments mostly at low tide (Billerbeck et al.,
2006a). Those porewater exchange processes drive trace metal cycling
in porewater (Beck et al., 2008; Moore et al., 2011; Riedel et al., 2011),
enhance benthic photosynthesis (Billerbeck et al., 2007) and release dissolved nutrients and methane from sediments (Billerbeck et al., 2006a;
Grunwald et al., 2007; Ry et al., 2008). Previous studies attempting to
quantify porewater exchange in Wadden Sea intertidal ats relied on
dyes and seepage metres (Billerbeck et al., 2006a), hydrogeological
models (Riedel et al., 2010) and radium isotopes (Moore et al., 2011).
Radon (222Rn; half life 3.84 days) has been shown to be an effective
porewater (or groundwater) tracer because it is often naturally
enriched in water in contact with sediments, behaves conservatively
as a noble gas, and is now relatively easy and cheap to measure.
Radon is part of the 238U decay chain and is produced primarily from
226
Ra (half-life 1600 years) retained within or adsorbed on sediments
(Dulaiova et al., 2008). The high radon emanation rate creates a
disequilibrium in which dissolved 222Rn concentrations in porewater
are often orders of magnitude higher than its radioactive parent 226Ra
(Swarzenski, 2007). Once radon-enriched porewater enters surface waters, radon immediately starts exiting the system via atmospheric evasion, radioactive decay, and mixing (Burnett et al., 2010). As a result,
high radon concentrations in surface waters are often only found close
to where porewaters or groundwaters are released to surface waters.
The main advantage of using natural geochemical tracers such as
radon to assess porewater exchange is that the water column integrates
the porewater signal coming into the system from multiple pathways.
Small scale variations, which may not be of interest, are smoothed out
(Burnett et al., 2006).
Only a few preliminary radon observations are available for the
Wadden Sea. In studies focusing on radium isotopes, Schmidt et al.
(2011) and Moore et al. (2011) reported radon concentrations in
porewater and surface water samples from the Wadden Sea. In both
studies, discrete radon samples were taken and analysed in the laboratory. While the laboratory-based approaches used in these previous
studies provide reliable data, they may not be ideal for obtaining high
temporal resolution datasets that are important for characterizing
highly-dynamic tidally-driven systems. Radon can also be measured
using automated, portable instrumentation to obtain real time results
(Dulaiova et al., 2005; Stieglitz, 2005). Several high resolution
(i.e., hourly time steps) radon datasets are now available for a number
of other coastal systems which provided insight into porewaterexchange processes on time scales ranging from a few hours to seasons
(Burnett et al., 2006; de Weys et al., 2011; Dulaiova et al., 2010; Kim and
Hwang, 2002; Santos et al., 2009a; Santos et al., 2011).
In this paper, we combine automated radon and pCO2 observations
to obtain insight into how porewater exchange may drive carbon
cycling across a Wadden Sea coastal transect. We hypothesize that
(1) radon can be used as a tracer of porewater exchange in the Wadden
Sea in spite of windy conditions driving outgassing, and that
(2) porewater exchange is a major source of carbon dioxide to surface
waters. We also investigate whether porewater exchange is a source
of dissolved organic carbon, total dissolved nitrogen and alkalinity to
surface waters. This paper builds the literature by applying a coupled

11

radonCO2 approach to an intertidal at for the rst time and reporting

the rst detailed radon observations in the Wadden Sea.
2. Material and methods
2.1. Study site
Field experiments were performed across a coastal transect in Northern Germany in the area between the coastal town of Neuharlingersiel
and Spiekeroog Island (Fig. 1). The region is characterized by barrier
islands, tidal ats, and coastal marshlands. Pleistocene sediment deposits consisting of a basal peat, intercalated peat beds and negrained sand, silt, and clay layers have accumulated in the region in
the last 7500 years. The tidal ats of the Wadden Sea extend for almost
500 km from the Netherlands to Denmark forming the largest continuous area of sand- and mudats worldwide, accounting for 60% of all
tidal areas in Europe and North Africa. The Wadden Sea sustains a rich
and diverse ora and fauna and has been inscribed on the World Heritage List in 2009 (Beck et al., 2012 and references therein).
In this study, we have investigated the Spiekeroog basin and its catchment. The local intertidal at is emerged for 68 h during low tide and is
covered by 1.52 m of water during high tide. The area inundated during
low tide is up to 20 km2 during spring tide conditions (Stanev et al.,
2003). The at margins are narrow (about 80 m) and relatively steeper
(1.6% slope) than the inner at (Beck and Brumsack, 2012). Sulphatedepleted seeps that are highly enriched in methane have been observed
at the low tide water line of the Janssand intertidal sand at (Ry et al.,
2008). The tidal at sediments are dominated by sands (grain size
140 mm, porosity ~ 0.4, permeability 1011 m2) in the western part
(Janssand), while in the eastern part and closer to the mainland ner
sediments prevail (Beck et al., 2009; Chang et al., 2006).
The hinterland of Neuharlingersiel is characterized by a dense network of channels and small rivers in a at catchment of about
125 km2 receiving about 830 mm of annual rainfall (Beck and
Brumsack, 2012; Beck et al., 2012). The coastal zone is lined by dikes
and oodgates that control the hinterland hydrology. The runoff from
the catchment converges to a oodgate in Neuharlingersiel located
just upstream of a small shing harbour (Station TS 3 in Fig. 1). The
oodgate prevents the penetration of marine waters into the catchment
and is opened when needed at low tide to release excess freshwater
from the catchment to the Wadden Sea. During periods of high precipitation, freshwater may be pumped to the Wadden Sea at high tide to

Fig. 1. Map of the study site showing the location of the ve surface water time series stations and the porewater sampling location in the Janssand intertidal at. The station colour
code matches Figs. 2, 5, and 6. (For interpretation of the references to color in this gure
legend, the reader is referred to the web version of this article.)

12

I.R. Santos et al. / Marine Chemistry 171 (2015) 1020

prevent hinterland oods. The hinterland watercourses may be brackish

due to leakages of seawater through the oodgates and discharge of
brackish terrestrial groundwater to the creeks (Beck et al., 2012). The
catchment watercourses drain marsh and fen areas and have variable
pH (6.2 to 8.8) and high dissolved organic carbon, alkalinity and iron
concentrations (Beck et al., 2012).

2.2. Experimental approach

We have performed a series of experiments in which high temporal
resolution radon, pCO2, and associated variables were measured for
about 24 h at ve surface water stations located along a coastal transect
from the hinterland to the Wadden Sea intertidal at area (Table 1). We
also investigated the chemistry of porewater in the major local intertidal sand at (Fig. 1).
For the time series experiments, we used a coupled radon and pCO2
system described in detail elsewhere (Santos et al., 2012c). Surface
water was continuously pumped at about 3 L min1 into a shower
head gas exchanger device that equilibrates the stream of owing
water with a stream of air which was re-circulated through gas
detectors in a closed loop. We used a RAD7 radon detector and a Licor
820 CO2 detector connected to a laptop computer that was used as a
datalogger. The gas detectors were powered by 12 V batteries and run
in a continuous mode (30 min time steps for radon; 5 min time steps
for CO2). The RAD7 uses an electric eld with a silicon semiconductor
detector to attract the positively charged polonium daughter (218Po+)
which is then counted as a measure of the radon concentration in air.
The full radioactive equilibrium between 218Po (half life = 3.1 min)
and 222Rn takes about 15 min. The Licor is a non-dispersive infrared
gas analyser. Calculations were made to determine the dissolved
radon (Schubert et al., 2012) and pCO2 (Pierrot et al., 2009; Weiss,
1974) values in water using well established equations that are a function of temperature and salinity. The main limitation of this system is
that there is a response time of about 30 min for radon and 10 min for
pCO2. The data were corrected to account for those time lags.
Ancillary data were obtained from a calibrated Hydrolab multisonde
(DS5x) that measured pH, DO (Hach Luminescent Dissolved Oxygen
LDO), temperature, and salinity. The multisonde was set to log at
15 min intervals and was attached to the water pump from the 222Rn/
CO2 system at a depth of about 50 cm below the water surface. The
pH was initially calibrated using pH 7 and 10 solutions on the National
Bureau of Standards (NBS) scale. At the end of the experiments, we veried a 0.01 drift at pH 7 and a +0.03 drift at pH 10. Considering the
broad pH range observed in the eld observations (shown later), no corrections were made to the pH dataset. No detectable calibration drifts
were observed for the DO and conductivity probes when using 100%
saturated freshwater and 55 mS solutions, respectively. In addition,
we also deployed a CTD Diver (Van Essen Instrument) to measure
depths at 15 min intervals. Wind speeds were obtained from a weather
station located on Spiekeroog Island provided by Deutscher
Wetterdienst. All the data obtained from data loggers at different time
steps (from 5 min for pCO2 to 30 min for radon) were interpolated or averaged to obtain concentrations at 15 minute time steps that were used
for investigating correlations among the variables. A 3 point moving average was also applied to the time series data to highlight temporal
trends.

Discrete alkalinity, DOC, and TDN samples were collected every hour
for about 24 h during the Wadden Sea surface water time series (TS 1
and TS 2) and during contrasting times (i.e., low and high tide; day
and night) at the other time series stations. The discrete sample size at
each station ranged from 4 (one sample every ~6 h) to 24 (hourly sampling) depending on the station (Table 1). The discrete samples were ltered through disposable 0.7 m Whatman GF/F syringe lters.
Replicate samples were collected after discarding a small amount of ltered water. DOC and TDN samples were acidied to pH 2 with HCl and
sealed into acid-cleaned glass vials. DOC and TDN concentrations were
measured using a Shimadzu TOC-VCPH analyser. Aliquots of deep
seawater reference material from the Consensus Reference Material
Project (CRM, University of Miami) were analysed to check the precision and accuracy of the DOC analyses. Analyses of the CRM deviated
by less than 5% from the reported value for these standards (41 to
44 mol L 1 DOC). Routine minimum detection limits are 2.8
0.3 mol L1 DOC and standard errors are typically 1.7 0.5% of the
DOC concentration (Stubbins and Dittmar, 2012). Alkalinity samples
were kept in a fridge until analysis. We used triplicate 1 ml samples
and a spectrophotometric method (Sarazin et al., 1999) that yielded
an average uncertainty of 3% (average standard deviation of all triplicate
samples). For the Wadden Sea surface water time series stations, we
also performed conventional Gran titrations to decrease uncertainties
to about 1%. Pre-standardized 0.01 mol L1 HCl was used as the titrant.
Porewater samples were collected at low tide from horizontal and
vertical transects extending from near the low tide mark to the upper
Janssand intertidal at. The horizontal transect consisted of ve boreholes installed about 25 m apart from the low tide mark to 100 m
onto the intertidal at. The boreholes were dug with a hand auger and
a slotted PVC pipe with a 0.5-m screen was installed at about 0.5 m.
The vertical transect consisted of a permanent multilevel piezometer
use in previous trace metal and nutrient investigations in the Janssand
intertidal at (Beck et al., 2008). A total of 9 samples were taken from
the vertical transect from 0.1 m down to 4.5 m using a syringe. Radon
and pCO2 observations could be made in the horizontal transect only because the ports of the vertical prole could not be used to retrieve large
volumes of water required for our radon and pCO2 methods. Radon and
alkalinity data from Moore et al. (2011) at the same location were used
to complement our porewater observations.
2.3. Calculations
A radon mass balance was used to estimate porewater exchange
rates in the Wadden Sea. We used a general approach similar to the
radium-based method of Moore et al. (2011) to estimate porewater exchange in the same location, and to radon-based methods previously
used in tidal creeks and estuaries (Gleeson et al., 2013; Peterson et al.,
2010). Our radon mass balance relied primarily on data from station
TS 1 located at the seaward boundary of the Wadden Sea because this
station presumably integrates all processes taking place in the
Spiekeroog Basin. At steady state, the porewater exchange rate (Qpw)
can be obtained as follows:
Q pw Q ebb RnTS 1 Jatm A RnTS 1 222 V
Q flood RnTS 1

226

Rasur 222 V Q di f AHT Q riv Rnriv =Rnpw

Table 1
Location of the ve time series stations displayed in Fig. 1, and number of discrete (DOC, TDN, and alkalinity) samples taken during each time series.
Station ID

Coordinates

TS 1 outer Wadden Sea

TS 2 mid-Wadden Sea
TS 3 harbour
TS 4 oodgate
TS 5 upstream creek

534457.68N
534320.29N
534204.78N
534155.97N
534124.32N

74005.84E
74313.94E
74217.31E
74211.02E
74114.25E

Time started

Discrete sample size

Distance from oodgate (km)

4 Sep 2013 9:29

3 Sep 2013 7:28
5 Sep 2013 14:21
7 Sep 2013 10:25
8 Sep 2013 11:34

21
24
4
4
6

6.3
2.9
0.28
0.05
1.8

I.R. Santos et al. / Marine Chemistry 171 (2015) 1020

where Qebb is the export of water from the Wadden Sea to the North Sea
occurring at ebb tide (m3/s); RnTS 1 is the 222Rn concentration at station
TS 1 (dpm/m3); Jatm is the 222Rn ux to the atmosphere (dpm/m2/s); A
is the Wadden Sea area; 222 is the 222Rn decay constant (0.181 day1);
V is the volume of the Wadden Sea (m3); Qood is the import of water
from the North Sea to the Wadden Sea occurring during ood tide;
226
Ra is the concentration of dissolved 226 Ra in the Wadden Sea
(dpm/m3); Q dif is the 222Rn ux via molecular diffusion at the sediment
water interface (dpm/m2/s); AHT is the Wadden Sea area at high tide;
Qriv is the ux of water from creeks and rivers into the Wadden Sea
(m3/s); Rnriv is the 222Rn concentration in rivers draining to the
Wadden Sea (dpm/m3); and Rnpw is the 222Rn concentrations in
Wadden Sea porewaters (dpm/m3).
The radon mass balance was applied to the Spiekeroog Basin area located between station TS 1 and the Neuharlingersiel Harbour. All terms
of the mass balance were estimated for individual time steps and integrated over two complete tidal cycles (i.e., about 24 h; from high tide
to the second next high tide). The water ow rates (Q ebb and Q ood)
were estimated using a simple tidal prism approach that relied on the
change in depth (and volume) over time. Atmospheric evasion of
222
Rn was estimated as a function of piston velocities and the difference
between water and air concentrations (Burnett and Dulaiova, 2003 and
references therein). A linear interpolation between the low tide (volume: 39 106 m3; area: 14 106 m2) and high tide (volume:
184 106 m3; area: 71 106 m2) Spiekeroog Basin volume and area
(Stanev et al., 2003) was used to estimate atmospheric evasion and
222
Rn decay at each time step. In order to estimate molecular diffusion
from sediments, we used a depth independent approach that relies on
the average porewater radon concentrations (1916 Bq m3), sediment
porosity (assumed to be 0.5), and the average surface water concentration in the Wadden Sea (12.7 Bq m3) (Corbett et al., 1998). 226Ra concentrations for the same location were obtained from Moore et al.
(2011). The input of radon from river sources (Qriv Rnriv) was considered negligible (shown later).
The exchange of CO2 between surface waters and the atmosphere
was estimated using gas exchange equations from Wanninkhof (1992).
In summary, the CO2 ux across the water-air interface (F) was calculated as follows:
F kKH pCO2

where k is the CO2 gas transfer velocity (or piston velocities), KH is the
solubility of CO2 (Weiss, 1974) and pCO2 is the difference between
sea and air (pCO2sea pCO2air). The piston velocities k were estimated
as follows:
2

1=2

k 0:31 u Sc=660

13

3. Results
3.1. Surface water time series observations from automated monitors
The surface water time series experiments revealed highly variable
radon and pCO2 values along the coastal transect under investigation
(Fig. 2; Table 2). As expected, the highest radon and pCO2, and the lowest salinity, pH, and DO values were observed in the most upstream station (TS 5) located about 2 km from the oodgate in a creek draining
coastal wetlands. Station TS 4 (just upstream of the oodgate) had
pCO2 and radon values less than half those observed in TS 5 implying
signicant gas exchange as upstream creek waters travel downstream.
Interestingly, both TS 4 and TS 5 had dynamic concentrations over a
24 h cycle even though these stations are not tidal. In both TS 4 and TS
5, an increase in salinity lasting for 34 h was related to a major drop
in pH and DO, a signicant increase in pCO2 and no clear change in
radon (see shaded area in Fig. 3). A second feature observed in TS 5
was a steady increase in radon starting at 0.7 days coinciding with
an increase in pCO2 and decrease in pH. These short-term observations imply an initial decoupling between groundwater seepage and
pCO2 followed by a gradual pCO2 increase likely driven by groundwater
seepage.
The observations at TS 3 revealed different patterns within the
Neuharlingersiel Harbour. Even though the harbour is tidal, pH and
DO decreased to about 7.7 and 60% saturation when the salinities
were comparable to the Wadden Sea (~ 29 psu). The highest pCO2
values within the harbour were clearly related to the initial pH and
DO drop. During the night-time low tide, the oodgates were open
and released fresh upstream water to the harbour resulting in a drop
in salinity from 29 to nearly 5 within 1 h. The freshening of the harbour
raised the pH, DO, and radon values and decreased pCO2 from 1100 to
800 atm. During the incoming high tide towards the end of the experiment, all the variables investigated returned to levels comparable to
those early in the experiment.
The two Wadden Sea stations (TS 1 and TS 2) had similar tidal trends
for all the variables investigated. Both radon and pCO2 increased at low
tide while pH and DO decreased. The night-time low tide was about
12 cm lower than the day-time low tide and characterized by
100 atm higher pCO2 relative to the day time low tide in both TS 1
and TS 2. A similar night-time increase was also observed for radon, implying that tidally-driven porewater exchange, not pelagic respiration,
was the major driver of pCO2 at night. Interestingly, average radon
and pCO2 values in TS 1 (outer Wadden Sea) were 17% and 8% higher
than in TS 2 (mid Wadden Sea) (Table 2). Even though those gradients
may be related to unmonitored temporal changes (TS 1 was performed
one day after TS 2), this spatial variability is consistent with porewater
inputs from the Janssand, the largest local sand at which is located in
between TS 1 and TS 2.

3
3.2. Discrete DOC, TDN, and alkalinity samples

where u is the wind speed (m s1) at a height of 10 m and Sc is the

Schmidt number of CO2 at in situ temperature and salinity. To estimate
CO2 uxes, we assumed a constant atmospheric pCO2 of 388 atm (average measured with a Licor 820 for 24 h just before and after the surface
water observations). The Wanninkhof (1992) piston velocities are likely
to underestimate gas exchange in the Wadden Sea because they ignore
current-driven turbulence that cannot be accounted for with the data
available. Therefore, our gas exchange estimates should be seen as conservative values.
Porewater-derived solute uxes were estimated by multiplying the
radon-derived porewater exchange rate by the average endmember
concentration in porewaters. Porewater pCO2 values and free CO2 concentrations values in the vertical prole were calculated from pH (NBS
scale), alkalinity, temperature and salinity observations using carbonate
system constants from Millero (2010) and the CO2SYS programme.

The average DOC and TDN concentrations were about 3-fold higher
in upstream creek waters than in the Wadden Sea (Table 2). Alkalinity
was about 10% higher in the creeks (stations 4 and 5) than in the
Wadden Sea (stations 1 and 2). Both DOC and TDN had clear tidal trends
during the 24 h time series performed at station 2 (Fig. 3) similar to the
radon patterns at the same station (Fig. 2). The DOC and TDN increase
during the ebb tide was much slower than the associated decrease during the ood tide. The alkalinity tidal trends were unclear perhaps due
to the relatively high analytical uncertainty (about 3%) in high alkalinity
seawater subject to relatively minor variability on short time scales. Unfortunately, the less detailed temporal resolution (see Table 1) of DOC,
TDN, and alkalinity samples at stations other than TS 2 prevented a
more comprehensive assessment of their temporal dynamics (data
not shown).

14
I.R. Santos et al. / Marine Chemistry 171 (2015) 1020
Fig. 2. Results of time series observations at the ve surface water stations. The vertical grey bars highlight major features described in the text. The Y axis scales are not necessarily the same to highlight gradients. The time zero for each location are
shown in Table 1. The horizontal black bars near the bottom of the X axes represent the approximate time of dark hours.

2.53 0.02
2.49 0.03
2.56 0.03
2.73 0.31
2.83 0.31
11.37 2.38
10.29 2.94
15.32 1.83

5.5 2.0
4.4 2.0
7.8 0.7
7.4 5.0
6.0 3.1
na
na
na

2.5 1.4
1.6 1.5
4.6 0.8
6.0 6.5
3.3 3.7
na
na
na

20 15
74
122 34
93 160
381 356
na
na
na

15

271 75
282 93
762 266
996 94
960 40
352 58
284 55
599 89
644 57
597 86
1174 190
637 222
3616 943
6010 2391
4100 2777
13,011 863
TS 1 outer Wadden Sea
TS 2 mid-Wadden Sea
TS 3 harbour
TS 4 oodgate
TS 5 upstream creek
All porewaters
Shallow porewater
Deep porewater

13.7 6.2
11.7 6.7
38.6 11.2
59.2 4.9
112.7 19.4
1916 408
1755 412
3958 1218

18.5 0.2
18.1 0.2
19.5 0.4
20.2 0.1
18.2 0.6
16.3 0.2
16 0.2
16 0.2

28.9 0.0
28.9 0.1
23.6 7.6
17.8 2.2
7.2 1.5
31.1 0.4
31.0 0.5
31.2 0.2

8.03 0.03
8.01 0.05
7.87 0.12
7.85 0.09
7.69 0.14
7.96 0.15
8.08 0.17
7.54 0.03

99.3 3.0
101.8 5.5
79.9 15.6
88.5 10.4
74.0 12.6
na
na
na

25 4
26 4
62 9
74 14
72 8
475 144
285 131
1172 65

CO2 evasion
mmol m2 day1
Piston velocity
m day1
Wind m s1
Alkalinity
mmol L1
TDN mol L1
DOC mol L1
pCO2 atm
DO % sat.
pHNBS
Salinity
Temp. C
Rn Bq m3
222

Table 2
Average (standard deviation) concentrations of selected variables at the ve time series stations and porewater samples. na = not available or not applicable. The piston velocities were calculated using equations from Wanninkhof (1992).

I.R. Santos et al. / Marine Chemistry 171 (2015) 1020

Fig. 3. Time series of DOC, TDN and alkalinity at station TS 2 (Mid Wadden Sea). A 3 point
smoothing was applied to the raw data to better illustrate trends.

3.3. Porewater observations

The porewater observations revealed lower salinities in the upper
metre of sediments (Fig. 4). The pH was highly variable along the horizontal transect reaching N9 in samples with alkalinity N20 mM. In the
vertical prole, pH decreased from 7.93 in shallow samples to 7.50 at
4.5-m deep. Alkalinity and pCO2 slightly increased with depth until
about 2 m and then had a sharp increase between 2 and 3 m. The
radon concentrations in the shallow samples from the horizontal transect were lower than 1000 Bq m 3 probably reecting fast surface
water recirculation. In the vertical prole conducted by Moore et al.
(2011), no clear radon trends were observed with depth. The deeper
porewaters are about 2 orders of magnitude higher in radon than in surface waters. DOC and TDN concentrations were about 3- and 10 fold
higher in porewaters deeper than about 2 m than in the shallower
samples.

3.4. Radon mass balance

Integrating the radon uxes over a 24 hour cycle at TS 1 revealed
total 222Rn losses from the Spiekeroog Basin to be 3.4 109 Bq day1.
Exports of radon to the North Sea accounted for 67% of those losses,
while atmospheric evasion and 222Rn decay accounted for 27 and 7%
of the total losses, respectively. Molecular diffusion from sediments
and decay of dissolved 226Ra are the only sources of radon to surface waters other than porewater advection. The concentrations of dissolved
226
Ra in surface waters of the Wadden Sea averaged 2.0 Bq m3 and
ranged between 1.2 and 3.2 Bq m 3 over multiple seasonal

16

I.R. Santos et al. / Marine Chemistry 171 (2015) 1020

Fig. 4. Porewater observations in June and July 2008 (from Table 3 in Moore et al., 2011) and in September 2013 (original data).

observations (Moore et al., 2011). The average 226Ra concentrations are

identical to the lowest 222Rn values detected in the Wadden Sea during
our experiments (2 Bq m3; Fig. 3). Therefore, only the lowest 222Rn
values can be supported by dissolved 226Ra decay and nearly all 222Rn
observations were higher than 3 Bq m3. Using a depth-independent
approach (Corbett et al., 1998), radon diffusive uxes were estimated
to be 1.8 Bq m2 day1 which would upscale to 1.8 108 Bq day1 to
the entire area of the Spiekeroog basin during high tide (71 106 m2).
Therefore, the estimated radon inputs from diffusion from sediments
can account for only ~5% of the total radon losses from the Spiekeroog
Basin.
The excess radon losses that cannot be accounted by molecular diffusion and 226Ra decay were assumed to be related to porewater advection. By dividing the excess radon losses (3.2 109 Bq day1) by the
average porewater radon concentration (1916 Bq m3), we obtain
porewater exchange rates of 1.7 106 m3 day1. These volumetric
porewater exchange rates are equivalent to 1.1% of the tidal prism volume (1.45 108 m3). Using the area of the Spiekeroog Basin at low tide
(1.4 107 m2), we can convert the volumetric porewater exchange
rates to aerial exchange rates of 11.8 cm day1 (or 118 L m2 day1
as used by some authors).
Estimating uncertainties is difcult because porewater exchange
rates were estimated for a single day using mostly data from TS 1. The
three main sources of uncertainty are radon exports to the North Sea
(which accounted for 67% of all radon losses), atmospheric evasion
(27% of radon losses) and the groundwater endmember radon concentration. Uncertainties in other terms would have a negligible effect on
the nal estimates. We make a series of assumptions to provide a reasonable potential uncertainty for our radon-derived porewater exchange estimates. The radon exports were quantied from high
resolution radon observations and a tidal prism approach. We assume
a 5% analytical uncertainty for each radon observation and a 30% uncertainty in the tidal prism approach (i.e., unknown uncertainty related to
the volume and area of the Spiekeroog Basin). Our atmospheric evasion
calculations are considered a minimum value because we cannot account for turbulence driven by currents which may dramatically enhance gas exchange (Borges et al., 2004; Call et al., 2015). We assume

Table 3
Porewater derived uxes to the Wadden Sea. All uxes are in units of mmol m2 day1.
The minimum, maximum and most probable values were estimated using the shallow,
deep, and overall average concentrations in porewaters shown in Table 2.

Free CO2
DOC
Alkalinity
TDN

Minimum

Maximum

Most probable

6
34
1216
34

57
71
1811
139

18
42
1344
56

a ~ 50% uncertainty based on an independent approach to estimate

radon evasion (Dulaiova and Burnett, 2006). The standard error of
radon observations in porewater was 21% (Table 1). Propagating these
uncertainties through the mass balance would create a nal porewater
exchange uncertainty of 32% assuming that the analytical uncertainties
are negligible (individual observation uncertainty b 5%) and that the
porewater samples are representative of seeping waters.
3.5. Porewater-derived solute uxes
We multiplied the radon-derived porewater exchange rate by average solute concentrations in porewater to estimate porewater-derived
solute uxes to the Wadden Sea (Table 3). Radon alone cannot resolve
whether the surface water signal originated from shallow or deep
porewater. Considering that solute concentrations in shallow porewater
were much lower than deep groundwater (Table 2), we used the respective averages as the porewater endmember to constrain the likely
range in porewater uxes. The minimum values shown in Table 3 rely
on the assumption that 100% of the radon signal observed in the
Wadden Sea originated from porewater shallower than 1.5 m, while
the maximum values assume that 100% of the radon signal originated
from porewater deeper than 1.5 m. The real solute uxes are likely to
be in between these extreme values since an unknown proportion of
shallow and deep porewater seep into the Wadden Sea. Overall, a difference ranging from about 50% for alkalinity and 10-fold for free CO2 was
estimated using these minimum and maximum assumptions (Table 3).
The most probable uxes shown in Table 3 rely on the average concentration of all porewater samples.
4. Discussion
4.1. Porewater exchange
The radon observations in the Wadden Sea revealed a clear tidal
trend that is best explained by porewater exchange (or SGD) from intertidal ats. Sources other than porewater exchange, such as molecular
diffusion from sediments and dissolved 226Ra decay, were minor in
agreement with a number of previous studies in other coastal systems
(Burnett et al., 2006; Peterson et al., 2008; Santos et al., 2010;
Swarzenski, 2007). In the Wadden Sea, radon losses were dominated
by exchange with the North Sea in spite of windy conditions
(i.e., wind speeds around 5 m s1; Table 2). The radon mass balance required porewater exchange rates of 11.8 cm day1 which are equivalent to 1.1% of the surface water tidal prism volume in the Spiekeroog
Basin. These radon-derived porewater exchange rates are consistent
with a number of earlier studies using other approaches in the same region of the Wadden Sea. Pressure observations revealed that sand ats
act as one-way valves, passing water from the central surface through

I.R. Santos et al. / Marine Chemistry 171 (2015) 1020

17

Fig. 5. Radon and salinity scatter plot in the ve surface water time series stations. The inset highlights the two Wadden Sea stations.

the interior of the at to an outow zone at and below the low water
line with a velocity of mm to cm per day (Ry et al., 2008).
Porewater exchange rates of 1222 cm day1 in the upper 50 cm of
sediments were estimated for the Wadden Sea using dye tracer experiments (Billerbeck et al., 2006a). Porewater emerging from layers deeper
than about 1 m, however, had lower seepage rates ranging from 0.5 to
7 L m2 day1 (Ry et al., 2008). A numerical model based on pressure
gradients, in turn, revealed maximum groundwater velocities of up to
7 cm h1 in the upper 5 m of the intertidal at (Riedel et al., 2010).
Using a radium mass balance, Moore et al. (2011) estimated porewater
exchange rates of 24 105 m3 per tidal cycle (~ 12 h). Moore's estimates are 2- to 4-fold lower than the radon based estimates reported
here. While porewater ow rates obtained from these previous studies
are within one order of magnitude of those obtained from our radon
mass balance, comparing the techniques is difcult. First, while radon
integrates all physical processes driving porewater exchange on time
scales of at least a few days (Santos et al., 2012b), the modelling studies
focused on specic physical processes and may have not quantied dispersive transport. Second, a comprehensive seasonal assessment of
porewater exchange rates is not available for the Wadden Sea, which
complicates the direct comparison of studies performed at different
times of the year. Combining multiple chemical tracers and modelling
approaches may help to separate the relative contribution of shallow
versus deep porewater exchange in the Wadden Sea.
Resolving the relative contribution of fresh and saline groundwater
is fundamental to shed light into the global biogeochemical implications
of SGD and porewater exchange (Moore, 2010). While fresh SGD is a
source of new carbon and nutrients, saline SGD is a source of recycled
solutes (Santos et al., 2014). Radon builds up in any porewater or
groundwater on time scales set by its decay constant (3.84 days) regardless of salinity. Therefore, radon can be used as a tracer of both
fresh groundwater discharge or saline porewater exchange as long as
the water was in contact with sediment for at least several hours to
acquire a detectable radon signal (Swarzenski, 2007). Radon concentrations will reach steady state in porewater after about 20 days (~5 radon
half-lives). In the Wadden Sea, the residence time of seeping porewater
was estimated to reach 30 years (Ry et al., 2008).
We can use a simple salinity scatter plot to gain further insight into
radon sources to the Wadden Sea. In spite of a general trend of increasing radon concentrations in freshwaters upstream of the oodgate, no
signicant correlations were observed between radon and salinity in
the two Wadden Sea time series stations (Fig. 5). This contrasts to locations where radon distribution in surface waters may be dominated by
fresh groundwater (Cyronak et al., 2013; Peterson et al., 2009), which is
clearly not the case in the Wadden Sea where seepage is diffuse and
dominated by surface water recirculation in sediments (Moore et al.,
2011). Therefore, the radon dynamics in the Wadden Sea was unrelated
to any terrestrial freshwater inputs during our experiments. It has

previously been suspected that fresh groundwater ows underneath

the dike towards the Wadden Sea (Beck et al., 2012). However, the
lack of correlations between radon and salinity, and the negligible variability in salinity over a tidal cycle within the Wadden Sea (Fig. 3) imply
that both fresh surface and groundwater inputs were minor during our
experiments. Investigations during periods of higher terrestrial freshwater discharge (i.e., January; Beck and Brumsack, 2012) would be
needed to further assess whether terrestrial inputs can be a source of
radon to the Wadden Sea.
4.2. Carbon dynamics
While resolving the specic biogeochemical processes producing
and consuming CO2 within sediments is out of the scope of this study,
our observations revealed that the Spiekeroog Basin in the Wadden
Sea was a net source of CO2 to the atmosphere during our experiments
(Table 2). The adjacent North Sea is considered a sink for CO2 (Borges
et al., 2005; Lorkowski et al., 2012), whereas several estuaries
draining to the North Sea act as sources of CO2 to the atmosphere
(Frankignoulle et al., 1998). Our study also revealed that porewater exchange was a major driver of CO2 supersaturation in the Wadden Sea
during our short term investigation.
In contrast to the noble gas radon which has a single major source to
the Wadden Sea, CO2 is a biogenic gas with multiple drivers including
benthic and pelagic respiration and photosynthesis and a number of
biogeochemical processes within sediments. The main two drivers of
CO2 in estuaries are net heterotrophy and the freshwater CO2 input
from surrounding rivers and creeks (Borges and Abril, 2011). We can
use dissolved oxygen as a proxy for respiration and photosynthesis,
and salinity as a proxy for terrestrial freshwater inputs into the Wadden
Sea. The predominantly diel trend of DO (Fig. 2) in the outer Wadden
Sea station (TS 1) is consistent with a diel cycle of photosynthesis and
respiration suggesting these processes as the major drivers of DO. However, the dominant tidal trend for pCO2 implies that the processes driving DO are not necessarily the same processes driving pCO2 in the
Wadden Sea. This is further supported by DO supersaturation (N 100%)
coinciding with pCO2 N 550 atm well above equilibrium with the atmosphere (~ 390 atm). The concurrent supersaturation of both DO and
CO2 implies that photosynthetic uptake of CO2 during times of
DO N 100% was small compared to other CO2 sources such as porewater
as also observed in an Australia estuary (Macklin et al., 2014).
The signicant correlations between radon (an unambiguous
porewater tracer in the Wadden Sea) and pCO2 imply that porewater
exchange was a major source of free CO2 to surface waters in the
Wadden Sea in line with the estimated porewater uxes (Table 3)
being comparable in magnitude to the CO2 degassing rates (Table 2).
The non-signicant relationship between pCO2 and salinity (Fig. 6)
demonstrate that CO2-enriched freshwater inputs from upstream

18

I.R. Santos et al. / Marine Chemistry 171 (2015) 1020

Fig. 6. Correlations between pCO2 and some potential controls in the ve surface water time series stations. The inset highlights the trends in the two Wadden Sea stations. The p values for
all the correlations in the Wadden Sea Stations were b0.01 except for the pCO2 vs. salinity relationships.

creeks were unlikely to be an important driver of CO2 in Wadden Sea

surface waters. This is consistent with the minor release of freshwater
through the oodgates (i.e., no freshwater pulses were detected in the
Wadden Sea salinity data). The equations describing the radon vs.

pCO2 relationship at TS 1 (pCO2 = 8.0 ( 0.4)Rn + 530 ( 7)) and TS

2 (pCO2 = 11.8 ( 0.6)Rn + 460 ( 8)) imply that in the absence of
porewater exchange (i.e., radon approaching zero), pCO2 would still
occur in excess of atmospheric equilibrium likely due to respiration in

I.R. Santos et al. / Marine Chemistry 171 (2015) 1020

shallow sediments. Sediment chamber incubations in the Wadden Sea

demonstrated that emerged sediments may be an important source of
CO2 to the atmosphere (Klaassen and Spilmont, 2012). When emerged
at night, those sediments are likely to release CO2 to Wadden Sea surface waters. Indeed, a ~ 100 atm excess pCO2 during the night time
low tide relative to the day time low tide was observed at both stations
TS 1 and TS 2. A similar combination of diurnal (biological) and tidal
(groundwater/porewater inputs) was suggested to drive pCO2 in an
Australian subtropical estuary (Maher et al., 2015).
There are multiple ways in which porewater exchange can drive CO2
dynamics in coastal waters: (1) by supplying nutrients that stimulate
primary production and DIC uptake; (2) by acting as a direct source of
metabolic CO2 to coastal waters; (3) by supplying organic carbon that
stimulates respiration; and (4) by acting as a sink of CO2 in systems
where porewater CO2 is consumed during CaCO3 dissolution. The production of alkalinity via CaCO3 dissolution or sulphate reduction may increase the capacity of seawater to absorb atmospheric CO2 (Andersson
et al., 2008; Cyronak et al., 2014). In the Wadden Sea, alkalinity generating processes such as sulphate reduction can mineralize an average of
78 g C m2 year1 in the upper 15 cm of sediments which is equivalent
to about 25% of total OM mineralization in sediments (Al-Raei et al.,
2009). Alkalinity generating processes in sediments may act in synergy
with primary productivity to decrease pCO2 in the Wadden Sea. A total
pelagic and benthic primary production in the Wadden Sea was estimated to range between 30 and 950 g C m2 year1 (Billerbeck et al.,
2006b and references therein), well above the rates of alkalinity production in sediments.
If we upscale the estimated CO2 outgassing rates in the two Wadden
Sea stations (Table 2) to an annual basis, they would range from 31 to
88 g C m 2 year 1 (or 720 mmol m2 day1). These estimated CO2
outgassing rates would represent a minor fraction of the C uptake estimated by Billerbeck et al. (2006b). However, it is difcult to compare
our CO2 outgassing rates to annual rates of net productivity observed
in the Wadden Sea because we have short term CO2 observations
only. The productivity rates observed by Billerbeck et al. (2006b)
imply that the Wadden Sea is a sink of CO2, while our CO2 observations
imply the Wadden Sea was a net source of CO2 to the atmosphere.
Billerbeck's observations in the Wadden Sea were based on water column productivity and near surface sediments rather than direct pCO2
observations. Our radon and CO2 observations presumably integrate
all processes occurring in the water column, shallow and deep sediments. Some of our observations in shallow porewater (Fig. 4) revealed
low pCO2 consistent with Billerbeck's observation that these shallow
sediments may be autotrophic. Much higher CO2 concentrations were
usually observed in deeper porewaters (Fig. 4). Therefore, we suspect
that the CO2 and radon signal observed in Wadden Sea surface waters
is a response of deep (not captured in previous productivity estimates)
rather than shallow porewater exchange.
This suggestion is consistent with previous experimental and
modelling investigations. For example, DOM degradation was observed
in deeper Janssand sediments (Seidel et al., 2014). Organic matter entering the tidal ats is subjected to degradation, rst aerobically, then by
sulphate reduction, and nally by methanogenesis (Ry et al., 2008).
All of those processes may produce CO2 or alkalinity that are eventually
released to surface waters. The prevalence of deep rather than shallow
porewater as a source of CO2 is further supported by the correlations observed between radon and pCO2 in surface waters. Using the average
radon concentrations in porewater (1916 Bq m3), and the equations
describing the Rn vs. pCO2 relationship shown above, we can predict
that the pCO2 values of porewater entering the Wadden Sea would
range from 15,000 to 24,000 atm. This predicted value is only slightly
higher than the average pCO2 values observed in deep porewater
(~13,000 atm) but much higher than the pCO2 of shallow porewaters
(1300 atm; Table 2). Therefore, the projection of surface water observations to the porewater endmember implies that deep porewater
was the major source of both radon and CO2 to the Wadden Sea.

19

5. Conclusions
Radon can be an effective porewater tracer even in Wadden Sea conditions (i.e., strong winds and well mixed surface waters). The radon approach employed here revealed a 24-h integrated porewater exchange
rate of 11.8 cm day1 (upscaling volumetric uxes to the submerged
area at low tide) which was equivalent to 1.1% of the Wadden Sea
tidal prism volume. These results were consistent with a number of earlier studies in the Wadden Sea that demonstrated active porewater exchange in the intertidal at. The radon method integrates all porewater
exchange processes taking place on time scales of at least a few days
(i.e., comparable to the radon half-life) and is suitable for long term
observations.
The estimated porewater-derived free CO2 uxes were 6
57 mmol m2 day1, which was on the same order of magnitude as the
average CO2 outgassing rate observed in the two Wadden Sea stations
(720 mmol m2 day1). These uxes and signicant correlations between radon and pCO2 revealed that the Wadden Sea was a net source
of CO2 to the atmosphere, and that porewater exchange was a major
driver of CO2 outgassing from the Wadden Sea during our week-long
investigation.

Acknowledgements
The Otzum and the ICBM staff provided valuable help during eld
and laboratory work. We thank Matthias Friebe for running DOC and
TDN samples, and Carola Lehners for performing alkalinity analysis. IRS
acknowledges nancial support from the Australian Research Council
(DP120101645 and LE120100156). DTM acknowledges funding through
an Australian Research Council DECRA fellowship (DE150100581). Most
of this work was performed during IRS sabbatical at the HanseWissenschaftskolleg (HWK) in Delmenhorst, Germany. We thank the
HWK staff for outstanding support during this investigation.

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