LIMNOLOGY

and

OCEANOGRAPHY

Limnol. Oceanogr. 00, 2014, 0000

C 2014 Association for the Sciences of Limnology and Oceanography
V

doi: 10.1002/lno.10004

High CO2 evasion during floods in an Australian subtropical estuary

downstream from a modified acidic floodplain wetland
Sergio Ruiz-Halpern,* Damien T. Maher, Isaac R. Santos, Bradley D. Eyre
Centre for Coastal Biogeochemistry Research, School of the Environment, Science and Engineering, Southern Cross University, Lismore, New South Wales, Australia

Abstract
Dissolved CO2 dynamics associated with flooding and postflood recovery were investigated in the lower
estuary of the Richmond River and a tributary draining an acidic wetland. Heavy rains (up to 133 mm d21)
resulted in large discharge volumes (up to 250 3 106 m3 d21) flushing the estuary in less than a day. Maximum values of the partial pressure of CO2 (PCO2 , 2006 Pa or 19,801 latm) occurred during the postflood
recovery period. High PCO2 values were related to the transport of floodplain metabolic products via surface
runoff and groundwater as well as the low pH (4.22) of waters draining a modified wetland with coastal acid
sulphate soils. Aerobic respiration alone could not explain the high concentrations of CO2 in the estuary and
an area of low buffering developed in the 020 salinity range. PCO2 was correlated with freshwater discharge
in the Richmond River main channel (R2 5 0.82; p < 0.05; n 5 9) but not in the acidified tributary (R2 5
0.17; p > 0.05; n 5 7). Air-water fluxes of CO2 were at the high end of the range for aquatic systems (maximum 1413 mmol C m22 d21, mean 252 mmol C m22 d21). This study highlights the large spatiotemporal
variability of PCO2 , the importance of episodic flooding events, the role of adjacent modified acidic wetlands,
and the role of groundwater discharge as a source of CO2 to estuaries. Global estimates of CO2 air-water
fluxes in estuaries may be under estimated due to the lack of high-resolution data to capture short-term
episodic events (e.g., flooding), in tropical and subtropical areas.

The partial pressure of CO2 (PCO2 ) within estuarine waters

is usually higher than equilibrium, therefore, they are generally considered to be a source of CO2 to the atmosphere
(Borges et al. 2005; Cai 2011), although autotrophic estuaries
may represent atmospheric CO2 sinks (Maher and Eyre
2012). The high PCO2 generally found in estuarine ecosystems is attributed to several processes including ecosystem
heterotrophy (Borges and Abril 2011), inputs of CO2 rich
surface water (Cole et al. 2007), or groundwater (Atkins et al.
2013) and precipitation of carbonate and silicate minerals
(Hagedorn and Cartwright 2010). Of these processes, in situ
respiration and inputs of CO2 enriched water are often considered the main drivers. The relationship between heterotrophy and CO2 in aquatic ecosystems has been well
established (Borges and Abril 2011), with inputs of allochthonous dissolved and particulate organic carbon subsidizing
a large portion of the respiration in the water column. The
influence of allochthonous inputs of CO2 is less well understood but the available studies suggest that lateral inputs
from soils by surface runoff and groundwater are an

important source of CO2 (Cai 2011; Atkins et al. 2013). This

may be particularly true in modified acidic wetlands that
have low O2 and low pH waters (Ferguson and Eyre 1999)
with most of the inorganic carbon as dissolved CO2 resulting
in high PCO2 (Atkins et al. 2013).
Wet and dry (sub) tropical estuaries have a highly variable
hydrology reflecting their episodic rainfall patterns (Eyre
1998). The hydrology of Australian subtropical estuaries has
been broadly categorized into four stages (flood conditions,
estuarine recovery, dry with minor rains, and dry conditions;
Eyre and Twigg 1997; Eyre 1998). Flood conditions are understudied, as they are often difficult to capture. Most biogeochemical processes in the estuarine basin are largely bypassed
during flooding in riverine estuaries (Eyre and Twigg 1997;
Eyre and Ferguson 2006), and most of the catchment load of
materials is transported to near shore coastal waters (McKee
and Eyre 2000).
Floodplain wetlands of many subtropical estuaries have
been extensively drained, mostly for agriculture, producing
coastal acid sulphate soils (CASS; Sammut et al. 1996), which
can deliver low pH and low oxygen waters to the estuary (Sammut et al. 1996; Eyre et al. 2006; de Weys et al. 2011). This

*Correspondence: Sergio.ruiz-halpern@scu.edu.au

Ruiz-Halpern et al.

CO2 evasion in modified wetlands

delivery of low pH and low oxygen waters can be enhanced by

groundwatersurface water interactions (Santos and Eyre
2011). CASS are distributed all around Australia, but are also a
prominent feature of densely populated highly modified
coastal areas around the world, mostly in tropical regions but
they are also common in temperate regions (Sullivan et al.
2012), with an estimated total area of 50 million hectares
worldwide (Ritsema et al. 2000). CASS soils develop when
reduced inorganic sulphides accumulate. This occurs when
there is a supply of organic material, reducing conditions conducive to sulphate reduction, delivery of sulphate (tide water
or other saline ground and surface waters), and a supply of
iron for the formation of iron sulphides, conditions generally
found in tidal swamps, and saltmarshes (Sullivan et al. 2012).
The effect of flooding events on material cycling in estuaries adjacent to modified wetlands with CASS has mainly
focused on: (1) nutrient processing, where most nutrients are
exported during the flood stage and groundwater contributes
a substantial portion of the nutrients delivered to the estuary
(Eyre and Twigg 1997; Santos et al. 2013), (2) groundwater
surface water interactions, where draining the landscape
may enhance groundwater inputs and their associated solutes (Santos and Eyre 2011), (3) estuarine acidification, triggered by groundwater discharge of H1 produced during
exposure of the sediments to air (de Weys et al. 2011), (4)
the deoxygenation potential of CASS environments and its
link to fish kills (Eyre 1997; Eyre et al. 2006), and (5) metal
exports and toxicity (Wilson and Hyne 1997; Santos et al.
2011). However, estuaries also play an important role in the
global carbon cycle relative to their size (Borges et al. 2005;
Cai 2011), but the effects of flooding (freshwater discharge)
and the contribution of groundwater to CO2 evasion, especially in areas with modified wetlands with CASS is not yet
well understood (Borges and Abril 2011). However recent
evidence suggests that CASS may be hotspots for CO2 and
CH4 production (Gatland et al., 2014).
Most of the studies on carbon cycling in estuaries have
been performed in temperate areas in the northern hemisphere, mainly Europe and North America, where the hydrology has been found to have an important effect on CO2
emissions (Borges and Abril 2011; Cai 2011). Consequently,
the paucity of high-resolution data in tropical and subtropical
environments, subject to distinct hydrological regimes is a
major limitation in our ability to constrain the influence of
estuaries to the global carbon budget. Yet the few studies performed in low latitudes demonstrate high PCO2 concentrations
following floods (Sarma et al. 2011) or associated to seasonal
monsoons (Yuan et al. 2011) and identify groundwater as an
important driver in the export of carbon and a major factor in
CO2 evasion to the atmosphere (Atkins et al. 2013).
The aim of this study is to elucidate the effect of short
duration flooding events on air-water CO2 efflux of the lower
section of a subtropical estuary adjacent to a modified wetland with CASS. We hypothesize that (1) CO2 emissions to

Fig. 1. Map of the Richmond River detailing the starting point of the
surveys in Ballina and the ending point in the Tuckean Swamp. The
shaded grey area represents the extent of Coastal Acid Sulphate Soils
(CASS) in the Tuckean Swamp. The arrows mark the site of the gauges
where discharge was measured.

the atmosphere in subtropical estuaries are controlled by the

hydrological regime, (2) lateral inputs of wetland waters
enhance CO2 evasion to the atmosphere, and (3) groundwater is an important vector for the lateral transport of CO2
to estuaries from adjacent wetlands.

Methods
A series of surveys were conducted in the lower Richmond
River Estuary, New South Wales, Australia (Fig. 1). The Richmond River is a wave dominated barrier estuary located in
eastern Australias subtropical band, with a water area of
19 km2 and a catchment area of 6850 km2 (McKee et al.
2000). As a result of intense rain periods during the summer
(1800 mm average annual rainfall, 65% concentrated from
December to April) the estuary receives highly variable
catchment flows (Eyre and Pont 2003). This estuary is highly
modified with levee constructions, drainage networks, floodgates, and canals, as well as land clearing. The drainage
works in the flood plain wetlands, have lowered the groundwater table. As a result, the pyritic clays present in protected
estuarine embayments, and behind barrier systems formed
during the formation of the Richmond River floodplain in
the Holocene, have developed into CASS, which can deliver
very acidic water (pH < 4) after rain events (Sammut et al.
1996). These low pH waters can be found year round and are
primarily associated with groundwater inputs (de Weys et al.
2011).
2

Ruiz-Halpern et al.

CO2 evasion in modified wetlands

Fig. 2. Freshwater discharge (left axis) in the Richmond River, inverse of residence time (right axis), and rainfall (insert) during the study period. The
vertical lines mark the nine times that the samplings took place.

Discharge data for the Tuckean Swamp was obtained from

the Marom Creek (Sta. 203059) gauge, which captures 13.5%
of the Tuckean subcatchment discharge, and was also scaled
to the whole catchment by linear interpolation. Flushing
times for the Richmond were calculated using the relationships found by Hossain 1998 for the Richmond River:

The surveys started during the wet season on 30 January

2012, four days after a significant rain event (26 January
2012). Eight additional surveys (8, 18, 29, 36, 69, 119, 145,
and 245 d postflood) were conducted to assess PCO2 dynamics during the postflood recovery of the estuary to dry conditions (Fig. 2). The coverage of the surveys extended
approximately 30 km, from the mouth of the river to the
Tuckean Swamp, a modified wetland with CASS. The survey
track was recorded with a global positioning system (GPS,
Garmin GPS 72, 6 10 m accuracy) and all time-stamped data
matched to the relevant coordinates.
During the surveys, a boat was driven upstream, starting
at high tide, at 58 km h21, and continuous measurements
of PCO2 and 222Rn were recorded at 1 min and 10 min intervals, respectively. Ancillary data (temperature, salinity, pH,
and dissolved oxygen [DO]) were also recorded with a calibrated Hydrolab DS5X or an in situ multiparameter sonde
(troll 9500 series instrument) at five minute intervals. Rainfall and wind speed data were obtained from the Australian
government bureau of meteorology (Sta. 58061, Woodburn
at Cedar station, for rainfall and Sta. 58198, Ballina airport,
for wind speed). Discharge data for the Richmond catchment
was obtained from the New South Wales Department of
Water Resources Service for three gauges located in Casino
(Sta. 203004), Leycester creek at Rock Valley (Sta. 203010),
and the Wilsons river at Eltham (Sta. 203014, Fig. 1). These
three gauging stations capture 32% of the river discharge and
were scaled to the whole catchment by linear interpolation.

LnF 5 15:13 2 0:84 LnQ

(1)

where F is the flushing time (days) and Q the is flow

(m3 d21). For the Tuckean a mean depth of 1.6 m (Santos et
al. 2011) and an area of 1.6 km2 were used to calculate the
flushing time of the Tuckean swamp by dividing the
discharge onto the Tuckean swamp by the calculated volume
of the swamp.
PCO2 and 222Rn where measured using a coupled automated system that equilibrates dissolved CO2 and 222Rn
using a gas equilibration device (GED) into a closed loop air
circuit (Santos et al. 2012). The GED consists of a showerhead exchanger that sprays water, pumped from a depth of
approximately 50 cm below the surface, into a sealed chamber. The recirculating air passes through an anhydrous calcium sulphate column (drierite) before flowing through the
CO2 and 222Rn analyzers. Both CO2 and 222Rn are degassed
and the air-water equilibration time in the headspace for our
configuration was about 10 min for PCO2 and 30 min for
222
Rn. CO2 was measured with a LiCor 820 (calibrated to
2026.5 Pa, with an accuracy of better than 3% across the
whole range) and 222Rn with a Rad7 (Durridge).
3

Ruiz-Halpern et al.

CO2 evasion in modified wetlands

velocity and TSS, our evasion rates should be seen as minimum estimates.
Excess CO2, defined as free dissolved CO2 in excess of
atmospheric equilibrium was calculated following Zhai et al.
2005:
CO2
Excess CO2 5 CO2  2 KH
3 PCO2 air

where [CO2 ] is the concentration of total free CO2 ([CO2 ] 5

CO2
CO2
[CO2] 1 [H2CO3] 5 KH
3 PCO2 in water). KH
is the solubility coefficient of CO2.
Apparent oxygen utilization (AOU) 5 [O2eq] 2 [O2].
Where [O2eq] is the DO concentration (in lmol kg21) at
equilibrium with the atmosphere, calculated from equations
in Benson and Krause 1984.
The CO2sys Microsoft excel macro was used to obtain the
missing carbonate system parameters (total alkalinity [TA],
dissolved inorganic carbon [DIC], and the Revelle factor [R]).
Constants from Mehrbach et al. 1973, refit by Dickson and
Millero 1987, and National Bureau of Standrads (NBS) pH
scale were used in the calculations. The accuracy of the pH
is better than 0.2, which may induce large errors in the calculated parameters (DIC, TA, and R); however, given the
large gradients found in the estuary with pH values ranging
close to four units and PCO2 spanning several orders of magnitude, the calculated parameters still give an adequate
description of the gradients and variability found in this system. Because both temperature and salinity affect the solubility of CO2, we used the calculated DIC and TA at in situ
conditions, to calculate PCO2 at starting conditions (temperature and salinity at the beginning of the survey). The concentration of CO2 in lmol kg21 was used to calculate,
together with the discharge data, the amount of dissolved
CO2 entering the Richmond River Estuary from upstream
and from the Tuckean Swamp.

Fig. 3. Surface salinity along the track of the surveys showing four
broad hydrological stages defined: Flood (four days), postflood (days 8
69), dry with minor rains (69145), dry (day 245).

As the LiCor measures the fraction of CO2, and the air

stream was dried, we used the equations given in Pierrot et
al. 2009 to calculate PCO2 in latm and then converted to Pa
(1 atm 5 1.01325 Pa), CO2 evasion rates are dependent on
the concentration gradient between air and water and the
gas transfer velocity (k):
F 5 kaDPCO2

(2)

where k is the gas transfer velocity of CO2 in cm h21 and

DPCO2 is the difference between PCO2 in surface water and
air, and a is the solubility coefficient of CO2 (Weiss 1974).
By convention, positive fluxes are directed toward the atmosphere. The gas transfer velocity depends on turbulence at
the aqueous boundary layer. In estuaries, this is dependent
on windspeed, currents and total suspended solids (TSS)
(Borges and Abril 2011). To estimate k, we used the predictive equation proposed by Raymond and Cole 2001, normalized to a Schmidt number of 600 (k600):
3U
k600 5 1:91 3 e0:35
10

(4)

Results
The data collected over the five month period showed a
high degree of variability. The sampling started four days
after a major rain event (133 mm d21 on 26 January 2012,
Fig. 2), with previous rains providing wet antecedent conditions that triggered a large discharge of surface water (250 3
106 m3 d21, Fig. 2). Freshwater discharge closely followed
the rainfall pattern. Four days after the large rain (30 January
2012), the estuary remained fresh to the mouth (Fig. 2), with
a residence time of only 0.34 d. The maximum discharge
rate for the Tuckean swamp (9.9 3 106 m3 d21) was 25-fold
times lower than in the Richmond River Estuary but with
similar flushing times (Fig. 2).
Brackish water started traveling upstream one week postflood and reached 25 km (mouth of the Tuckean Swamp) 69
d later (Fig. 3). Our observations were separated into the
main river channel (Richmond River Estuary) and Tuckean
Swamp (Table 1). The Tuckean Swamp experienced the

(3)

where U10 is the wind speed at a height of 10 m, k600 was

corrected to the Schmidt number of CO2 at in situ temperature and salinity (Wanninkhof 1992). To calculate estuarywide fluxes, flux rates from each individual points were
interpolated using the spline with barriers method in a Geographical Information System analysis package (ArcGIS;
Maher and Eyre 2012). As we do not have data on current
4

Ruiz-Halpern et al.

CO2 evasion in modified wetlands

Table 1. Mean and ranges for water quality (temperature, salinity, pH, and DO) in the Richmond River Estuary and Tuckean
Swamp during each survey. nd 5 no data
Temperature ( C)
Days postflood (d)

Salinity

DO ( lmol kg21)

pH (NBS)

Mean

Range

Mean

Range

Mean

Range

Mean

Range

4
8

23.77
25.22

23.5124.28
23.5725.68

0.05
0.99

0.040.08
0.0515.29

6.44
6.42

6.246.59
5.917.25

128.3
57.9

100.6146.7
24.4201.8

18

25.77

24.8527.1

2.42

0.0510.04

7.22

6.877.66

96.1

79.7124.5

29
36

24.52
25.76

23.1325.63
2427.135

11.74
3.99

0.0533.28
0.0712.46

7.66
7.09

6.948.07
6.197.65

170.5
190.9

107.4233.3
160.9200

69

24.67

24.0825.15

17.44

1.1933.79

7.78

7.058.13

246

219.6268

119
145

20.18
16.57

18.8422.16
15.4720.02

13.4
7.06

0.5536.3
0.0638.25

7.72
6.84

7.288.03
6.238.03

252.9
225.9

226.9287.8
218.7239.7

245

21.84

19.3623.63

23.43

6.635.4

7.73

7.37.95

246.5

223.6261.3

Tuckean Swamp
4

24.82

23.9325.06

0.03

0.0010.04

5.02

4.586.37

65.1

46.0126.9

25.59

25.3425.78

0.04

0.040.05

5.66

5.466.3

10

2.252.2

18
29

26.45
24.14

25.8427.5
23.5124.76

0.05
0.08

0.040.06
0.050.11

6.82
6.4

6.607.07
5.816.93

77.1
37.3

11.998
1.9109.6

36

27.95

27.1828.08

0.09

0.080.09

5.7

5.356.19

148.1

136.4159.7

69
119

24.38
17.56

23.6025.3
16.0218.99

0.31
0.22

0.081.14
0.020.7

5.81
6.18

4.227.37
4.897.4

204.1
207.8

191.6219.6
171.8245.6

145

14.51

14.115.77

0.05

0.050.07

5.34

5.136.38

210.3

199.5230.1

245

nd

Richmond River

Table 2. Mean and ranges for

nd

222

nd

nd

Rn, PCO2 , [CO2], TA, DIC, and %CO2 in the DIC pool, for the Richmond River Estuary during each

survey
222

Rn
(Bq m23)

PCO2
(Pa)

[CO2]
( lmol kg21)

TA
( lmol kg21)

DIC
( lmol kg21)

%CO2

Days
postflood (d) Mean Range

Mean Range

Mean Range

Richmond
4

55.9

40.270.4

601.5

509879

208.3

298.8 218.5392.4

507.1 449.5695.8

41.2

50.2

22.169.6

873.4

2041196

290

66.4394.7

468.8

1481542

758.2

4291703

42.4

7.469.4

18
29

47.1
40.5

5.675.9
2.859.7

681.8
281.3

128951
38647

221.7
93.3

41.1302.4 2002.2
11.6219.1 2093

10532718
6183787

2213
2133.2

13102920
6123899

18.6
3.9

3.119.8
0.817.7

36

11.5

0.633.3

275.1

52480

88.8

16.9157.2

117984

709.6

2511137

14.5

3.353.3

69
119

13.1
23.6

1.320.8
5.629.7

135.2
60.9

44.7584.7
38112

43.6
22.5

13.2197.1 1677.9
11.742.7
847.8

7092252
3281525

1623.5
826.8

8212079
3421364

2.9
3.7

0.713.9
0.99.2

145

37.1

20.180.0

242.6

41399

103.4

13.3175.4

394.5

1051652

486.1

2221489

28.5

0.956.7

245

14.3

3.319.9

94.9

41232

31.3

13.678.7

1313.9

8841524

1277.3

9481441

2.5

1.17.5

Mean Range

177.8303.5

highest range in temperatures (14.128.1 C, Table 1) while

the Richmond River had average temperatures of 15.5
2.06 C (Table 1). Surface water salinity was variable in the
Richmond section reflecting the hydrological regime (Table
1; Fig. 2), but remained close to zero in the Tuckean Swamp
(Table 2; Fig. 3). Maximum pH values were typical of seawater conditions (8.13) and were found close to the mouth

625.4

Mean Range

Mean Range
32.952.1

in the Richmond River Estuary during the dry conditions.

The minimum pH observed in the Richmond River Estuary
was 5.91 on 02 February 2012 (Table 1). pH values in the
Tuckean Swamp were lower throughout the study, with a
mean of 5.88 and a range of 4.227.40 (Table 1).
The main arm and Tuckean Swamp remained hypoxic on
02 February (9.6% saturation, 9.9 lmol kg21 O2), one week
5

Ruiz-Halpern et al.

CO2 evasion in modified wetlands

Table 3. Mean and ranges for

222

Rn, PCO2 , [CO2 ], TA, DIC, and % CO2 in the DIC pool, for the Tuckean Swamp during each sur-

vey. nd 5 no data
222

Rn
(Bq m23)

PCO2
(Pa)

[CO2]
( lmol kg- 2 1)

TA
( lmol kg21)

DIC
( lmol kg21)

%CO2

Days
postflood (d) Mean Range

Mean

Tuckean Swamp
4
39.8

22.859.8

1422.9 6201581

478.6

213.5531.7

33

0265

525.4

422544

86.1

40.7

37.844.6

1757.5 8651891

579.4

284.8622.2

165.7

92459

747.3

569972

78.3

48.086.5

18
29

59.6
81.6

48.381.9
1148.5 7521873
53.2126.5 1183.6 6481863

368.8
407.5

243.1588.3 1263.1 10431612 1545.6 13201858

219.6650.3
557.4
209999
964.6
8301216

18.6
43.9

13.531.3
18.174.8

36

59.5

28.3115.8 1220.8 4182006

377.6

131.3619.8

90.9

53.888.8

69
119

32
60.3

19.863.7
33.9117.9

nd
345.6

95618

nd
145.8

37.6268.8

nd
177.7

145

97.2

60.2134.6

545.5 536692

249.5

155.2317.8

25

245

nd

nd

Range

Mean Range

nd

Mean

Range

Mean

65130

Mean Range
44.796.9

227698

14.5

0515

nd
326

215557

nd
48.9

7.595.9

8166

279.1

174340

89.5

48.394.7

nd

471.2

Range

nd

nd

Fig. 4. Salinty relationships with PCO2 , 222Rn, O2 pH, TA, and DIC.
most downstream river section of the Richmond River Estuary (Tables 2, 3; Fig. 4). The highest PCO2 value measured in
the Richmond River Estuary was 1196 Pa seven days after
the flood. The minimum value was slightly lower than
equilibrium (38 Pa 119 d after the flood, atmosphere 5 40
Pa; Table 1). The maximum value in the Tuckean Swamp
was 2006.2 Pa 36 d after the flood and the minimum value
95 Pa 119 d after the flood, the overall mean for the swamp
was 1171.7 Pa, a value 2.7-fold higher than the mean PCO2
in the river section (439.5 Pa) (from Tables 2, 3).
In general, there was an increase in PCO2 and 222Rn during
the postflood recovery of the estuary from flood conditions,

postflood, but reached super saturation at the mouth of the

Richmond River two months after the flood (maximum of
138% saturation, 226.9 lmol kg21 O2; Table 1). The Tuckean
Swamp was hypoxic (3.9% saturation, 2.2 lmol kg21 O2),
following the flood and remained under saturated throughout the study period (Table 1). 222Rn values were higher in
the Tuckean Swamp than in the Richmond River except during the first two sampling events following the flood. The
mean 222Rn value in the river was 39.2 Bq m23 (Table 1),
and 61.5 Bq m23 for the swamp (from Tables 2, 3). The maximum value reached 134.6 Bq m23 in June in the Tuckean
Swamp and the minimum value was 0.6 Bq m23 in the
6

Ruiz-Halpern et al.

CO2 evasion in modified wetlands

Fig. 5. Estuarine PCO2 distribution along the surveys. Data for 29 d at the mouth and 68 and 245 d in the Tuckean Swamp are missing due to equipment failure.
222

with a concurrent decrease in pH and DO (Tables 2, 3). As

the estuary returned to dry conditions, pH and DO increased
and PCO2 and 222Rn decreased (Tables 13). pH, O2, and calculated TA and DIC, generally increased with increased salinity, while Rn and PCO2 decreased. However, at low salinity
there was a high degree of variability in all parameters (Fig.
4). PCO2 distribution in the Richmond River Estuary
increased in an upstream direction and remained high in
the Tuckean Swamp throughout the study period (Fig. 5).
AOU and excess CO2 were positively correlated in all surveys in both the main channel and the Tuckean swamp
(Fig. 6), while the ratio of PCO2 from in situ to starting conditions remained close to 1 during flood conditions but
reached close to 0.5 on returning to dry conditions (Fig. 7).

Rn had a positive relationship with PCO2 and an inverse

relationship with oxygen and pH, in both the main channel
and the Tuckean Swamp (Table 4; Fig. 8). The R followed a
bell-shaped curve, with a minimum buffering zone around
the 315 salinity range, concurrent with the areas where TA
were closer in value to DIC (Fig. 9).
CO2 flux from the estuary was high (Table 5), with most
fluxes directed toward the atmosphere. The maximum fluxes
always occurred in the Tuckean Swamp with a maximum
integrated value of 1413 mmol m22 d21 29 d after the flood.
System wide averages, showed fluxes generally higher during
the recovery period, although fluxes were modulated by
windspeed, peak fluxes occurred shortly after the heavy rains
in January (Table 3), with a maximum flux for the whole
7

Ruiz-Halpern et al.

CO2 evasion in modified wetlands

Fig. 6. Scatterplots of excess CO2 vs. AOU in the Richmond River and
Tuckean swamp sections. All relationships are statistically significant (p <
0.05). R2 values and slopes of best fit are summarized in Table 4.

estuary of 10.11 3 106 mol d21 for the area surveyed seven
days after the flood. The highest export of dissolved CO2
into the estuary occurred during flooding with 19.75 3 106
mol d21 (5.5 times higher than atmospheric evasion). The
Tuckean Swamp is 11.3% of the area covered by the Richmond section; however, the flux of CO2 to the atmosphere
ranges from 18% to 265% of the lower Richmond River Estuary flux depending on the hydrological stage, but the export
of dissolved CO2 to the estuary was always lower than from
the river (Table 5). The mean overall flux to the atmosphere
during the study was 252 mmol m22 d21 (Table 6, calculated
from Table 5) and is among the highest average flux measured in worldwide estuaries (Table 6).
To test whether hydrology controlled PCO2 in the Richmond River Estuary, we tested relationships between freshwater discharge and mean PCO2 . We tested 1, 7, 14, and 30 d
cumulative freshwater discharge but only 14 d cumulative
discharge was found to have a significant relationship on
mean PCO2 in the Richmond River Estuary (R2 5 0.82, p <
0.05, n 5 9) but not in the Tuckean Swamp (R2 5 0.17, p >
0.05, n 5 7) (Fig. 10). The relationship found in the Richmond River Estuary was used to model PCO2 over the course
of the year (Fig. 10).

Fig. 7. Ratio of PCO2 at in situ temperature and salinity and PCO2 calculated at the temperature and salinity of the stating point of the survey
(most downstream point).

a day and the flood transported material is directly

exported to the shelf (Eyre and Twigg 1997). This has
been observed in other estuaries in the region (Eyre and
Ferguson 2006) and seems to be a prominent feature in
Australian subtropical environments. Both the river channel and Tuckean Swamp behaved similarly with low pH
and low oxygen waters with high concentrations of CO2.
The high PCO2 values during this stage reflect processes
occurring in the floodplain due to the rapid flushing
times in the estuary. The higher 222Rn values during this
stage are consistent with previous observations in this
catchment (Santos et al. 2011). As the floodplain is largely
inundated at this stage, most of the water is still delivered
via surface runoff.
2. The recovery stage started eight days postflood (run 2, 02
February 2012) and lasted 69 d (run 6, 04 April 2012). During this stage, flushing times become progressively longer
and salt water slowly intrudes upstream. The tributary
creek (Tuckean Swamp) and main arm become uncoupled.
The main arm transports water with moderate values of
pH (mean 5.89), 222Rn, and moderately high PCO2 . These
moderate values are due to an integrated signal in the
main channel, from upstream waters. Not all tributaries
are surrounded by CASS, and there is less influence from
groundwater discharge (Santos and Eyre 2011). As water
travels from the tributaries, CO2 and 222Rn are lost to the
atmosphere before reaching the lower estuary. In the
lower part of the estuary, water starts mixing with the oceanic endmember, with higher DIC and TA values with a
titration effect on CO2 and dilution effect on 222Rn.

Discussion
In spite of small regular rainfall events occurring in mid
March, the end of May, and mid June, affecting the estuary
recovery, surface salinity in the Richmond River Estuary
(Fig. 2) reflected the four broad hydrological stages, and
associated distinct biogeochemistry, typical of subtropical
estuaries (Eyre and Twigg 1997; Eyre and Ferguson 2006):
Flood stages
1. The flood stage lasted at least four days after the large rain
event (run 1, 30 January 2012) during which the estuary
remains flushed to the mouth. During this stage, the
residence time of the water in the estuary is shorter than
8

Ruiz-Halpern et al.

CO2 evasion in modified wetlands

Table 4. Correlation coefficients and slopes of key parameters during each survey in the Richmond River Estuary and Tuckean
Swamp (from Figs. 6, 8). Statistically significant correlations (p < 0.05) are shown in bold
Excess CO2 vs.
AOU

Days
postflood (d)

222

R2

Slope

Richmond
Tuckean

0.62
0.91

1.99
3.93

0.1
0.7

Richmond

0.91

1.68

0.59

10.11

18

Tuckean
Richmond

0.77
0.75

4.01
3.54

0.45
0.2

51.5
5.83

29

R2

Rn vs. PCO2
Slope
2.4
213.5

222

Rn vs. O2

222

Rn vs. pH

R2

Slope

R2

Slope

0.18
0.53

20.5
1.16

0.15
0.73

20.004
0.031

0.51

1.68

0.41

20.019

0.44
0.21

23.7
20.39

0.23
0.3

20.053
20.006

Tuckean

0.88

2.54

0.85

17.28

0.98

22.13

0.81

20.008

Richmond
Tuckean

0.91
0.8

1.21
2.96

0.7
0.83

10.17
14.7

0.76
0.51

21.86
21.08

0.42
0.92

20.007
20.013

36

Richmond

0.78

4.26

0.84

10.13

0.49

20.38

0.74

20.024

69

Tuckean
Richmond

0.75
0.81

3.3
1.21

0.89
0.28

18.97
9.09

0.97
0.54

21.97
21.53

0.83
0.4

20.009
20.031

Tuckean
119

Richmond
Tuckean

nd

nd

nd

0.74
0.97

0.35
2.42

0.21
0.92

nd

0.67

20.46

0.71

20.069

1.59
5.23

0.33
0.8

21.29
20.77

0.26
0.9

20.02
20.027

145

Richmond

0.79

2.05

0.51

7.5

0.11

20.14

0.59

20.035

245

Tuckean
Richmond

0.67
0.96

4.57
0.88

0.65
0.21

3.49
5.01

0.15
0.25

20.14
21.04

0.37
0.22

20.009
20.018

Tuckean
All

nd

nd

nd

nd

0.83

1.48

0.44

10.9

nd

nd

0.4

21.8

nd
0.43

nd
20.02

inputs (i.e., radon likely decayed away by the time it

reached the lower estuary surveyed here). The Tuckean
Swamp has higher 222Rn values indicating a larger contribution of groundwater and shorter residence times. However, minor rain events deliver pulses of groundwater as it
recharges the soil and seeps out within several days to
weeks (Santos and Eyre 2011).
4. The truly dry stage is generally observed commencing in
the mid to end of July, and continues until the first rains
start in the summer months (Santos et al. 2013). This
event was captured in the last survey (245d postflood)
and the estuary had similar characteristics to the dry with
minor rains period but without the disturbance of intermittent rain events.

In the Tuckean Swamp, a modified CASS wetland, and

a previously recognized discharge point of acidic groundwaters (Santos et al. 2011), PCO2 values peaked at the
beginning of the recovery stage and the lowest values of
pH were recorded. The surface water overlaying the floodplain infiltrated into the soil, where intense respiration
further increases PCO2 , depletes O2, and lowers pH by a
combination of respiration and acid production through
pyrite oxidation in the acid sulphate soils. This low O2
low pH waters enriched in CO2 that now reach the estuary
have a higher proportion of groundwater, as indicated by
the increasing concentrations of 222Rn. The positive relationships between 222Rn and PCO2 (Fig. 8; Table 4), further
support groundwater as an important contributor to the
high PCO2 in estuarine waters as found also in another
nearby CASS tributary (Atkins et al. 2013).
3. A dry stage with minor rains. In this stage, seawater is
diluted by freshwater as it moves upstream. Small rain
events during postflood and dry conditions may slightly
modify the normal salinity gradient or delay the progression of the estuarine recovery, but they generally do not
flush the estuary fresh to the mouth. Although flushing
times can be strongly reduced during most rain events,
that are often in the order of a month. As the estuary further recovers postflood, 222Rn values decrease, as lateral
groundwater inputs decrease relative to upstream water

Drivers of CO2
A number of biogeochemical processes may be associated
with surface water PCO2 in the estuary. A close exploration of
the drivers of CO2 dynamics allows for the identification of several underlying mechanisms that contribute to PCO2 in the
lower Richmond River Estuary and Tuckean Swamp that vary in
intensity depending on the hydrologic regime of the estuary.
Ecosystem metabolism
Heterotrophic metabolism appears to be an important
source of CO2 in the estuary, but the relative contribution
9

Ruiz-Halpern et al.

CO2 evasion in modified wetlands

Fig. 9. Scatterplot of the Revelle factor vs. salinity showing a minimum

buffer zone (MBZ) in the 315 salinity range. The ratio of TA to DIC
(TA : DIC) is shown in the insert, buffering capacity diminishes as
TA : DIC approaches unity (equal values).
(Table 4) from the minimum and maximum respiratory quotients of 0.6 and 0.9 (Zhai et al. 2005). These deviations
imply that other sources of CO2 aside from aerobic OM degradation must be contributing to the observed PCO2 . Flooded
wetlands have high rates of anaerobic metabolism, including
sulphate reduction and methanogenesis (Borges and Abril
2011; Gatland et al., 2014), which produces CO2 without
consuming O2. Indeed, the period of maximal CO2 and the
lowest O2 occurred during the recovery period, when water
in the floodplain had become anoxic due to aerobic metabolism, which is then transferred via shallow groundwater
seepage to wetlands draining to the estuary. During the dry
stage, the slope of the relationship between the excess CO2
and AOU is within the theoretical limit indicating that CO2
is produced in situ by the mineralization of OM (Table 4).
Likewise, the addition of mineral acid from CASS soils,
which shifts carbonate equilibrium toward higher [CO2 ]
(Tables 2, 3) may also increase PCO2 beyond the concentrations expected from aerobic respiration.

222
Rn vs. pHNBS, O2, and PCO2 in the Richmond
Riverand Tuckean Swamp sections. R2 values and slopes are summarized
in Table 4.

Fig. 8. Scatterplots of

and location may vary with the different hydrological

regimes. During flooding, most of the CO2 is produced by
high rates of respiration occurring in the floodplain, increasing CO2 concentrations all the way to the mouth (Fig. 5).
This CO2 is very quickly transported via overflow to coastal
waters or fluxed to the atmosphere. These waters can
become anoxic (Eyre et al. 2006) and have been shown to
trigger fish kills in the estuary (Eyre et al. 2006).
During the postflood recovery stage, as water infiltrates
the floodplain, respiration of organic matter (OM) in the soil
increases PCO2 which is then transferred to the estuary along
with dissolved OM and nutrients through groundwater discharge. The OM in the estuary, fuels in situ respiration further increasing PCO2 in the river. The initial stages of post
flood recovery reflect peak PCO2 , especially in the Tuckean
Swamp. During the dry with minor rains stage, most of the
processes occur directly in the river as most of the water
comes from upstream. At this stage, most of the PCO2 is likely
supported by respiration within the estuary.
The strong relationships between excess CO2 and AOU
indicate that the metabolic processes occurring both in the
water column and the catchment are driving PCO2 . However,
there are large deviations on the slopes of these relationships

Temperature and salinity

There was a negligible effect on PCO2 due to changes in
solubility brought by differences in temperature and salinity
during the first three surveys as these parameters remained
quite constant throughout the study area, except at the
mouth of the river. However, starting a month after the
flood event, the changes in salinity and temperature in the
upstream direction had a greater influence on PCO2 . Recalculated PCO2 at the conditions found at the mouth of the river,
showed up to a 50% decrease in solubility compared to the
10

Ruiz-Halpern et al.

CO2 evasion in modified wetlands

Table 5. Average daily CO2 fluxes for each survey for the Tuckean Swamp and Richmond River Estuary. Air-water flux and area
computed as % flux of the Tuckean Swamp and Richmond River Estuary. Estuary flux % of CO2 (moles 3 106 d21) evaded to the
atmosphere compared to CO2 transported by the water from upstream of the Richmond River Estuary or from the Tuckean Swamp
into the lower Richmond River. nd 5 no data. The total area surveyed is 15.4 km2, with the Richmond River having13.8 km2, and
the Tuckean Swamp 1.6 km2, 11.3% of the total area
Days
postflood
4

Section
Richmond
Tuckean
Whole estuary

19

29

Richmond
Tuckean

69

119

U10
(m s21)

200
507.6

2.76
0.79

28.8

2.23

Estuary flux
(mol 3 106 d21)

Estuary %
flux (%)

19.4
0.35

12.5
69.3

231.4

3.55

19.75

15.2

576.4
1379.6

7.95
2.16

4.17

2.53
0.21

75.9
91.1

27.2

658.2

10.11

2.73

78.7

363.6
564.3

5.02
0.88

3.62

1.54
0.22

76.5
80.0

Whole estuary

384

5.89

1.76

77

nd
1413.5

nd
2.21

5.56

0.72
0.13

nd
94.5

Richmond
Tuckean

17.6

nd

nd

nd

0.84

nd

Richmond
Tuckean

138.8
641.8

1.91
1.01

4.21

0.33
0.06

85.3
94.4

Whole estuary

190

2.92

0.39

88.2
90.8
nd

52.5

Richmond
Tuckean

81.2
nd

1.09
nd

5.56

0.11
nd

Whole estuary

nd

nd

nd

nd

15.2
354.9

0.21
0.55

3.89

0.013
0.02

94.2
96.5

49.8

0.76

0.033

95.8

440.9
1319.5

6.09
2.06

6.67

0.26
0.2

95.9
91.2

Richmond
Tuckean
Richmond
Tuckean
Whole estuary

245

% Flux
(%)

Whole estuary

Whole estuary
145

Air-water flux
(mol 3 106 d21)

Richmond
Tuckean

Whole estuary
36

Air-water flux
(mmol m2 d21)

nd

265.2

33.9

530.4

8.15

0.46

94.7

Richmond
Tuckean

33.4
nd

0.46
nd

0.0027
nd

99.4
nd

Whole estuary

nd

nd

nd

nd

nd

once the salinity is below the MBZ salinity, there are very
low levels of CO23 2 , so further additions of DIC lead to an
increase of CO2 (Hu and Cai 2013). In the Richmond River
Estuary, the MBZ was located in the 315 salinity region,
similar to the Mississippi river (Hu and Cai 2013). Hence,
high reductions in PCO2 occur in this area. However, during
the flood stage, when the estuary is flushed fresh several
times a day, all the material is exported directly into the
coastal shelf as there was no mixing in the estuarine basin.

most upstream station, which corresponds to a doubling of

the PCO2 in the water. The solubility effect was in the opposite direction of the PCO2 gradient, with higher PCO2 further
upstream in the colder, less-saline waters. This implies that
much of the CO2 is lost to the atmosphere or buffered on
mixing with oceanic water.
Buffering
The mixing of freshwater high in PCO2 with oceanic water
high in DIC and TA is subject to complex dynamics arising
from changes in solubility, pH, and TA. Hu and Cai 2013
identified a minimum buffer zone (MBZ) within various
types of estuaries. To identify this area in the Richmond
River Estuary, we plotted the R, a measure of the fractional
change in PCO2 to the fractional change in DIC against salinity (Fig. 9). R gives an indication of the buffering capacity,
and is highly dependent on the ratio of TA to DIC. Indeed,

Groundwater inputs
Although the relative contribution of CASS groundwater
inputs is only approximately 6% in the Tuckean Swamp
(Santos and Eyre 2011), groundwater can be highly enriched
in inorganic carbon relative to fresh surface waters in the
region (Atkins et al. 2013). A groundwater survey upstream
from the Tuckean Swamp (authors unpubl. data) showed
11

Ruiz-Halpern et al.

CO2 evasion in modified wetlands

Table 6. Average fluxes for different estuarine systems around

the world. (Borges et al. 2005; Sarma et al 2011; Maher and
Eyre 2012). *This study

Estuary

Type

PCO2 range
Flux
(Pa)
(mmol m-2 d21)

Randers fjord

Temperate

22.3348.5

Elbe

Temperate

58.8111.5

145

Ems
Rhine

Temperate
Temperate

56.8380.5
55.2201.6

184.4
108.7

Thames

Temperate

51.2526.9

201.6

Scheldt
Tamar

Temperate
Temperate

12.7955
38.5223

172.6
204.9

Loire

Temperate

63.8294.9

176.4

Grionde
Douro

Temperate
Temperate

4652860
134.8222.9

84.4
208.2

Sado

Temperate

58.3577.6

85.7

York River
Satilla River

Temperate
Temperate

35.5192.5
36.5830.9

17
116.4

Tropical

8.1154

13.9

Hooghly
Godavari
Godavari

Tropical(premonsoon) 22.350.7
Tropical(monsoon)
293447.7

(m3 3 106 d21). Closed circles correspond to the Richmond River (PCO2
5 0.74 6 0.19 3 discharge 1 142 6 83.8, R2 5 0.68, p 5 0.0063, n 5
9); open circles correspond to the Tuckean Swamp (relationship not significant). (B) Modeled PCO2 from equations derived in (A). Dashed line
represents the upper and lower bounds of the estimates. The crosses
represent the mean PCO2 for the Richmond River and Tuckean Swamp
sections measured during the surveys.

the Swamp. This is consistent with high 222Rn values during

the postflood stage and a decrease during dry conditions.
Sulphides oxidise and produce sulphuric acid when CASS
are drained resulting in severe acidification events in the
Richmond River Estuary (Sammut et al. 1996; de Weys et al.
2011). Low pH induces a low buffering capacity of the water
with very little HCO32 but relatively high DIC (Table 3). As
such, the discharge of low pH waters favors the presence of
inorganic carbon as dissolved CO2 with as much as 96% of DIC
in the form of CO2, enhancing evasion to the atmosphere.

15
240

MandoviZuari

Tropical

50.7354.6

38.9

Hastings River
Camden Haven

Warm temperate
Warm temperate

21.3184.7
1969.2

20.4
21.8

Wallis Lake

Warm temperate

16.855

22

Subtropical

382006.2

252.1

Richmond River*

Fig. 10. (A) mean PCO2 (Pa) vs. 14d cumulative freshwater discharge

average values of 222Rn and PCO2 of 2506 Bq m23 and 10,005

Pa, 20- and 5-fold times higher than the maximum values in
the Tuckean Swamp (Fig. 8), respectively. In a nearby creek
in the region, PCO2 concentrations in groundwater were on
average 8087 Pa (or up to 20-fold higher than surface waters)
demonstrating that even small groundwater inputs may
drive surface water CO2 dynamics (Atkins et al. 2013).
Although our 222Rn survey was not designed to provide a
quantitative estimation of groundwater discharge, the significant correlations found between PCO2 and 222Rn provide an
indication that groundwater is a likely source of CO2 to the
estuary as found in other nearby estuaries (Atkins et al.,
2013; Macklin et al, 2014; Maher et al., In Press). During
flooding, most of the water entering the estuary comes from
overland flow. However, relatively high 222Rn values were
measured throughout the system. Indeed, this is consistent
with previous observations of groundwater increasing sixfold
during the wet season while surface runoff increases only
twofold (Santos and Eyre 2011). During the postflood stage,
most of the water entering the lower Richmond River comes
from upstream of the Tuckean Swamp, where lower groundwater inputs have been detected (Santos and Eyre 2011). In
the Tuckean Swamp however, groundwater represents a
small (minimum estimate of 6% Santos and Eyre 2011), but
biogeochemically significant portion of the water entering

Surface water hydrology

We considered 1, 7, 14, and 30 d cumulative freshwater
discharge to model PCO2 concentrations in the lower Richmond River estuary and Tuckean Swamp, however, only 14
d cumulative discharge gave statistically significant results in
the Richmond. In the Tuckean Swamp PCO2 concentrations
were unrelated to freshwater discharge. Indeed, this is consistent with previous findings in the area demonstrating a
lag between rainfall and changes in surface water chemistry
(Santos and Eyre 2011). Furthermore, this integration
encompasses all processes occurring in the catchment at the
different scales. For example, the initial stages of flooding
are marked by surface runoff and respiration in the floodplain, while anaerobic metabolism and groundwater discharge become more important during the recovery phase,
when all oxygen has been depleted and groundwater is
allowed to seep into the river and nearby wetlands. During
the drier periods, reoxygenation of the sediments produces
sulphuric acid in areas with CASS, contributing low pH
waters to the Tuckean swamp (Table 3).
CO2 evasion and implications
Enhanced fluxes of CO2 to the atmosphere occurred during large freshwater discharge events, associated with heavy
12

Ruiz-Halpern et al.

CO2 evasion in modified wetlands

tion of OM released as CO2. The relative magnitude attributable to each of these mechanisms is currently uncertain and
further investigations are required to unravel the long-term
effects of flooding on the global carbon cycle.
This study highlights several key points that may have
implications for our understanding of CO2 fluxes in estuaries
worldwide. (1) The importance of hotspots and hot
moments in annual estimates of CO2 fluxes, recognizing
the necessity of capturing short-term phenomena, which
requires high resolution spatio-temporal surveys, (2) the
poor representation of (sub) tropical estuaries subject to distinct and/or modified wetland and hydrological conditions
in current estimates of global CO2 emissions from estuaries,
and (3) the lack of data in most areas of the southern hemisphere especially Australia, where the hydrological regime,
groundwater inputs, and large areas of modified wetlands
with CASS in many of the catchments may have implications for global carbon budgets, but are poorly quantified.
Current estimates usually overlook these hotspots and hot
moments of CO2 evasion. Adequate coverage of representative estuaries worldwide is important if we want to better
constrain the global carbon budget.

rainfall due to the transport of large quantities of OM and

respiration products from the floodplain to the estuary in a
short period of time. Similar processes driving enhanced
fluxes of CO2 to the atmosphere have been seen in estuaries
in India, U.S.A., and Australia (Hunt et al. 2011; Sarma et al.
2011; Bianchi et al. 2013; Gatland et al., 2014). The significant correlation between PCO2 and the 14 d cumulative freshwater discharge (Fig. 7) provides an indication of an
approximate two week lag between the onset of heavy rainfall and high rates of CO2 evasion in the estuary. As surface
hydrology appears to heavily control PCO2 in the lower Richmond River Estuary, but not the Tuckean Swamp, we can
use the PCO2 freshwater discharge relationship to model PCO2
over a full year (Fig. 7) in the estuary, allowing the identification of periods of high potential CO2 evasion rates.
Although extreme CO2 effluxes are observed only in short
periods of time, and in small areas, it may have important
implications in the evaluation of global carbon budgets. For
example, the Tuckean swamp represents only 11.3% of the
lower Richmond River Estuary area, but has CO2 effluxes up
to 2.65 times higher than the main channel (Table 5).
Flooding has been shown to enhance CO2 fluxes to the
atmosphere in contrasting temperate estuaries of New England (Hunt et al. 2011). Sarma et al. 2011 reports even
higher PCO2 (3448 Pa) in the tropical Godavari estuary following monsoon river discharges and concludes that the
annual CO2 flux from this estuary may double the previous
estimate given by Borges et al. 2005 for the entire tropical
and subtropical band. Our fluxes are similar to those presented by Sarma et al. (2011; Table 4), indicating global
emission estimates from estuaries may be severely underestimated, because subtropical systems, especially those adjacent
to modified wetlands with CASS are poorly represented.
As climate change has already produced (Hughes 2003),
and is likely to produce more extreme events, such as
increased precipitation and floods or recurring drought periods (Whetton et al. 1993; Lehner et al. 2006), adequate
understanding on the effects of these events on carbon efflux
from estuaries is necessary to improve our understanding of
global carbon budgets. Indeed, extreme events are disproportionately important in riverine carbon transport, so that
modification of climatic patterns may affect the timing, location, and intensity of the CO2 released. For example, greater
than historical frequency of floods, may enhance CO2 evasion by not allowing enough time for organic carbon to be
buried permanently (i.e., geological timescale). Hence, an
overall increase in CO2 and CH4 emissions would be expected
(Gatland et al. 2014). Conversely, recurring droughts or longer lasting periods with absence of floods may; change the
timing and magnitude of CO2 evasion to the atmosphere,
allowing for the potential of more carbon storage in the flood
plain wetland, and shift the pathway of CO2 evasion by having the OM respired in situ and released through the soil, or
create conditions more favorable for fires with the combus-

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Acknowledgments
We thank Lindsay Golsby-Smith, Justin Gleeson, Uriah Makings, Marnie Atkins, Paul Kelly, Tyler Cyronak, and Perrine Mangion for skilful
assistance in the field, and Matheus Carvalho for skilled laboratory analysis. We also thank the insightful comments of the reviewers, which
helped to greatly improve this manuscript.
DTM is funded through an S.C.U Postdoctoral Fellowship. This
research was supported by Australian Research Council grants
(DP110103638, LP110200975, LP100200732, and DP120101645) and
partially inspired by the Coastal Carbon Cluster.

Submitted 31 March 2014

Revised 2 September 2014
Accepted 31 August 2014
Associate editor: George W. Kling

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