Continental Shelf Research 31 (2011) 1357–1364

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Continental Shelf Research

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Research papers

Air–sea CO2 exchange of beach and near-coastal waters of the Chukchi Sea
near Barrow, Alaska
Hiroki Ikawa n, Walter C. Oechel
Global Change Research Group, San Diego State University, 5500 Campanile Dr., San Diego, CA 92182-4614, USA

a r t i c l e i n f o abstract

Article history: Partial pressure of CO2 in equilibrium with sample water (pCO2) for the coastal water in the Chukchi
Received 26 May 2010 Sea was continuously observed in summer, 2008. Average daily CO2 flux calculated from the pCO2 and
Received in revised form gas transfer coefficients ranged from  0.144 to  0.0701 g C m  2 day  1 depending on which gas
9 March 2011
transfer coefficient was used. The pCO2 before the landfast ice sheets melted appeared to be highly
Accepted 25 May 2011
Available online 12 June 2011
biologically controlled based on the following information: (1) the diurnal pattern of pCO2 was strongly
correlated with Photosynthetic Photon Flux Density (PPFD); (2) high chlorophyll density was observed
Keywords: during periods of peak uptake; and (3) the day-to-day variation in the pCO2 strongly correlated with
Carbon cycle the presence or absence of near-shore ice sheets. The lowest pCO2 of 35 ppm together with the highest
Arctic zone
PPFD of 1362 mmol E m  2 s  1 were observed in the afternoon on June 28 in the presence of sea ice. The
CO2 flux
very low pCO2 observed in late June was likely caused by high photosynthetic rates related to high
Beach and near-shore coastal sea
Landfast ice phytoplankton densities typically observed from spring to early summer near the ice edge, and by
Phytoplankton bloom water low in salinity and CO2 released by melting sea ice early in the season.
& 2011 Elsevier Ltd. All rights reserved.

1. Introduction Ocean has mostly been ignored by global carbon studies

Uncertainty exists over the extent to which coastal seas are
sinks or sources of carbon dioxide with respect to the atmosphere.
This uncertainty is related to the fact that even the latest oceanic
carbon model excludes coastal seas from the analysis (Gruber
et al., 2009; Takahashi et al., 2009). Despite their relatively small
area, coastal seas potentially account for up to 30% of the total
air–sea CO2 exchange of the global ocean (Chen and Borges,
2009). Intensive studies of the metabolism and gas exchange of
coastal seas started in the early 1990s by, for example, the
formation of LOICZ (Land–Ocean Interaction in the Coastal Zone).
Recently, Chen and Borges (2009) estimated that the global
continental shelf was a sink of CO2, absorbing 0.33–0.36 Pg C
annually. However, estimations of CO2 exchange are still highly
uncertain even in relatively well studied coastal seas because of
the high spatial and temporal heterogeneity of the coastal water
(Gattuso et al., 1998). Thus, additional observations in the coastal
seas and better mechanistic investigations are necessary for a
better understanding of the coastal carbon cycle.
The Arctic coast is one of the most understudied coastal seas
(Takahashi et al., 2002). Because of its relatively small size and
difficult logistics (including the dominance of sea ice), the Arctic
n
Corresponding author.
E-mail address: hikawa@sunstroke.sdsu.edu (H. Ikawa).
(Semiletov et al., 2007). Investigations have revealed, however,
that high seasonal variation in atmospheric CO2 at high northern
latitudes may in part be attributed to seasonal changes in the
air–sea CO2 exchange of the Arctic Ocean (Semiletov et al., 2004).
The extensive coastal shelf, which accounts for 58% of the total
sea surface in the Chukchi Sea, is potentially highly biologically
active, due, in part, to the mechanism known as ‘‘continental shelf
pump’’ (Tsunogai et al., 1999). The large amounts of carbon in
ocean sediments and in the land of the coastal margin of the
Arctic being called ‘‘Arctic hyper carbon pool’’ and the formation
and movement of the ice sheets over the vast continental shelf
add complex characteristics of carbonate chemistry to the Arctic
coastal sea (Semiletov et al., 2007).
Past studies showed the western Arctic Ocean to be a sink of
CO2 during the summer due to both physical and biological
controls (Murata and Takizawa, 2003; Semiletov et al., 2007).
Sea water entering into the Chukchi Sea through the Bering Strait
is cooled rapidly, increasing the solubility of CO2 during the
summer. Ice sheets in the Arctic host ice-algae that are known
to be highly productive often grow up to 2.6 g C m  2 day  1
(Gosselin et al., 1997). When these ice sheets break up in the
spring, melted ice releases the ice-algae on the surface where
there are high light levels, e.g., Quillfeldt et al. (2003) observed
high density of diatoms in first year ice in the Chukchi Sea.
Despite clear evidence of high biological activities in spring to
early summer along the Arctic coast, very few studies have

0278-4343/$ - see front matter & 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.csr.2011.05.012
1358 H. Ikawa, W.C. Oechel / Continental Shelf Research 31 (2011) 1357–1364
attempted to quantify air–sea CO2 exchange (CO2 flux) from the
shelf water during the phytoplankton bloom (Anderson et al.,
1998). CO2 flux at the biologically active water surface is highly
responsive to environmental factors, such as temperature
and light availability (Bates, 2001; Bozec et al., 2006; Gruber
and Keeling, 1999; Hales et al., 2005; Schiettecatte et al., 2007;
Thomas et al., 2004). Oceanographic carbon studies tend to lack
temporal resolution (especially when compared to terrestrial
counterparts), and it is often difficult to identify the environ-
mental and biological factors primarily controlling the variation
in CO2 flux.
This study continuously examined partial pressure of CO2 in
equilibrium with sample water (pCO2) over the summer at a fixed
location on the Chukchi Sea off the coast of Barrow, Alaska, and
compared the pCO2 measurements with micrometeorological and
oceanographic parameters. Generally, pCO2 varies to a much
greater extent than atmospheric CO2 and therefore, the proximal
control on CO2 flux is primarily the surface pCO2 (Feely et al.,
2001). The specific purposes of this study are to understand the
patterns and controls on pCO2 over the coastal water of the
Chukchi Sea with time changes.
2. Methods
2.1. Site description
The study was conducted in the beach zone of the Chukchi Sea
off the coast of Barrow, Alaska during the summer season in 2008
(N711190 5000 , W1561400 4000 ) (Fig. 1). The intertidal area was
covered with beach sands and inland was dominated by wet
sedge tundra. There were a few isolated homes along the coast in
the area with no apparent impact on the coastal physical
chemistry. A long term observation site for terrestrial carbon flux
and a large scale research project (Barrow Environmental Obser-
vatory) on the terrestrial carbon cycle are located in the vicinity of
the coast (Kwon et al., 2006; Zona et al., 2009).
The Alaskan Coastal Current (ACC) is the dominant ocean
current on the west side of the coast and carries relatively warm
and nutrient rich water from the Pacific Ocean to the Barrow
Canyon (e.g., Okonen et al., 2009). Winds were predominantly
from the northeast. The coast was totally covered with landfast
Fig. 1. Study site in Barrow, Alaska. White arrow indicates Alaskan Coastal
Current (ACC). The black arrow shows the location where the stationary observa-
tion was conducted. The bathometric data was provided by Dr. Stephen Okkonen
(University of Alaska, Fairbanks).
ice sheets (ice sheets that are secured with the sea bed) until the
middle of June. The landfast sea ice sheets broke loose and those
near the shore started drifting away from the coast on June 25–28.
No sea ice was visible after July 11 until stormy weather pushed
ice sheets back to the coast during the period of August 1–5.
The weather conditions were mostly overcast and occasionally
drizzling lightly throughout the season. The average annual pre-
cipitation in Barrow is about 110 mm.
2.2. Site selection and representativeness
Because of a high maintenance required for the pCO2 system
due to unpredictable weather and a necessity of relocating the
water inlet due to moving ice sheets, we were able to operate the
continuous measurement system at only one point near a lightly
residential area.
Upon the site selection, a preliminary investigation of pCO2
was conducted along the coast of Barrow in 2007 (Fig. 2). The
variation of pCO2 along the west side of Barrow was relatively
smaller with the average pCO2 of 249 ( 714) ppm, much more so
than those found on the north-east side of Barrow, facing the
Beaufort Sea. A similar value of pCO2 was observed at 30 km
offshore of the west side of the coast. This preliminary result
reflects that the water off the west coast of Barrow was greatly
influenced by ACC, while the north-east side had a higher
terrestrial influence. Although the spatial measurement was
taken only during the ice-free period, geological features of the
west coast of Barrow are extensively homogeneous, and relatively
strong water currents, which enhanced mixing the water, were
observed throughout the measurement season. Thus, the selected
study point likely represents an extensive beach and near-shore
coastal water of the west coast of Barrow, but not the north east
coast of Barrow.
2.3. Measurements
pCO2, surface salinity (SS), sea water temperature (SWT), and
dissolved oxygen (DO) were measured at a fixed point from June
pCO2
71.42 450
71.4
400
71.38
350
71.36
Latitude
71.34 300
71.32
250
71.3
71.28
156.8 156.7 156.6 156.5 156.4 156.3
Longitude
Fig. 2. A preliminary result from the boat cruise measurement of pCO2 along the
coast of Barrow conducted on August 1–6, 2007. The black arrow indicates the
selected site in this study.
 H. Ikawa, W.C. Oechel / Continental Shelf Research 31 (2011) 1357–1364
Fig. 3. The pCO2 measurement system. Solid arrows show the air flow, and dashed arrows show the flow of water samples. Water temperature in the equilibrator and sea
water temperature were monitored by a copper–constantan thermocouple, and Takahashi’s temperature-pCO2 equation (Takahashi et al., 1993) was applied to correct the
pCO2 at the temperature in the equilibrator to the pCO2 at the sea water temperature.
15 to August 18 in 2008. The pCO2 measurements were made
using a headspace equilibrator on the shore (Fig. 3). Sea water
was sampled from the beach where water depth was less than
1 m. When the landfast ice sheets were present, the sample water
was taken at the edge of the ice sheets. The sampled water was
continuously pumped from the upper 20 cm of the water column,
and was sprayed into and drained from the equilibrator continu-
ously at 3 l min  1. A 5 m 19 mm ID neoprene hose with a float at
the water inlet to raise the intake near the surface was used to
obtain the water sample for pCO2 analysis. The equilibration
chamber was shaded and located adjacent to the water’s edge
to ensure the chamber temperature was close to SWT to minimize
the effect of the temperature changes. The chamber temperature
was slightly higher than SWT by 0.5–1 1C, and the temperature
correction following the Takahashi’s pCO2-temperature
equation (Takahashi et al., 1993) modified the pCO2 value by
2–4%. The water volume in the equilibration chamber was
maintained at 500 ml with the excess volume draining freely.
A laboratory test showed the system reached to 99% of air–water
equilibration within 5 min of a change in the pCO2 of the sample
water. Thus, the CO2 concentration in the headspace at a certain
time represents a running average of pCO2 for a period of
approximately 5 or fewer minutes. Air circulated through the
headspace into a non-dispersal infrared gas analyzer, LI-840
(Li-Cor, USA), at 2 l min  1 and back in a closed loop. One
complete air circulation took about 30 s. The pressure inside the
chamber was monitored with LI-840 gas analyzer and was
maintained at ambient pressure. To calibrate the gas analyzer,
the analyzer was disconnected and returned to an adjacent
laboratory and was calibrated against air with known CO2 con-
centrations of 0 and 550 ppm every 24 h. The pCO2 concentra-
tions were recorded every minute. After the ice sheets drifted
offshore, maintaining a fixed water inlet was challenging as the
moving ice sheets often destroyed the water inlet, thereby
interrupting measurements until the inlet could be repositioned.
Atmospheric CO2 concentrations were sampled at 3 m above the
sea surface twice a day with the same infrared gas analyzer that
was used for the pCO2 measurements. Our pCO2 system (SDSU-
pCO2) was tested against a manufactured pCO2 system (SAMI-
pCO2, Sun-Burst Sensors, USA), and the following relationship was
obtained: SDSU-pCO2 (ppm)¼0.9477  SAMI-pCO2 (ppm)þ29.37
1359
(R2 ¼0.99). The discrepancy is partly attributable to the fact that
the SAMI-pCO2 sensor guarantees the reading between 150 and
700 ppm, while the infrared gas analyzer for the SDSU-pCO2
system was calibrated with known CO2 concentrations of 0, 330,
and 550 ppm.
The SS, SWT, and DO were measured with a sonde (YSI 600R,
YSI Incorporated, USA) one to three times a day when the pCO2
system was operated. Because of the technical difficulty of
measuring the temperature of the surface water, SWT was
determined in the upper 20 cm of the water column. Apparent
oxygen utilization (AOU) was calculated by subtracting DO
from the saturated oxygen concentration at given SS and SWT.
The sonde was calibrated with a conductivity calibrator (YSI 2169,
YSI Incorporated, USA) for salinity and copper-constantan ther-
mocouples for temperature immediately before the measurement
season.
Chlorophyll density was estimated with a fluorometer (FLNTU,
WET Labs) about once a week throughout the measurement
season. The fluorometer was calibrated by WET Labs immediately
before the measurement season.
2.4. Micrometeorological parameters
The hourly averaged micrometeorological parameters (wind
speed, wind direction, Photosynthetic Photon Flux Density (PPFD),
and air temperature) were obtained from a 3 m tall weather
station located a half mile inland from the coast at the Global
Monitoring Division (GMD) of the Climate Monitoring and Diag-
nostics Laboratory (CMDL).
2.5. CO2 flux calculations
The CO2 flux was calculated using a bulk method by the
following equation (Wanninkhof and McGills, 1999):
CO2 flux ¼ ak (pCO2–CO2atm)
The solubility, a, was computed by SWT and SS based on Weiss
(1974). The gas transfer coefficient, k, was calculated following
Wanninkhof (1992), Liss and Merlivat (1986), and Wanninkhof
and McGills (1999). CO2atm is the atmospheric CO2 concentration.
1360 H. Ikawa, W.C. Oechel / Continental Shelf Research 31 (2011) 1357–1364

2.6. Statistical analysis
To investigate relationships between environmental factors
controlling the diurnal and day-to-day variability in pCO2 and the
pCO2 normalized by the temperature at 3 1C following the
Takahashi’s pCO2-temperature equation (Takahashi et al., 1993)
the (pCO2-3 1C) values were averaged for every hour and every
day. Physical effects due to temperature changes on pCO2 are
standardized when pCO2 is normalized by temperature. Then,
stepwise linear regressions were applied on the hourly and daily
averaged pCO2 against averaged environmental parameters
(presence or absence of ice sheets, PPFD, air temperature, wind
speed, wind direction, SS, SWT, and AOU). The stepwise
linear regression first investigates the correlation of the pCO2
with the most correlated environmental parameter and next
investigates the next environmental parameter that correlates
to the residual.
3. Results
3.1. A pCO2 and environmental parameters
Extremely low pCO2 was detected in late June to early July and
the lowest instantaneous value measured was 35 ppm at the local
standard time of 15:30 on June 28. A short measurement taken on
June 25 in 2007 showed a pCO2 value of 150 ppm, similar to those
recorded in late June 2008. The pCO2 increased around mid July
when the landfast ice sheets broke loose. The daily averaged CO2 flux
was calculated for each pCO2 measurement and k estimated using
measured wind speeds (Fig. 4a–c). Cumulative CO2 fluxes over the 57
days were calculated for each of the three estimations of k (Fig. 4d).
The low pCO2 observed in late June resulted in high CO2 uptake with
daily averaged CO2 flux of 0.398 g C m  2 day  1 on July 7 calcu-
lated with the k following Wanninkhof (1992) (W92 method).
The overall average of the CO2 flux was  0.144 g C m  2 day  1
following Wanninkhof (1992) (W92 method),  0.0701 g C m  2
day  1 following Wanninkhof and McGills (1999) (W&M99 method),
and 0.0779 g C m  2 day  1 following Liss and Merlivat (1986)
(L&M86 method).
The daily averaged PPFD and wind speeds indicate relatively
sunnier and less windy days in the early season (Fig. 5a and c).
The fraction of wind coming from each direction is shown in
Fig. 5d. DO was higher at the beginning of the season and
decreased toward the end of the season (Fig. 6a). SS was
extremely low in the beginning of the season. A rapid increase
in SS around mid-July corresponded to the period when the
landfast ice sheets broke free of the sea bed and the pCO2
increased from the range of about 50–200 ppm to the range of
about 200–400 ppm (Fig. 6c). The SWT and AOU did not show
clear temporal pattern by themselves (Fig. 6b and d). The highest
chlorophyll density of 15 mg Chl m  3 was observed on June 15,
and the chlorophyll density rapidly decreased after the first
measurement (Fig. 6e).
3.2. Comparisons of pCO2 and environmental parameters by the
stepwise linear regressions
3.2.1. Diurnal variations
Diurnal patterns of pCO2 and pCO2-3 1C and meteorological
parameters are shown in Fig. 7. Before the sea ice drifted off
shore, both hourly averaged pCO2 and pCO2-3 1C showed negative
diurnal correlations to the hourly averaged PPFD (pCO2: p o0.05,
pCO2-3 1C: po0.001). However, no correlation between hourly
averaged pCO2 or pCO2-3 1C and PPFD was found after the ice
sheets retreated. Both pCO2 and pCO2-3 1C were positively corre-
lated to wind speed (pCO2: p o0.001, pCO2-3 1C: po0.005) in the
presence of the ice sheets, because the air–water mixing by
higher wind speeds changed the pCO2 toward the air–sea equili-
brium status, and higher winds also enhanced mixing the water
from offshore.
3.2.2. Day-to-day variations
The presence or absence of ice sheets was a strong predictor of
pCO2 and pCO2-3 1C (po 0.001). Negative correlations were found
between pCO2-3 1C and SWT (po0.005) (Fig. 8).

50 10
W&M99
0 8 W92
dpCO2 (ppm)

-50
k (cm hr-1)

L&M86
-100 6
-150 4
-200
2
-250
-300 0
6-Jun 26-Jun 16-Jul 5-Aug 25-Aug 6-Jun 26-Jun 16-Jul 5-Aug 25-Aug

0.05 0
CO2 flux (g C m-2 day-1)

0
C-CO2 flux (g C m-2)

-1
-0.05
-0.1 -2
-0.15 -3
-0.2
-0.25 W&M99 -4
-0.3 W&M99
W92 -5
-0.35 W92
L&M86 -6
-0.4 L&M86
-0.45 -7
6-Jun 26-Jun 16-Jul 5-Aug 25-Aug 6-Jun 26-Jun 16-Jul 5-Aug 25-Aug

Fig. 4. Daily average dpCO2 (dpCO2 ¼ pCO2  atmospheric CO2) in parts per million (a); gas transfer coefficient, k (J: Wanninkhof and McGills (1999), D: Wanninkhof
(1992),  : Liss and Merlivat (1986)) (b); CO2 flux calculated by dpCO2 and k (c); and cumulative CO2 flux over 57 days (d).
 H. Ikawa, W.C. Oechel / Continental Shelf Research 31 (2011) 1357–1364 1361

10

PPFD (µmol E m-2s-1)

600
500 8

AirT (°C)
400 6
300 4
200 2
100 0
0 -2
6-Jun 26-Jun 16-Jul 5-Aug 25-Aug 6-Jun 26-Jun 16-Jul 5-Aug 25-Aug

N
30
14
NW NE Before July 11
12 20
WS (ms-1)

10 After July 11
10
8
6 W 0 E
4
2
0 SE
6-Jun 26-Jun 16-Jul 5-Aug 25-Aug SW

Fig. 5. Seasonal changes in daily average Photosynthetic Photon Flux Density (PPFD mmol E m  2 s  1) (a), air temperature (AirT 1C) (b), daily average wind speed (WS
ms  1) (c), and frequency (%) of prevailing wind direction before and after June 11 (d). Meteorological data were collected every 10 s, averaged over 30 min, and recorded.
Daily averages were calculated from the 30 min averages. The vertical bar for each data point shows standard error but may not be seen due to relatively lower daily
variations than seasonal variations.

4. Discussion 4.3. Arctic coast as a sink in summer

4.1. Biological effects on pCO2
pCO2 values as low as 100–150 ppm have been observed near the
ice edge in the high latitude (Pipko et al., 2002). Even lower pCO2
was similarly observed in our study in the early season. The highest
chlorophyll density, 15.3 mg Chl m  3, was observed on June 21, and
this is of a similar order as the chlorophyll density during the
chlorophyll bloom observed in the MODIS satellite image (http://
aoos.org/). Springer and McRoy (1993) reported up to 50 mg Chl m  3
in July in the Beaufort Sea, which is adjacent to our study site.
High correlation between pCO2 and PPFD during the presence
of landfast ice sheets also supports high biological activities near
the ice edge. Interestingly, the highest PPFD of 1362 mmol
E m  2 s  1 during the measurement season was also recorded at
the same time as the lowest instantaneous pCO2 value of 35 ppm.
Once landfast ice sheets retreated offshore, pCO2 increased and
no significant correlation was found between pCO2 and PPFD
presumably due to mixing of coastal water with water from the
open ocean, loss of biological activity, and likely enhanced mixing
with the atmosphere.
4.2. Day-to-day variations of pCO2
Daily averaged pCO2 was most strongly correlated to the
presence or absence of ice sheets, and there was no significant
correlation between pCO2 and PPFD over the season implying that
the diurnal variations in pCO2 due to PPFD were less important on
a day-to-day scale.
The negative correlation between pCO2-3 1C and SWT may be due
to biological activities or upwelling events. No simultaneous correla-
tion was found between pCO2 and wind direction. However, north-
westerly winds typically prevail in the area and this wind creates
upwelling along the west coast of Barrow (Okkonen et al., 2009), and
upwelling likely has an influence on the local carbonate system
(Anderson et al., 2009; Fransson et al., 2006; Gago et al., 2003).
Comparing our CO2 flux result from the ice-free period (July
20–August 18) with other studies by Semiletov et al. (2007), Pipko
et al. (2002), and Murata and Takizawa (2003), our result showed
less CO2 uptake (Table 1). The lower CO2 uptake, compared to
these previous studies, may be attributed to the greater mixing in
the shallow near shore area and the higher SWT observed in our
study. Higher SWT was partly due to the fact that our study was
conducted close to the shore, and the solar radiation during the
daytime quickly heated the shallow water. However, it should be
noted that the sea water temperature has increased dramatically
in past few years (NOAA Arctic Report Card 2008, http://www.
arctic.noaa.gov/). If the carbonate system in the Arctic Ocean in
late summer is controlled by physical factors such as solubility
more than biological factors (Murata and Takizawa, 2003), further
increases in SWT may result in a source of CO2 from the coastal
margin of Chukchi Sea in mid-summer.
The extremely low pCO2 in our measurement in early season
may also be attributed to the relatively CO2 free water melting
from the sea ice. A tank experiment conducted by Nomura et al.
(2006) showed that atmospheric CO2 concentration near the
surface of the seawater increased with ice formation as dissolved
inorganic carbon (DIC) was excluded from the freezing water. This
process is also inferred by the low SS likely due to partially
desalinated water from the melting ice (Vancoppenolle et al.,
2007) in late June.
4.4. Estimations of the gas transfer coefficient
Cumulative CO2 flux over the 57 days was calculated using
three different estimates (W92, W&M99, and L&M86) of the gas
transfer coefficient, k. The W92 estimate of k yielded a sink that
was twice as large as that of the other two methods (Fig. 4d).
These estimation methods of k were developed empirically from
various locations and conditions, and we could not conclude
which estimation method of k was more applicable. Uncertainties
1362 H. Ikawa, W.C. Oechel / Continental Shelf Research 31 (2011) 1357–1364

15 9
14
7
13

DO (mg/l)
5

SWT (°C)
12
11
3
10
9 1
8
-1
7
6 -3
6/6 6/26 7/16 8/5 8/25 6/6 6/26 7/16 8/5 8/25
Day (2008) Day (2008)

35 1
30 0.8

AOU (molO2m-3)
25 0.6
SS (ppt)

20
0.4
15
0.2
10
5 0
0 -0.2
6/6 6/26 7/16 8/5 8/25 6/6 6/26 7/16 8/5 8/25
Day (2008) Day (2008)

3
Chlorophyll (mg Chl m-3)

(June 21, 15.3 mg Chlm-3)

2.5
2
1.5
1
0.5
0
6/6 6/26 7/16 8/5 8/25
Day (2008)

Fig. 6. Seasonal changes in oceanographic parameters: dissolved oxygen (DO) (a), surface temperature (SWT) (b), salinity (SS) (c), apparent oxygen utility (AOU) (d), and
chlorophyll density (e). AOU is the balance of dissolved oxygen and saturated dissolved oxygen at given SWT and SS.

in estimating k are well documented by Wanninkhof et al. (2009).
Currently, the estimation based on wind speed is most commonly
used (e.g., Murata and Takizawa, 2003; Pipko et al., 2002;
Semiletov et al., 2007; Takahashi et al., 2009). However, properties
of air–water gas exchanges are also influenced by various factors
such as surface bubbles and chemical properties (Keeling, 1993;
McKenna and McGillis, 2004; Smith and Jones, 1985). The presence
of the ice sheet over the surface would have an even larger
influence on k. Although ice sheets were found to be permeable to
CO2 gases (Gosink et al., 1976; Semiletov et al., 2004), the k
estimation method should be modified largely for estimating gas
exchange through ice sheets. Thus, our estimation of CO2 flux
during the presence of the ice sheets is only reliable for the
exposed water surface adjacent to ice sheets. For understanding
CO2 flux at a larger spatial level in the Arctic region, under-
standing distribution patterns of the ice sheets, and developing an
estimation method, for example, by comparing pCO2 data with
direct flux measurements, such as the eddy covariance technique
(e.g., Iwata et al., 2004; Kondo and Tsukamoto, 2007), are
necessary.
5. Conclusion
The coastal waters of the Chukchi Sea were characterized by
extremely low pCO2 in the presence of landfast ice sheets.
The pCO2 before the landfast ice sheets melted appeared to be
highly biologically controlled. This conclusion is supported by the
following information: (1) the diurnal pattern of pCO2 was
strongly correlated with PPFD; (2) high chlorophyll density
was observed; (3) the day-to-day variation in the pCO2 was
correlated to the presence or absence of the landfast ice sheets.
Thus, the very low pCO2 observed in late June was likely
caused by high phytoplankton densities typically observed
from spring to early summer near the ice edge. Water from the
melting ice sheets also affects the pCO2 physically due to its
low CO2 content. The formation of ice sheets likely impedes sink
activity of CO2 (Bates and Mathis, 2009; Nomura et al., 2010)
and likely further increase pCO2 during the reformation of the ice
sheets. The relationship between the CO2 flux and sea ice proper-
ties may be one important key to explain the high seasonal
amplitude in atmospheric CO2 at high northern latitudes.
Uncertainty remains as to the cause of the negative correla-
tion between daily averaged pCO2-3 1C and SWT. Furthermore,
the bulk method we used to estimate CO2 flux in this study
is applicable only for the air–water gas exchange, and the
gas transfer through ice sheets is still uncertain. Future investi-
gations will be necessary to study melting patterns of sea
ice and local oceanic currents as well as the refined flux
measurements to understand CO2 flux at larger scales in the
Arctic region.
 H. Ikawa, W.C. Oechel / Continental Shelf Research 31 (2011) 1357–1364 1363

Fig. 7. Hourly averaged pCO2, pCO2 normalized to 3 1C, PPFD, air temperature (AirT), wind speed (WS), and hourly mode of wind direction (WD) for June 22–July 9 (left
side), and July 20–August 18 (right side). The vertical bars indicate standard errors at each data point.

450 450
400 ICE_ON 400 ICE_ON
350 ICE_OFF 350 ICE_OFF
pCO2-3°C (ppm)
pCO2 (ppm)

300 300
250 250
200 200
150 150
100 100
50 50
0 0
0 2 4 6 0 2 4 6
SWT (°C) SWT (°C)

Fig. 8. pCO2 and the pCO2 normalized by temperature at 3 1C (pCO2-3 1C) followed by Takahashi et al. (1993) as a function of presence (ICE_ON) or absence (ICE_OFF) of
fast ice sheets and sea water temperature (SWT).

Table 1
Summary of the CO2 flux calculated from pCO2 values obtained in the coastal shelf of the Chukchi Sea.

CO2 flux (g C m  2 day  1) pCO2 (ppm) Wind speed (ms  1) Period Reference

W&M99 W92 L&M86

– –  0.343  160n 9.0 September, 1996 Pipko et al. (2002) (L-12 transect)
– –  0.132  118n 7.42 August–September, 1996 Semiletov et al. (2007)
– –  0.0924  161n 5.13 August–September, 2000 Semiletov et al. (2007)
– –  0.204  137n 7.61 August–September, 2002 Semiletov et al. (2007)
– – – 280–410 February–March, 2003 Semiletov et al. (2007)
 0.0924  0.144 –  84.9n 7.27 August–September, 1998–2000 Murata and Takizawa (2003)
 0.0864  0.181  0.0932 152 4.69 June 22–July 9, 2008 This study
 0.0446  0.0864  0.0537 277 5.37 July 20–August 18, 2008 This study
 0.0701  0.144  0.0779 200 4.96 June 22–August 18, 2008 This study

n
dpCO2 ¼ pCO2  atmospheric CO2.
1364 H. Ikawa, W.C. Oechel / Continental Shelf Research 31 (2011) 1357–1364
Acknowledgments
We thank Dr. Douglas Deutschman for the helpful suggestions
on the statistics analysis, Mr. Joseph Verfaillie and Dr. Stephen
Okkonen for their valuable advice, and Barrow Arctic Science
Consortium (BASC) for the logistic support.
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