PUBLICATIONS

Journal of Geophysical Research: Oceans

RESEARCH ARTICLE
10.1002/2014JC009856

Special Section:
Pacific-Asian Marginal Seas
Key Points:
 Spring biological drawdown of DIC
was estimated in the northern East
China Sea
 The Yellow Sea water intrusion
counteracted CO2 uptake in the
northern ECS
 The earlier DIC drawdown had
durative effects on carbonate system

Spring carbonate chemistry dynamics of surface waters in the

northern East China Sea: Water mixing, biological uptake of
CO2, and chemical buffering capacity
Wei-Dong Zhai1, Jian-Fang Chen2,3, Hai-Yan Jin2,3, Hong-Liang Li3, Jin-Wen Liu4, Xian-Qiang He2,
and Yan Bai2
1

National Marine Environmental Monitoring Center, Dalian, China, 2State Key Laboratory of Satellite Ocean Environment
Dynamics, Second Institute of Oceanography of State Oceanic Administration, Hangzhou, China, 3Key Laboratory of
Marine Ecosystem and Biogeochemistry of State Oceanic Administration, Second Institute of Oceanography of State
Oceanic Administration, Hangzhou, China, 4State Key Laboratory of Marine Environmental Science, Xiamen University,
Xiamen, China

Abstract We investigated sea surface total alkalinity (TAlk), dissolved inorganic carbon (DIC), dissolved
Correspondence to:
W. Zhai,
wdzhai@126.com

Citation:
Zhai, W.-D., J.-F. Chen, H.-Y. Jin, H.-L. Li,
J.-W. Liu, X.-Q. He, and Y. Bai (2014),
Spring carbonate chemistry dynamics
of surface waters in the northern East
China Sea: Water mixing, biological
uptake of CO2, and chemical buffering
capacity, J. Geophys. Res. Oceans, 119,
56385653, doi:10.1002/
2014JC009856.
Received 29 JAN 2014
Accepted 11 AUG 2014
Accepted article online 14 AUG 2014
Published online 2 SEP 2014

oxygen (DO), and satellite-derived chlorophyll-a in the connection between the Yellow Sea and the East
China Sea (ECS) during April to early May 2007. In spring, Changjiang dilution water (CDW), ECS offshore
water, and together with Yellow Sea water (YSW) occupied the northern ECS. Using 16 day composite
satellite-derived chlorophyll-a images, several algal blooms were identied in the CDW and ECS offshore
water. Correspondingly, biological DIC drawdown of 73 6 20 lmol kg21, oversaturated DO of 10110 lmol
O2 kg21, and low fugacity of CO2 of 181304 latm were revealed in these two waters. YSW also showed
CO2 uptake in spring, due to the very low temperature. However, its intrusion virtually counteracted CO2
uptake in the northern ECS. In the CDW and the ECS offshore water, Revelle factor was 9.311.7 and 8.9
10.6, respectively, while relatively high Revelle factor values of 11.413.0 were revealed in YSW. In the ECS
offshore water, the observed relationship between DIC drawdown and oversaturated DO departed from the
Redeld ratio, indicating an effect of chemical buffering capacity on the carbonate system during air-sea
reequilibration. Given the fact that the chemical buffering capacity slows down the air-sea reequilibration of
CO2, the early spring DIC drawdown may have durative effects on the sea surface carbonate system until
early summer. Although our study is subject to limited temporal and spatial coverage of sampling, these
insights are fundamental to understanding sea surface carbonate chemistry dynamics in this important
ocean margin.

1. Introduction
Despite comprising only a small portion of the worlds ocean surface area, coastal waters play an important
role in the global oceanic carbon cycle and have received increasing attention [e.g., Walsh et al., 1981; Smith
and Hollibaugh, 1993; Bauer et al., 2013; Chen et al., 2013; Dai et al., 2013]. Understanding carbonate chemistry and the variability of the air-sea CO2 ux in coastal waters remains a huge challenge [Bauer et al., 2013;
Chen et al., 2013; Dai et al., 2013]. This is because coastal waters are tremendously heterogeneous and thus
far insufciently sampled [Laruelle et al., 2010; Cai, 2011; Chen et al., 2013; Sabine et al., 2013].
The East China Sea (ECS) is a midlatitude shelf system, and together with the Yellow Sea to its north represents a globally important ocean margin at its western boundary, characterized by its widest shelf and highest terrestrial inputs from Changjiang (the Yangtze River) (Figure 1a). The ECS serves as an annual net sink
of atmospheric CO2 [Zhang et al., 1997; Tsunogai et al., 1999; Wang et al., 2000; Hu and Yang, 2001; Tseng
et al., 2011], while the South Yellow Sea serves as a net annual source of atmospheric CO2 [Xue et al., 2011].
So far, the extent to which the neighboring CO2-saturated Yellow Sea water (YSW) may affect the carbonate
system in the northern ECS remains unclear because information in most literatures on this carbonate system is based on limited stations with insufcient spatial coverage [Chen and Wang, 1999; Peng et al., 1999;
Tsunogai et al., 1999; Wang et al., 2000; Chou et al., 2009a, 2009b, 2011, 2013a, 2013b]. Although Zhai and
Hong [2012] have suggested that the YSW contained both higher total alkalinity (TAlk) and higher dissolved

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120oE

(a)
Bo

i
ha

40

NYS
25

Huanghe

South Yellow Sea

50

Jeju Is.

W
YS

CC
YS

35oN

50

Se a

TMW
C

Changjiang

m
10
0

C
W

East China Sea

0

TW

Zh
Pr ejia
ov n g
i nc
e

30oN

HZB

hio
ros
u
K
20

25oN

TW

120oE

125oE

1000 m

Water discharge (10 3 m3 s-1)

40oN

125oE

30

10.1002/2014JC009856

(b)
Changjiang
Datong Station

20
10
0
4
3

(c)
Huanghe
Lijin Station

2
1
0

J F M A

M J

J A

S O N

Figure 1. (a) Area map and sampling sites, (b and c) daily evolution of water discharge from Changjiang (Datong Station) and Huanghe
(Lijin Station) rivers in 2007 (daily water discharge data from the China Bureau of Hydrology, http://xxfb.hydroinfo.gov.cn/). In Figure 1a,
depth contours of 25, 50, 100, 200, and 1000 m are sketched by thin gray lines. The framed region indicates the area under study. Sampling sites in April to May are shown by open circles, while the early July sampling locations of Chou et al. [2009a, 2009b] are marked by
cross-shaped symbols. The dashed line from the northern corner of the Changjiang Estuary to Jeju Island is the traditional boundary
between the South Yellow Sea and the East China Sea. NYS indicates the North Yellow Sea. HZB 5 Hangzhou Bay. TW 5 Taiwan Island.
Gray arrows sketch major currents in northeast monsoon seasons in the two marginal seas [Zang et al., 2003; Chen, 2009], including the
Kuroshio, TsushiMa Warm Current (TMWC), Yellow Sea Warm Current (YSWC), Yellow Sea Coastal Current (YSCC), and TaiWan Warm Current (TWWC). In Figure 1b, the gray curve shows the long-term average of monthly water discharge from Changjiang River from 1963 to
1999 [Liu et al., 2002], while open diamonds represent monthly mean water discharge in 2007 [China MWR-BH, 2008]. Gray vertical columns
in Figure 1b show sampling periods.

inorganic carbon (DIC) than those in usual ECS waters, based on eld data in the connection between the
South Yellow Sea and the ECS (Figure 1a), they only present an overview of the ECS carbonate system
parameters to common readers. Shim et al. [2007], Zhai and Dai [2009], Tseng et al. [2011], and Kim et al.
[2013] have studied surface partial pressure of CO2 (pCO2) in the northern ECS. However, they only aim to
estimate air-sea CO2 uxes.
The northern ECS accounts for a majority of the ECS CO2 sink [Chou et al., 2009a; Tseng et al., 2011]. Therefore, a better understanding of the northern ECS carbonate system is fundamental before the ECS CO2 ux
can be placed in a global context. In this study, we reanalyzed the Zhai and Hong [2012] spring carbonate
system data that were sampled from early April to early May 2007. Together with simultaneous dissolved
oxygen (DO) data [Li et al., 2011] and qualied satellite-derived sea surface chlorophyll-a distributions [He
et al., 2013], this data set provides an opportunity to examine the spring carbonate chemistry dynamics in
this important continental shelf area, including water mixing (among Changjiang dilution, ECS, and Yellow
Sea waters), biological uptake of CO2, and air-sea exchange after a spring algal bloom. We also attempted
to better explain the offshore CO2 uptake observed by Chou et al. [2009a] in early July 2007 in the same
region.

2. Materials and Methods

2.1. Study Area and Hydrological Backgrounds
The ECS has a temperate climate with a cold/dry winter (from December to early March of the following
year) and a warm/wet summer (from June to early September). Climatic variations are primarily dominated
by the East-Asian Monsoon. The northeast monsoon lasts from October to April of the following year, driving strong coastal currents in the Yellow Sea (Yellow Sea Coastal Current, or YSCC for short) and in the ECS
(Zhejiang-Fujian coastal current) (Figure 1a). From May to July, however, the southwest monsoon comes
and carries signicant rainfall (widely known as plum rain, or Mei-Yu in Chinese) into the study area. Meteorologically, the Mei-Yu rainy season is induced by a slow-moving and occasionally quasi-stationary

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convergence zone (i.e., Mei-Yu front) at the beginning of southwest monsoon period. This Mei-Yu front
affects the southern ECS from May to mid-June every year [Chen and Chen, 2003; Chen et al., 2012], and
migrates to the northern ECS during June and July.
In 2007, a plum rain was recorded in early June at a north site of the Taiwan Island, with the total rainfall of
414 mm over a week [Chen et al., 2012]. Ten days later, the rainy weather migrates northward, as indicated
by a heavy rainfall (average 29.4 mm over 24 h) around the study area (http://news.xinhuanet.com/society/
2007-06/14/content_6243001.htm). In that month, the total rainfall in nearby coastal Zhejiang Province,
China was recorded from 74 to 256 mm (http://www.zjwater.com/pages/document/47/document_990.
htm). The heavy rainfall can decrease freshwater end-member values of DIC and TAlk in summer due to the
dilution effect.
The study area covers a 5.5 3 4 area (the rectangle in Figure 1a, excluding the areas in the west side of
122 E), representing >30% of the total ECS surface area. Its western part lies outside the Changjiang River
mouth, where high pCO2 waters discharged from the river meet with highly productive ECS waters [Zhai
et al., 2007; Chen et al., 2008; Yu et al., 2013]. The YSW also inuences this area, especially in the northerly
wind-prevailing seasons [Zang et al., 2003; Chen, 2009]. Partially due to the higher nutrient supply from
Changjiang, algal blooms, and signicant surface pCO2 drawdown frequently occur in this region in the
ooding months from April to August [Chen et al., 2003; Tan et al., 2004; Zhou et al., 2008; Tseng et al., 2011;
He et al., 2013].
In the central and eastern parts of the study area, YSW, Changjiang dilution water (CDW), TaiWan Warm Current (TWWC) water, and Kuroshio water are encountered in different seasons (Figure 1a) [Chen, 2008, 2009].
If effects of tidal currents are negligible, the ushing and exchange of the open ocean waters in the study
area should be controlled by horizontal volume transports of the Kuroshio [Chen et al., 1995]. Both observation and model-derived studies have suggested that both along-shelf and cross-shelf volume transports of
the Kuroshio are insignicant from May to July in the study area [e.g., Zhao and Guo, 2011; Guo et al.,
2012a]. For example, the Kuroshio-induced horizontal volume transports along the shelf are mainly
observed in the east side of 126 300 E [Guo et al., 2012a]. In the west side of 126 300 E, however, horizontally
averaged velocities are summarized at 0.03 6 0.10 m s21 [Guo et al., 2012a], suggesting a very long ushing
time of the offshore seawater of 5.7 months in the latitude span of 4 (from 29 N to 33 N, Figure 1a). Therefore, the open ocean end of the study area may persist there from late spring to early summer, which is consistent with the slow-moving local weather system at the beginning of southwest monsoon period. This
hydrological status is also evidenced by the frequent occurrence of the bottom oxygen depletion (hypoxia)
and DIC accumulation in summer in this shallow-water region [e.g., Li et al., 2002; Chen et al., 2007; Wei
et al., 2007; Chou et al., 2009b], which will disappear in a dynamic environment [e.g., Zhai and Dai, 2009].
In 2007, water discharge from Changjiang (data collected at Datong, the farthest major downstream hydrological station in Changjiang) increased from <25,000 m s21 before June to 55,800 m s21 in early August
(Figure 1b). By comparison, the long-term average from 1963 to 1999 was characterized by a water discharge peak in July [Liu et al., 2002]. The time lag of the water discharge peak may have resulted from
manipulation of water discharge by the Three-Gorges Dam [Zhai et al., 2007], which entered its rst lling
stage in June 2003. Thus, our spring data set represents a transitional season between the dry/cold and
wet/warm seasons, while the early July data set of Chou et al. [2009a, 2009b] represents the early stage of
the ood season in 2007. This may explain why Chou et al. [2009a] dene CDW (Sal < 31) in a limited area
(west of 124 000 E), although CDW with salinity <31 usually spreads to 125 000 or 126 000 E in summer in
the northern ECS [Lie et al., 2003; Kim et al., 2009; Bai et al., 2013]. Note that CDW may spread into the East
China Sea with a time lag of 1 or 2 months after discharge at Datong station [Kim et al., 2009].
However, water discharge from Huanghe (the Yellow River) remained at <500 m3 s21 from January to midJune (Figure 1c). Water discharge reached the highest peak (3910 m s21) on 1 July (Figure 1c), which was
less than 10% that of Changjiang. During the past 60 years, annual water discharge from Huanghe has signicantly declined from 50 3 109 m3 yr21 in the 1950s and 1960s to <5 3 109 m3 yr21 in 20002002
[Wang et al., 2007]. Since 2003, water ux from Huanghe into the Bohai Sea has been modulated by the
manipulation of water discharge from several major dams (SanMenXia and XiaoLangDi) located 800
1000 km upstream of the estuary [Wang et al., 2006; Yu, 2006]. Although Huanghe is still an important large
river due to its signicant catchment basin, its water discharge and alkalinity export only have minor impact
on China seas [Peterson et al., 2008; Wang et al., 2011; Zhai et al., 2014].

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Table 1. Summary of Cruise Informationa

Sampling Date

Sampling Area

Number of Stations

Number of Samples

46 Apr
811 Apr
2425 Apr
2627 Apr
27 May

North transect
Off the river mouth 1 central area
River mouth 1 off the river mouth
Central area
Eastern and southern areas

7
5
4
2
14

21 (TAlk) 1 18 (DIC)
13 (TAlk) 1 14 (DIC)
9 (TAlk) 1 9 (DIC)
6 (TAlk) 1 6 (DIC)
42 (TAlk) 1 39 (DIC)

See Figure 2 for locations.

2.2. Sampling and Analyses

Since Zhai and Hong [2012] skipped the details of sampling and analyses, we describe them here. From
April to early May 2007, totally 164 grid stations (from riverine ends of the Changjiang Estuary and the
Hangzhou Bay to the sea area) were sampled for multidisciplinary purposes [e.g., Li et al., 2011]. Among
them, 32 sampling sites including two Changjiang River mouth stations were selected for seawater DIC and
TAlk analyses (Figure 1a and Table 1).
Water samples were collected at two or three differing depths (typically 2, 5, and 10 m) using 8 L Niskin bottles mounted with a calibrated Conductivity-Temperature-Depth/Pressure (CTD) unit (SBE-917-plus, Sea Bird
Co.). They were stored in 60 mL borosilicate glass bottles (for DIC, bubble free) and 140 mL high-density
polyethylene bottles (for TAlk), immediately mixed with 50 lL of saturated HgCl2, sealed, and preserved at
room temperature until determination. Based on Huang et al. [2012] results, there are no differences
between measurement results from our procedure and from Dickson et al. [2007] sampling procedure.
Both DIC and TAlk samples were unltered but allowed to settle before measurement. Their data were collected in the Xiamen University laboratory in late May, using commercial analytical systems (models AS-C3
and AS-ALK11, Apollo SciTech Inc., USA). Briey, DIC was measured by infrared detection following acid
extraction of a 0.5 mL sample with a KloehnV digital syringe pump, as described in Cai et al. [2004]. TAlk
was determined at 25.0 C by Gran acidimetric titration on a 25 mL sample with a KloehnV digital syringe
pump, using a precision pH meter and an OrionV 8102BN Ross electrode for detection. Both DIC and TAlk
determinations were referred to Certicated Reference Materials from Andrew G. Dicksons lab at Scripps
Institute of Oceanography (batch 77, http://cdiac.ornl.gov/oceans/Dickson_CRM/batches.html) at a precision
of 62 lmol kg21 [Dickson et al., 2007; Zhai et al., 2007, 2014]. The uncertainties of the certicated DIC and
TAlk values of this batch are better than 0.3 and 0.6 lmol kg21, respectively.
R

The associated salinity (Practical Salinity Scale of 1978) and in situ temperature were obtained from the SBE917-plus CTD. DO data were collected on board [Li et al., 2011] following the classic Winkler procedure. The
DO saturation was calculated from eld-measured DO concentration, as divided by the DO concentration at
equilibrium with the atmosphere. The latter was calculated from temperature, salinity, and local air pressure,
as per the Benson and Krause [1984] equation. We also calculated oversaturated O2 via the eld-measured
DO concentration minus the DO concentration at equilibrium with the atmosphere.
2.3. Calculation of Aqueous CO2 Fugacity and Revelle Factor
The fugacity of CO2 (fCO2) and Revelle factor (homogenous buffer factor, RF for short) were calculated from
in situ temperature, salinity, and measured DIC and TAlk, using the CO2SYS.XLS (version 16) program developed by Pelletier et al. [2011], which is an updated version of CO2SYS.EXE [Lewis and Wallace, 1998]. The Millero et al. [2006] dissociation constants of carbonic acid and the Dickson [1990] dissociation constant for ion
HSO2
4 were used, while the phosphate and silicate required by the program were unavailable and replaced
by zero.
Wanninkhof et al. [1999] recommend the Mehrbach et al. [1973] constants (ret by Dickson and Millero
[1987]) as the optimal carbonate dissociation constants for determining surface water fCO2 and RF from
TAlk and DIC. In this study, we attempted to compare carbonate properties obtained from the Mehrbach
et al. [1973] and Millero et al. [2006] constants. Results showed that, in the data ranges of temperature, salinity, DIC, and TAlk of this study, the calculated carbonate property differences were 0.5% for fCO2 and
0.05% for RF. Therefore, no signicant differences in the calculation results by using different constants
were observed in our research. However, the Millero et al. [2006] constants have much broader applicable

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122

34

124

22 Mar to 06 Apr

32

30

Ch

124

126

128
Jeju Is.

07 Apr to 22 Apr
Ch
ang
jia
ng

(a)

(b)
23 Apr to 08 May

Latitude (oN)

Jeju Is.

Ch
ang
jia
ng

34

32

Latitude (oE)
126
128
122

10.1002/2014JC009856

Jeju Is.

Jeju Is.

09 May to 24 May
Ch
ang
jia
ng

ang
jia
ng

30
(c)

( d)

34
25 May to 09 Jun

32

30

Ch

ang
jia
ng

Jeju Is.

Jeju Is.

26 Jun to 11 Jul
Ch
ang
jia
ng

191
180

247 211
160

259

351

(e)

(f)

361

325

360

Figure 2. Evolution of 16 day composite satellite-derived (SeaWiFS) sea surface chlorophyll-a distribution in the study area. Corresponding
sampling sites are plotted. In Figure 2c, closed circles represent sampling sites from 24 to 27 April, while open circles are sampled from 2
to 7 May. The gray dashed line from the northern corner of the Changjiang Estuary to Jeju Island is the traditional boundary between the
Yellow Sea and the East China Sea. The white-dashed-line ellipse shows an offshore CO2 sink area in early July, associated with extremely
low chlorophyll-a and nitrate concentrations, as noted by Chou et al. [2009a]. White numbers in Figure 2f are the sea surface fugacity values of CO2 (in latm) determined by Chou et al. [2009a].

range of temperature (from 0 C to 50 C) and salinity (from 0 to 50) than the Mehrbach et al. [1973]
constants.
2.4. Satellite-Derived Chlorophyll-a
The 8 day composite sea surface chlorophyll-a data retrieved by SeaWiFS were acquired from the NASA
ocean color website (http://oceancolor.gsfc.nasa.gov), with a spatial resolution of 50 3 50 . Data validation
and correction has been done by He et al. [2013]. To improve spatial coverage of valid data, the original 8
day composite data were merged into 16 day composite sea surface chlorophyll-a distribution images (Figure 2). To avoid highly turbid waters, only data east of 123 E were used.

3. Results
3.1. Evolution of Sea Surface Chlorophyll-a Distributions
From spring to early summer, chlorophyll-a exhibited highly dynamic distributions (Figure 2). In the northwestern region near the Changjiang River mouth, very high sea surface chlorophyll-a values of >10 lg L21
persisted from early April to mid-May (Figures 2a2d), indicating the occurrence of spring algal blooms,
which are common in this region [e.g., Chen et al., 2003; Zhou et al., 2008; He et al., 2013]. At the open ocean

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33

(a)

32

April to early May

+
+

31

(b)

10.1002/2014JC009856

Early July

30
DO%

DO%

Latitude (N)

33

April to early May

(c)

(d)

Early July

YSW

32
CDW

31

Offshore water

30
Salinity

33 (e)

Salinity
April to early May

(f)

Early July

32
31
30
SST

SST

29
122

124

122

126

124

126

Longitude (E)
Figure 3. Contour maps of (a and b) DO saturation, (c and d) salinity, and (e and f) temperature in spring and early summer 2007 in the
study area. Sea surface salinity and temperature in July are from Chou et al. [2009a]. The spring water-type zoning is demonstrated in
Figures 3c and 3e.

end (southeastern corner of the study area), however, extremely low sea surface chlorophyll-a values (<0.5
lg L21) were observed (Figure 2). Between the two areas, sea surface chlorophyll-a exhibited considerable
variation. In the southern part of the study area, a large-scale bloom occurred in early April, as indicated by
high sea surface chlorophyll-a values of 510 lg L21 (Figure 2a). For the north survey transect, however, sea
surface chlorophyll-a values were relatively low (0.53 lg L21) during survey (Figure 2a). From May to early
June, another offshore algal bloom occurred in the area enclosed by white-dashed-line ellipses in Figure 2,
and was associated with high sea surface chlorophyll-a values of 510 lg L21 (Figures 2d and 2e). In midJune, satellite-derived chlorophyll-a data were unavailable since the rain-bearing southwest monsooninduced cloudy weather (see section 2.1 for details). From late June to early July, the southeastern low
chlorophyll-a (<0.5 lg L21) water extended into the earlier bloom areas. At several Chou et al. [2009a,
2009b] stations, enclosed by the white-dashed-line ellipse in Figure 2f, relatively low sea surface
chlorophyll-a values of 0.52 lg L21 were revealed during their survey.
3.2. Sea Surface Distributions of Field-Measured Parameters
The above mentioned offshore algal bloom events affected the water chemistry, as indicated by sea surface
DO saturation data (Figures 3a and 3b). In April, sea surface DO saturation was measured from 97% to 140%
in the area under study. The highest DO saturation of 140% was revealed in the algal bloom area near the
Changjiang River mouth, while other very high DO saturation values of 116%135% were associated with
the two high chlorophyll-a sampling sites as shown in Figure 2c. In the southern part of the study area, however, sea surface DO saturation was 106%114% in early May (Figure 3a), corresponding to a past bloom
event 30 days before (Figure 2a). In early July, DO saturation values of 105%118% were identied (Figure
3b) along the north transect of Chou et al. [2009a, 2009b], where another offshore bloom event occurred
3060 days before (Figures 2d and 2e).

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33

(a)

(b)
YSW

32
CDW

Latitude (N)

31

10.1002/2014JC009856

Offshore water

< 1940

30
29
33

< 2260

TAlk

(c)

32

(d)

340

31

29

fCO2

DIC:TAlk ratio

122

30

< 1940

DIC

124

122

126

124

126

Longitude (E)
Figure 4. Contour maps of (a) TAlk, (b) DIC, (c) DIC:TAlk ratio, and (d) fugacity of CO2 during April to May 2007, with the water-type zoning
as per Figure 3.

Contour maps of sea surface salinity showed that low-salinity (<32) water extended west of 123 E in spring
to west of 124 300 E in early summer (Figures 3c and 3d). In spring, sea surface salinity increased from 13.01
at the Changjiang River mouth to 34.49 in the northeastern corner of the surveying area, while sea surface
temperature (SST) increased from 10.54 C in the northern part to 18.45 C in the southeastern corner of the
surveying area (Figure 3e). The SST distribution showed that colder water from YSCC met with warmer
waters from TWWC and/or Kuroshio (Figure 1a). The sea surface salinity distribution demonstrated a highly
restrained CDW area (Figure 3c) due to limited water discharge from Changjiang during the surveying
period (Figure 1b). Between nearshore and offshore waters, a rough boundary with a salinity of 33.0 was
identied at 124 E (Figure 3c).
Sea surface TAlk in spring ranged from 2025 to 2305 lmol kg21, while sea surface DIC ranged from 1907 to
2115 lmol kg21. Both parameters presented their lowest values at the lowest salinity of 13.01 (the Changjiang River mouth), while their highest values were located at the most northwest site with a surface salinity
of 30.68 (Figures 4a and 4b). At those south sampling sites, most sea surface DIC were measured at comparatively low levels of 19191980 lmol kg21 (Figure 4b), although the corresponding TAlk was relatively
high and varied in a narrow range from 2254 to 2288 lmol kg21.
The sea surface DIC:TAlk ratio in spring ranged from 0.845 to 0.945 (Figure 4c). In the southeastern offshore
area, the low sea surface DIC:TAlk ratios of 0.8450.880 were comparable to those of typical ECS surface
water masses [Chen and Wang, 1999], while the extremely high DIC:TAlk ratios of 0.9410.945 were found at
the Changjiang River mouth (salinity from 13.01 to 20.17), showing riverine water intrusion (with a DIC:TAlk
ratio of 1.0) [Zhai et al., 2007]. In the northwestern area, despite moderate salinity of 30.6832.97, relatively
high sea surface DIC:TAlk ratios of 0.9050.918 were also revealed (Figure 4c).
Sea surface fCO2 in spring was usually lower than the air-equilibrium level (Figure 4d), ranging from 181 to
358 latm. The two exceptions were located at the Changjiang River mouth (salinity from 13.01 to 20.17),
where very high surface water fCO2 values of 368420 latm were determined. This small area was likely
dominated by the high pCO2 water discharged from Changjiang [Zhai et al., 2007; Chen et al., 2008; Yu et al.,
2013]. Off the Changjiang River mouth, the lowest surface water fCO2 value of 181 latm was obtained at
the nearshore bloom station along with the highest DO saturation (140%). Except for these nearshore
extreme values, our north sampling sites usually had higher sea surface fCO2 (from 286 to 358 latm) than
those south sampling sites (most sea surface fCO2 from 212 to 265 latm, Figure 4d).

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Table 2. Location, Temperature, Salinity, and Carbonate System Parameters of the Three Water Types Dened in This Studya

Water Type

Latitude
( N)

Longitude
( E)

Temperature
( C)

YSW
CDW
Offshore water

31.532.4
30.031.8
29.832.4

122.0125.0
122.5123.5
124.0127.0

10.5412.19
13.0717.48
13.8818.52

Salinity

TAlk
(lmol
kg21)

DIC
(lmol
kg21)

DIC:TAlk
Ratio

Revell
Factor

fCO2
(latm)

30.6532.99 22612305 20552122 0.9010.921 11.413.0 310377

28.7432.77b 22242272 19202037 0.8560.906 9.311.7 181369
32.6334.49 22542291 19192026 0.8450.889 8.910.6 212304

All depth data from 2 to 10 m were included.

The extremely high salinity of 32.77 was from a depth of 10 m at a highly stratied station with a relatively low surface salinity of
29.84.
b

Sea surface RF showed a similar pattern to DIC:TAlk ratios and fCO2 values (Table 2). At the Changjiang River
mouth, extremely high RF values of 15 and 16 were obtained at salinities of 13.01 and 20.17. Away from the
Changjiang River mouth, relatively high RF values of 11.413.0 were observed at the northwest sampling
sites, where sea surface DIC:TAlk ratios ranged from 0.905 to 0.918. At the southern and/or eastern sampling
sites, however, relatively low or moderate RF values of 8.910.6 were determined, compared with typical
open ocean values of 910 at the same latitude [Sabine et al., 2004].
3.3. Water Mixing Behaviors of Surface Water Carbonate System
3.3.1. Definition of Water Types
On the basis of hydrographic structures (Figures 3c and 3e), the T-S diagram (Figure 5a), and the classication delineated by Chou et al. [2009a], surface waters off the Changjiang River mouth were classied into
three different types. Note that the two Changjiang River mouth stations (salinity from 13.01 to 20.17) were
excluded from our sea area water-type classication.
The northerly YSW was indicated by the lowest temperature of 10.5412.19 C, while the salinity of YSW was
less than 33 [e.g., Li et al., 2012]. Around the Changjiang River mouth, the CDW was indicated by the low
sea surface salinity of 28.7432.50 together with moderate temperatures of 13.0717.48 C. The remaining
shelf waters (ECS offshore water) had relatively high salinities of 32.6334.49 and moderate temperatures of
13.8818.52 C. The temperature and salinity variations in these various water types are listed in Table 2,
while the spatial settings of the three water types are shown in Figures 3c and 3e. In summary, the spring
CDW and YSW only occupied limited areas of the northern ECS.
The three water types were further evidenced by variations in the carbonate system parameters (Table 2
and Figure 4). As reported by Zhai and Hong [2012], YSW was characterized by high TAlk, high DIC, and
high RF, compared with CDW and the ECS offshore water. Its TAlk (22612305 lmol kg21 at the salinity of
30.6532.99, Table 2) was also much higher than the July TAlk values (21732257 lmol kg21 at the salinity
of 28.6233.02) along the north transect of Chou et al. [2009a, 2009b], suggesting YSW in this study was different from the earlier dened YSW by Chou et al. [2009a].
Table 2 shows that, all those extremely high TAlk values of >2295 lmol kg21 were associated with relatively
low salinity of 30.6532.99, which were obtained at three north stations sampled during our 46 April survey (Figure 5b). They were consistent with high TAlk features of the North Yellow Sea water (TAlk5 2290 6 25 lmol kg21 at a salinity of 32) and of the Bohai Sea water (with the TAlk of 23002400 lmol
kg21 at the salinity of 31) [Zhai et al., 2014]. The two high TAlk waters (from the Bohai Sea and North Yellow Sea) mixed with several small coastal water sources during the long-distance transport in the northeast
monsoon period via YSCC (Figure 1a), leading to the composite YSW intrusion in our study area.
3.3.2. TAlk Versus Salinity
As a nearly conservative parameter, TAlk showed complicated water mixing behaviors in the study area
(Figure 5b), due to the above mentioned water-type settings. Generally, TAlk versus salinity varied among
three mixing lines (Figure 5b).
At the above mentioned three north stations with extremely high TAlk values (>2295 lmol kg21), TAlk versus salinity followed a linear relationship (Figure 5b), suggesting a water mixing between YSW and ECS offshore water (equation (1)):


TAlkYSW lmol kg21 523:9130 3 Salinity 1 2423:9 n58; r50:96

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Temperature (oC)

18

10.1002/2014JC009856

River mouth

16

CDW

14
12

(a)
10

2300

Offshore
water

YSW
YSW

2300
2200

-1

TAlk (mol kg )

TAlk

2250

2000
1900

2200

1800

ECS
waters

0 5 10 15 20 25 30 35

2150
2100
2050
2000

River mouth

04-06 April

08-11 April

24-25 April

26-27 April

02-07 May

01-11 July

x ECS seawater endmembers

(b)

1950

2100

YSW

2000
DIC

2100
2050

1900
1800

CDW

1700

-1

DIC (mol kg )

CDW

2100

2000

2026

0 5 10 15 20 25 30 35
S

1981

1950
1900

River mouth

1850
1800

(c)

1750
13
1

16

19

22

25

28

31

34

Salinity
Figure 5. (a) Temperature versus salinity, (b) TAlk versus salinity, and (c) DIC versus salinity in the study area, with various conservative mixing lines of TAlk and DIC as detailed in section 3.3. Explanation of data point refers to Table 1 and Figure 2. The early July data are from
Chou et al. [2009a], while the typical TAlk/Salinity values of diverse ECS offshore waters are as per Chen and Wang [1999]. In Figures 5b and
5c, the small plots are used for showing the extrapolated freshwater end-member values of our spring data. The two numbers (1981 and
2026) along the margin of Figure 5c are the DIC range of the high-salinity area in early April.

For water mixing in the CDW and the ECS offshore water, we developed a TAlk versus salinity relationship
(equation (2)) based on our 827 April and 27 May data (with the salinity of 13.0034.49), including 70
samples at 25 stations:

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TAlkCDW lmol kg21 513:5875 3 Salinity 1 1823:1 n570; r50:97

(2)

The intercept of TAlk of equation (2) (1823 lmol kg21) was consistent with the earlier reported spring freshwater end-member value (17111831 lmol kg21 in April 2005 at the freshwater end of the Changjiang
Estuary) by Zhai et al. [2007]. By comparison, TAlk data obtained in this region in early July (with the salinity
from 27.17 to 33.85) by Chou et al. [2009a] followed a water mixing function of TAlk (lmol kg21) 5 18.3583
3 Salinity 1 1641.3 (n 5 13, r 5 0.93) (retted based on the July data shown in Figure 5b). TAlk of their
freshwater end-member (1641 lmol kg21) was lower than our spring freshwater end-member value (1823
lmol kg21), presumably due to the dilution effects of regional rainfall in June, as mentioned in section 2.1.
During our 46 April survey, relatively lower TAlk values were revealed at two offshore stations (TAlk5 22622266 lmol kg21 at a salinity of 34.03 and TAlk 5 22732282 lmol kg21 at a salinity of 34.48), as
compared with the predicted values based on salinity via equation (2). At these two stations, TAlk versus
salinity ranged between our spring water mixing line of CDW and the ECS offshore water (equation (2)) and
the ideal rainwater dilution line of nearby Kuroshio and/or TWWC surface waters (TAlk 5 23002310 lmol
kg21 at a salinity of 35) [Chen and Wang, 1999]. The latter was characterized by equation (3):


(3)
TAlkKuroshio lmol kg21 52305=35 3 Salinity
Extrapolating to salinity 5 34.9, the TAlk values of above three equations were 2287 lmol kg21 (equation
(1)), 2297 lmol kg21 (equation (2)), and 2298 lmol kg21 (equation (3)). All of them were close to the previously dened TAlk value of Kuroshio Tropical Water, i.e., 2293 lmol kg21 at a salinity of 34.9 [Chen and
Wang, 1999]. Thus, the ECS open ocean end-members may have originated from Kuroshio surface water
[Chen et al., 1995].
Among the three equations, we reasonably regarded equation (2) as the primary water mixing model
of sea surface carbonate system in spring in the study area. Excluding those extremely high TAlk values (>2295 lmol kg21) at the three north stations, most spring TAlk values in the northern ECS sea
surface waters can be roughly predicted from salinity using equation (2) (Figure 5b). The bias of
630 lmol kg21 showed complicated inuences of other water sources and/or biogeochemical
processes.
3.3.3. DIC Versus Salinity
DIC is a nonconservative parameter. For example, biological removals were clearly observed in the
midsalinity zone during our 8211 April, 26227 April, and 227 May surveys (Figure 5c). However, a
rough mixing line for YSW and a relatively fair mixing line for CDW were still identied (Figure 5c).
For CDW, the regression line of the 24225 April data in the estuarine mixing zone (with the salinity
of 13.0131.98) is:


(4)
DICCDW lmol kg21 56:27503Salinity11820:9 n59; r50:97
Extrapolating equation (4) to salinity 5 0, the intercept of DIC (i.e., 1821 lmol kg21) was virtually the same
as the extrapolated freshwater end-member value of TAlk (1823 lmol kg21), within analytical errors. Since
most alkalinity (i.e., HCO2
3 ) in the Changjiang River results from carbonate and/or silicate weathering in the
catchment basin [Gaillardet et al., 1999], and moderately oversaturated free CO2 has been revealed in the
inner estuary [Zhai et al., 2007], nearly the same values of DIC and TAlk were expected at the freshwater
end-member [Zhai et al., 2007].
Extrapolating equations (2) and (4) to the mean salinity of the ECS offshore water (33.5, Figure 3c), the
TAlk and DIC values were 2278 lmol kg21 and 2031 lmol kg21, respectively. This high-salinity end-member
had a nearly air-equilibrium fCO2 of 352 latm at the mean offshore SST (17 C, Figure 3e), as calculated
from the DIC and TAlk.
If we assumed equation (4) to be the baseline conservative water mixing model of DIC between the Changjiang freshwater end-member and the Kuroshio surface water end-member, ECS offshore water showed DIC
values of 24108 lmol kg21 lower than the conservative values (Figure 5c), indicating net primary
production-induced DIC drawdown. See section 4.2 for details. In YSW, however, sea surface DIC was 31
109 lmol kg21 higher than the salinity predicted value via equation (4), indicating an external source of
DIC.

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4. Discussion

120
04-06 April

4.1. Influences of YSW on the

Northern ECS Carbonate
System
y
=
1.18
x
+
26.98
40
26-27 April
2
To better evaluate the inuences
=
0.91
R
02-07 May
0
of contrasting coastal processes
on the northern ECS carbonate
-40
system, we calculated the baseline TAlk and DIC at salinity,
-80
according to equations (2) and
(4). We then calculated the dif-120
ferences between the measured
-120
-80
-40
0
40
80
120
concentrations and the baseline
-1
TAlk (mol kg )
values along the mixing lines,
i.e., DTAlk and DDIC in equations
Figure 6. DDIC versus DTAlk in April to May 2007 in the study area, with the vertical
dashed line indicating DTAlk 5 0 and the horizontal dashed line showing DDIC 5 0.
(5) and (6), with positive values
Explanation of data point refers to Table 1 and Figure 2. The dashed-line ellipse
indicating addition of DIC or TAlk
shows YSW data (Figures 3c and 4), and the real line is the regression line of the
and negative values indicating
YSW data. The denitions of DTAlk and DDIC are as per equations (5) and (6),
respectively.
removal. Note that both of the
addition and the removal are relative to the baseline conservative water mixing between the Changjiang freshwater end-member
and the Kuroshio surface water end-member:
-1

DIC (mol kg )

80

08-11 April

YSW

24-25 April

DTAlk5TAlkTAlkCDW
CDW

DDIC5DICDIC

(5)
(6)

Figure 6 summarizes DDIC versus DTAlk in April to May 2007 in the study area. At those YSW sampling sites,
DDIC 5 1.18 3 DTAlk 1 26.98 lmol kg21 (n 5 18, r 5 0.95) (Figure 6). The intercept showed that YSW contained additional DIC of at least 27 lmol kg21 as compared with CDW and the ECS offshore water. And the
slope indicated that YSCC delivered 18% more additional DIC than additional TAlk into the northern ECS,
if effects of other biogeochemical processes were negligible.
Figure 4 shows that YSW was not only characterized by high TAlk and high DIC [Zhai and Hong, 2012], but
also associated with a relatively high DIC:TAlk ratio of 0.9010.921, compared with the CDW (0.8560.906)
and ECS offshore water (0.8450.888). According to Egleston et al. [2010], an increase in the seawater DIC:TAlk ratio to 1:1 leads to a decline in chemical buffering capacity. Based on the denition of RF [Revelle and
Suess, 1957; Sundquist et al., 1979], the fractional change in sea surface DIC after reequilibration with the
atmosphere can be expressed as dDIC/DIC 5 (dfCO2/fCO2)/RF, where prex d is the differential change.
Therefore, the relatively high RF values of 11.413.0 in YSW (Table 2) suggested that this water was unable
to store so much excess DIC as the CDW and the ECS offshore water, under the same forcing of atmospheric
CO2 rise. The later two waters had relatively low or moderate RF values from 8.9 to 11.7 (Table 2). This issue
needs more investigation.
Moreover, the YSW had relatively high fCO2 values of 310377 latm (even at very low temperatures of
10.5412.19 C), compared with the low fCO2 values of 212304 latm in ECS offshore water (at relatively
high temperatures of 13.8818.52 C) (Table 2). Similar pattern has previously been reported by Wang et al.
[2000]. Therefore, the YSW intrusion virtually counteracted CO2 uptake in the northern ECS, if no net primary
production occurred. When the cold YSW was warmed to the mean SST of the ECS offshore water (17 C,
Figure 3e), the fCO2 increased to a CO2 outgassing level of 392484 latm, if no other processes affected the
carbonate system.
4.2. Primary Production-Induced Sea Surface DIC Drawdown in Spring
Several algal blooms occurred in the northern ECS in the spring of 2007 (Figure 2). Correspondingly, both
DO production and DIC drawdown were observed (Figures 3a and 5c). To discuss biological DO production
and DIC drawdown since early April, we plotted Redeld lines of DIC versus DO (Figure 7a). At the nearshore
bloom station along with the highest DO saturation (140%), the DIC drawdown (88 lmol kg21) versus

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2150
Primary production
Net

-1

DIC (mol kg )

Air-sea exchange

2050

1950

1850
(a)

1750
450

f CO2 (atm)

400
350
300

Air p CO2

04-06 April
08-11 April
24-25 April
26-27 April
02-07 May
01-11 July

10.1002/2014JC009856

oversaturated DO (109 lmol O2 kg21)

roughly followed the Redeld ratio
of 2106:138 (Figure 7a). At many
southern stations, however, the
observed DIC drawdown versus oversaturated DO deviated from that of
the theoretical prediction based on
the Redeld relationship, i.e., many
DIC drawdown values were much
higher than those values predicted
based on the Redeld ratio and
observed oversaturated DO (Figure
7a). This was likely due to the slower
air-sea reequilibration of CO2 compared with that of DO [DeGrandpre
et al., 1997; Carrillo et al., 2004; Zhai
et al., 2009].

As mentioned in section 3.1, a largescale offshore algal bloom occurred

at those southern stations in early
200
spring (Figure 2a), presumably result(b)
ing in both DO production and DIC
150
drawdown. After 7 April, this early
-20
0
20
40
60
80
100
120
spring algal bloom disappeared and a
Oversaturated O2 (mol kg-1)
nonbloom status persisted for 30
days before our sampling (Figures 2b
Figure 7. (a) DIC versus oversaturated DO and (b) fugacity of CO2 versus oversaturated DO in the study area. Explanation of data point refers to Table 1 and Figure 2.
and 2c). During this period, sea surThe early July data are from Chou et al. [2009a, 2009b]. Thin vertical lines show the
face DO approached atmospheric
air-equilibrated DO level. Gray area in Figure 7a is between two Redeld functions
equilibrium (Figure 3a), while DIC
of DIC 5 20.7681 3 DO 1 2026 lmol kg21 (upper line) and of DIC 5 20.7681 3
DO 1 1981 lmol kg21 (lower line). The intercepts of DIC refer to Figure 5c. Gray
exhibited little change (see section
area in Figure 7b shows the air-equilibrated fCO2 range (380393 latm), calculated
4.3). Therefore, the DIC-DO slope
from the sole ask analysis datum of atmospheric CO2 concentration (392.5 parts
changed, as illustrated by arrows in
per million volume in dry air in April 2007) at the adjacent Tae-ahn Peninsula (TAP)
site (36 440 N 126 080 E), and all those survey-based barometric pressure at 10 m
Figure 7a. Similar intraseasonal
above the sea surface and sea surface temperature and salinity. The data processing
changes in the pCO2-DO relationship
and correction procedures refer to Zhai and Dai [2009].
have been reported in this region
previously [Zhai and Dai, 2009]. Note
that the saturated DO (calculated from in situ temperature and salinity) in a given salinity of 2834 should
decline by 2527 lmol O2 kg21 when SST changed from 12 C in early April to 17 C in early May. This possible temperature effect may enlarge our oversaturated DO results by 2527 lmol O2 kg21. As the result, biological DIC drawdown and oversaturated DO in Figure 7a may depart more from the Redeld ratio, if the
possible temperature effect of the oversaturated DO results was fully corrected. Therefore, the corresponding uncertainty of oversaturated DO value due to temperature effect does not affect our discussion.
250

In the CDW and the ECS offshore water, the biological DIC drawdown ranged from 24 to 108 lmol kg21
(average 73 6 20 lmol kg21) (Figure 6). Together with the mixed layer depth of 10 m and the sustained
algal bloom time of 16 days (Figure 2), ignoring the small changes in DIC induced by the air-sea exchange
and water mixing over 30 days, we estimated that the net community production (NCP) during the southern offshore bloom event was 45 6 12 mmol C m22 d21. This NCP value was comparable to the euphotic
zone integrated primary productivity of 3080 mmol C m22 d21 measured in March and June 1998 in the
inner shelf of the ECS [Gong et al., 2003], but was only 36% of the area-integrated primary productivity
(125 mmol C m22 d21) obtained in July 1986 in CDW and the northern ECS offshore water areas [Ning
et al., 1988]. Although the spring NCP value estimated in this study was lower than that in the northern Gulf
of Mexico (90 mmol C m22 d21 in spring in the Mississippi River plume [Guo et al., 2012b]), it was higher
than NCP values observed in the northern South China Sea (36 6 12 mmol C m22 d21 in the Pearl River

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plume and 23 6 26 mmol C m22 d21 in its summer coastal upwelling area [Cao et al., 2011]). Therefore, our
NCP result conrms again the high productivity feature of the study area.
The biological drawdown of DIC certainly affected sea surface fCO2. In areas with oversaturated DO,
seawater fCO2 was usually 110180 latm lower than the air-equilibrated level (Figure 7b), leading to a
signicant air-sea CO2 ux. During the survey cruise, eld-measured wind speed at 10 m height
ranged from 0.2 to 9.6 m s21 (average 4.5 6 2.6 m s21). Therefore, the offshore gas transfer velocity
was determined to be 5.05 cm h21 or 1.21 m d21 using the revised equation of Wanninkhof [1992] by
Sweeney et al. [2007]:
k50:273u210 3Sc=66020:5

(7)

where k is the gas transfer velocity (unit: cm h21), u10 is the wind speed at 10 m height, and Sc is the
Schmidt number in seawater [Wanninkhof, 1992]. During calculation, temperature was set to 17 C (mean
offshore SST, Figure 3e), while u10 was replaced by a constant value of 4.5 m s21 (the survey mean value).
The offshore air-sea CO2 ux was thus estimated as 58 mmol C m22 d21 in April to May 2007. This ux
value was comparable to the earlier estimate of 7.7 6 5.1 mmol C m22 d21 for the northwestern ECS in
spring [Zhai and Dai, 2009], which was based on multiple-year underway measurements and recalculated
using the Sweeney et al. [2007] gas transfer velocity.
4.3. Slow Recovery of Earlier DIC Drawdown and its Effects on the Carbonate System in Early
Summer
Zeebe and Wolf-Gladrow [2001] calculated an air-sea equilibration time (s) of 240 days for CO2 with a mixed
layer depth of 50 m and a global mean gas transfer velocity of 4.2 m d21, which was 20 times longer than
that for O2 [Zeebe and Wolf-Gladrow, 2001]. Carrillo et al. [2004] also showed that, under regional conditions
west of the Antarctic Peninsula, sea surface pCO2 only changed by approximately 12% within the 30 day
time frame, although DO had approached atmospheric equilibrium during the same time span. In the North
Yellow Sea, even under disturbance of the relatively high wind speed of 10 m s21 in winter, the s(CO2) was
as long as 100104 days [Zhai et al., 2014]. This is because free CO2 only accounts for a small part (0.5%)
of DIC. DIC buffers changes in the CO2 concentration and thereby slows down equilibration [Revelle and
Suess, 1957; Sundquist et al., 1979; Zeebe and Wolf-Gladrow, 2001; Egleston et al., 2010]. Thus, CO2 exchange
across the air-sea interface is a slower process than many other dissolved gases. Therefore, the biological
DIC drawdown in spring may have a durative effect on the marine carbonate system.
To demonstrate this issue, we also determined s(CO2). Following Zeebe and Wolf-Gladrow [2001],
s(CO2) 5 dML/k/KH 3 (DIC/fCO2/RF), where dML is the mixed layer depth (10 m), k is the gas transfer velocity (1.21 m d21), and KH is the solubility coefcient of CO2 [Weiss, 1974], i.e., 0.036 mol kg21 atm21 with
a temperature of 17 C (mean offshore SST, Figure 3e) and salinity of 33.5 (mean offshore sea surface salinity,
Figure 3c). During calculation, initial values of sea surface DIC and fCO2 were set to the medium offshore values in May, i.e., 1950 lmol kg21 and 240 latm (Figure 7), respectively, the corresponding RF was calculated
as 9.4. Ignoring the temperature effect on seawater fCO2, the offshore air-sea equilibration time of CO2 was
estimated at 10/1.21/0.036 3 (1950/240/9.4) 5 198 days. This s value meant that the air-sea disequilibrium
of fCO2 declined over 198 days to 37% (1/e) of its initial value [Zeebe and Wolf-Gladrow, 2001]. Therefore,
from May to July, the air-sea disequilibrium of fCO2 changed by approximately (1 (1 0.37)(60/198)) 5 13%
over the 2 months.
To estimate the air-sea exchange-induced DIC change after the past algal bloom stopped, we rewrote the
denition equation of RF [Revelle and Suess, 1957; Sundquist et al., 1979] as dDIC 5 DIC 3 (dfCO2/fCO2)/RF,
where the air-sea exchange-induced dfCO2 (from May to July) at the constant temperature of 17 C was 0.13
3 (375 240) 5 18 latm, initial DIC and fCO2 were set to 1950 lmol kg21 and 240 latm, respectively, and
RF was replaced by 9.4. Therefore, the air-sea exchange-induced dDIC from May to July was roughly estimated at 16 lmol kg21. This value accounted only for 17%30% of the spring biological DIC drawdown of
73 6 20 lmol kg21 (Figure 6).
To predict the evolution of sea surface fCO2, the temperature effect on fCO2 must be considered. First, the
July fCO2 at the constant mean offshore SST of spring (17 C, Figure 3e) should be 240 1 18 5 258 latm,
where 240 latm was the initial fCO2 in May (Figure 7b) and 18 latm was the air-sea exchange-induced
fCO2 change at a constant temperature, as mentioned above. Given the offshore temperature increase of

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9 C, i.e., 2527 C in early July (Figure 3f) [Chou et al., 2009a] 217 C in early May, using a temperature coefcient of 4.23%  C21 [Takahashi et al., 1993], a nearly air-equilibrated offshore fCO2 of 258 3 e0.042339 5 377
latm was expected at the July temperature. This expected offshore fCO2 value was comparable to Chou
et al. [2009a] eld data in early July in the southern part of our study area (351361 latm at three stations,
Figure 2f). If the ushing and exchange of the ECS offshore water was negligible in the study area (see section 2.1 for details), this result suggested that the recovery of earlier DIC drawdown was controlled by the
air-sea exchange and temperature effect. The two processes can explain most of the abiological variability
in fCO2 observed from late spring to early summer in the ECS offshore water.
The very low offshore sea surface fCO2 data in early July (160259 latm, Figure 2f) were likely independent
of any external source, as indicated by the ordinary water mixing behavior of TAlk (Figures 5b) observed by
Chou et al. [2009a]. Since high chlorophyll-a signals indicated that another offshore algal bloom occurred in
this region from mid-May to early June (Figure 2), these offshore low fCO2 data may have originated from
the earlier algal bloom. This algal bloom may also have affected water chemistry, as indicated by on-site sea
surface DO saturation signals of >100% in early July (Figure 3b) [Chou et al., 2009b]. And the DIC versus
oversaturated DO plot during the July survey (Figure 7a) suggested another biological DIC drawdown event
from mid-May to early June. The algal bloom disappeared in mid-June (Figure 2). Half a month later, chlorophyll may have sunk into the subsurface layer and surface nutrients sustained low levels due to insignicant
supplies via weak vertical mixing under summer stratication. However, sea surface CO2 was buffered by
the marine carbonate system, maintaining signicantly undersaturated levels for at least several weeks, as
discussed above. Therefore, to better understand sea surface carbonate chemistry dynamics in ocean margins, together with water mixing and biological DIC drawdown, insight into the chemical buffering capacity
of carbonate system is also essential.

5. Concluding Remarks
This study showed that sea surface carbonate chemistry dynamics in the northern East China Sea (ECS)
were inuenced by several contrasting coastal processes, including water mixing (among Changjiang dilution water, ECS offshore water, and Yellow Sea water), net primary production, and air-sea exchange under
the modulation of chemical buffering capacity. The northern ECS overall served as an atmospheric CO2 sink
in spring mainly due to signicant biological drawdown of DIC in the ECS offshore water and the Changjiang dilution water.

Acknowledgments
We thank Wen-liang Wang for his
assistance with sample collection, Da-ji
Huangs group (from the Second
Institute of Oceanography, SOA) for
providing salinity and temperature
data, and Christine Watts for her
assistance with English. The crew of
R/V Haijian 49 provided much help
during the sampling cruise. The
research was jointly supported by the
Key Laboratory of Marine Ecosystem
and Biogeochemistry, SOA, China
through open fund (contract
LMEB200802), National Basic Research
Program (973 Program) of China
through grant 2010CB428903, and the
National Natural Science Foundation
of China (grants 41276061, 41076044,
and 40876040). We appreciate critical
comments and valuable suggestions
from two anonymous reviewers, which
have improved the quality of this
paper.

ZHAI ET AL.

We must point out that our study was based on a limited data set, and therefore the specic results were
by no means general. However, this study revealed that the Yellow Sea water (YSW) had higher DIC:TAlk
ratio than the usual values in the other northern ECS surface waters. Although YSW also showed CO2 uptake
due to the very low temperature, its intrusion virtually counteracted CO2 uptake in the northern ECS. Given
the fact that chemical buffering capacity slows down the air-sea reequilibration of CO2, the early spring DIC
drawdown in the ECS offshore water may have durative effects on the sea surface carbonate system there
until early summer. These insights are fundamental to understanding sea surface carbonate chemistry
dynamics in this important ocean margin, and may also help to better understand the chemical dynamics
in many other marine systems.

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