1. Palmer LTER: Temporal and Spatial Variability of Oxygen Saturation,
Dissolved Inorganic Carbon and Fugacity of Carbon Dioxide in Sur-
face Waters West of the Antarctic Peninsula
S
ou
th
At
lan
tic Oc
ean
II
JGOFS•LTER
OCEAN TIME-S
ER
WA IE
Christopher J. Carrillo and David M. Karl
A S
PAL H • O • T
Ind
0°
Antarctica
H 158°W
ian Ocean
PALMER
22°45'N STATION STATION
Euphasia superba ALOHA
& 90° 90°
Department of Oceanography, University of Hawaii
W E
CO
S
IC
S
ou C
U
M
th
• O 180° • D N
1000 Pope Road, Honolulu, HI, 96822, U.S.A.
At LE
P
A
lant
ic Ocean
D • L Y
OC D
EAN &
GES
carrillo@soest.hawaii.edu, dkarl@soest.hawaii.edu
Pygoscelis adeliae
UN -ICE LINKA
IVER AII
SITY of HAW
Abstract Introduction
Chemical, physical and biological controls on in-situ Figure 1 Section of the LTER program study Accurate estimations of CO2 and O2 fluxes, coupled with an understanding
oxygen (O2) saturation, dissolved inorganic carbon area showing station locations on the 200 to 600 of the processes that control these fluxes, is necessary to predict the res--
(DIC) concentrations, and fugacity of carbon dioxide grid lines. During each austral summer LTER field ponses of the Southern Ocean to anthropogenic induced climate change.
season (Jan–Feb), a suite of hydrographic, opti- The Palmer Long-Term Ecological Research (LTER) program was estab-
(fCO2) in surface water induce temporal and spatial cal and biological measurements are made at lished in 1990 to study the Antarctic marine ecosystem west of the Antarc-
habitat variability in surface waters west of the Antarc- each location using a Bio-optical Profiling Sys- tic Peninsula, especially habitat variability and response to global climate
tic Peninsula. Geographic surveys of O2, DIC and tem (BOPS; Smith et al. 1984). The shelf break change (Smith et al. 1995).
fCO2 show large interannual and spatial variability is shown by the 1000 meter isobath (solid red
Our component of this multi-disciplinary project, “Microbiology and
line). O2 and DIC surface concentrations from
predicted for polar regions with seasonal ice cover. the Southern offshore area, (designated by
carbon flux,” includes measurements of carbon (C) and oxygen (O) inven-
The magnitude and timing of sea-ice coverage, fluctu- green box on left) and Central onshore area (des- tories (dissolved gases and solutes), C and O fluxes (production, particle
ations in the quantity of Antarctic Circumpolar Deep ignated by green box on right) are compared to export and air-sea gas exchange) and microbial community structure and
winter and spring “ice indices” expressed as ice function.
Water (CDW) upwelled onto the shelf and biological In the ice-dominated Southern Ocean, the seasonal advance and retreat
coverage in km2 for the LTER grid during the win-
production and consumption may explain the inter- ter and spring seasons (Smith et al. 1998). of sea ice may affect both C and O fluxes. Quantifying these fluxes requires
annual and spatial variability that are observed. that we sample the dissimilar ecosystems comprising the Southern Ocean.
Regional Variability
Methods
Oxygen and DIC samples were collected within the Palmer
LTER fixed sampling grid during the austral summer (Jan–Feb)
field seasons of 1993 to 1997 to facilitate both geographical and
interannual comparisons (Figure 1).
Oxygen concentrations were determined in seawater, drawn
into calibrated iodine flasks, by a automated potentiometric
Winkler titration (Carpenter 1965). Precision was typically 0.1%.
Accuracy was determined using CSK KIO3 certified reference
material (Wako Chemical). Oxygen saturation was calculated
using the constants of Weiss (1970) and surface seawater temper-
ature and salinities.
DIC was measured by coulometric determination of extracted
CO2 on stored 300 ml samples fixed with 100 µl of saturated mer-
curic chloride (Johnson et al. 1985). Precision was typically
0.05%. Accuracy was 1 µmol/kg as determined using A. Dickson
Certified Reference Materials (Dickson 1991). For comparison
among stations and years, DIC was normalized to a salinity of Figure 3 CO2 % saturation versus O2 % saturation using
33.5 (N-DIC). data from Figure 2A and 2B. Colors correspond to the sample
An automated underway CO2/O2 measurement system analyzed area shown by the ship track in plot 2C. The blue, green and
yellow points represent measurements from the LTER grid
surface seawater from the ships bow intake utilizing a counter
area while the orange and red points represent measure-
flow rotating disk equilibrator and a LICOR 6262 infrared CO2 ments from coastal inshore locations.
gas analyzer. The system was calibrated with NOAA-CMDL certi-
fied CO2 gas standards. During the 1997 and 1998 field seasons,
underway oxygen concentrations were determined with 4
Endeco oxygen electrodes. The electrodes were calibrated with
oxygen samples taken from the BOPS. Figure 2 Underway system measurements of fCO2 and O2 con-
centrations for the 1997 LTER field season. The colors in plots A
and B correspond to the sample area shown by the ship track in Figure 4 Measured and calculated fCO2 versus Julian day for
plot C. (A) Julian day versus fCO2 (µatm). (B) Julian day versus the LTER 1996 field season. Inset: Calculated versus measured
O2 concentration (µmol/l.) (C) Map showing the ship track of fCO2.The solid line is y=x.
Results the R/V Polar Duke.
Regional Variability
The ratio of O2 to CO2 varies from the air saturated equilibrium
Interannual Variability
state suggesting a combination of processes controlling O2 and
CO2 distributions within onshore to offshore areas (Figures 2
and 3).
A comparison of calculated fCO2 [using constants of Roy et
al. (1993) with the program of Lewis and Wallace (1995)] with
measured fCO2 values showed no significant differences (-6 ±
11 µatm; Figure 4).
Interannual Variability
During the 1993 and 1996 field seasons, supersaturated surface
water predominated throughout the study area (Figure 5). Dur-
ing the 1994 and 1995 field seasons, however, undersaturated
surface water occurred through much of the area (Figure 5).
Relatively low normalized DIC concentrations were wide-
spread during the 1994 field season compared to other years
(Figure 6).
Areas of surface ocean supersaturation (values above atmos-
pheric equilibrium) were found off the shelf, suggesting upwell-
ing as a source of CO2-enriched waters (Figure 7). Areas of Figure 5 Calculated oxygen saturation for the LTER study Figure 6 Salinity normalized DIC for the LTER 1993 to Figure 7 Surface water fCO2 represented as percent satura-
undersaturation (values below atmospheric equilibrium) occur- area in austral summer 1993 to 1997 field seasons (Jan–Feb). 1997 field seasons. The axes are the same as described in Fig- tion relative to the atmosphere for the LTER 1996 to 1998
red in coastal waters and were associated with increases in chlor- The x and y axes represent longitude and latitude, respectively. ure 5. field seasons. Unlike oxygen and DIC measurements, fCO2
ophyll, implying a biological control. Between 1996 and 1998, The z axis represents year. Each colored circle represents a sta- measurements were made with the automated underway CO2
tion location where an oxygen saturation calculation was made. system resulting in greater spatial resolution. The axes are the
supersaturated surface waters encroached onshelf (Figures 2
same as described in Figure 5.
and 7).
Correlation and Processes
Discussion & Conclusions
Figure 8 (left) Mean and
standard deviation of measured
Processes such as upwelling of CDW onto the shelf, parameters for the Central
ice dynamics and biological production and consump- onshore (red line) and South-
tion of organic matter all contribute to the complex ern offs- ore regions (yellow
h
line) for the 1993 to 1996
spatiotemporal variability observed in O2 and carbon
field sea- ons. (A) Normalized
s
pool dynamics. The relative significance of each pro-- DIC in µmol/kg. (B) Oxygen con-
cess in controlling O2, DIC and fCO2 has yet to be centration in µmol/l. (C) Chloro-
determined. phyll mg/m3 (D) Ice indices rep-
resented as ice coverage within
The increased onshelf intrusion of seawaters that the LTER area (Smith et al.
are supersaturated with respect to CO2 between 1996 1998). The yellow line repre-
and 1998 suggests that upwelling of CDW may con- sents the total ice coverage in
the winter and the red line rep-
trol CO2 concentrations offshore. resents the total ice cover dur-
O2 concentrations correlate strongly with the ice ing the spring.
indices, suggesting that ice dynamics are important in
controlling O2 distributions (Figure 8). Within the
Southern offshore region of the LTER grid, higher
O2 concentrations are present during years of lower
chlorophyll concentrations, and visa versa. This sug- References
Carpenter J.H. 1965. Limnology and Oceanography 10, 135–141.
gests that physical controls such as air-sea gas Dickson A.G. 1991. US JGOFS News 3, 4.
exchange may be important in controlling O2 concen- Johnson K.M., King A.E., Sieburth J.McN. 1985. Marine Chemistry 16, 61-82.
Lewis E.R. and Wallace D.W.R. 1995. Data report BNL-61827 informal Brook- aven National National Labora-
h
trations. tory.
Salinity normalized DIC does not correlate with Roy R.N., Roy L.N., Vogel K.M., Porter-Moore C., Pearson T., Good C.E. 1993. Marine Chemistry 42, 249–267.
Smith R.C., Baker K.S., Stammerjohn S. E. 1998. Bioscience 48, 83–93.
O2 or ice indices. Smith R.C., Baker K.S., Fraser W.R., Hofmann E.E., Karl D.M., Klink J.M., Quetin L.B., Prezelin B.B., Ross R.M.,
Trivelpiece W.Z., Vernet M. 1995. Oceanography 8, 77–86.
Smith R.C., Booth C.R., Star J.L. 1984. Applied Optics 23, 2791–2797.
Weiss R.F. 1970. Marine Chemistry 2, 203–215.
![Palmer LTER: Temporal and Spatial Variability of Oxygen Saturation,
Dissolved Inorganic Carbon and Fugacity of Carbon Dioxide in Sur-
face Waters West of the Antarctic Peninsula
S
ou
th
At
lan
tic Oc
ean
II
JGOFS•LTER
OCEAN TIME-S
ER
WA IE
Christopher J. Carrillo and David M. Karl
A S
PAL H • O • T
Ind
0°
Antarctica
H 158°W
ian Ocean
PALMER
22°45'N STATION STATION
Euphasia superba ALOHA
& 90° 90°
Department of Oceanography, University of Hawaii
W E
CO
S
IC
S
ou C
U
M
th
• O 180° • D N
1000 Pope Road, Honolulu, HI, 96822, U.S.A.
At LE
P
A
lant
ic Ocean
D • L Y
OC D
EAN &
GES
carrillo@soest.hawaii.edu, dkarl@soest.hawaii.edu
Pygoscelis adeliae
UN -ICE LINKA
IVER AII
SITY of HAW
Abstract Introduction
Chemical, physical and biological controls on in-situ Figure 1 Section of the LTER program study Accurate estimations of CO2 and O2 fluxes, coupled with an understanding
oxygen (O2) saturation, dissolved inorganic carbon area showing station locations on the 200 to 600 of the processes that control these fluxes, is necessary to predict the res--
(DIC) concentrations, and fugacity of carbon dioxide grid lines. During each austral summer LTER field ponses of the Southern Ocean to anthropogenic induced climate change.
season (Jan–Feb), a suite of hydrographic, opti- The Palmer Long-Term Ecological Research (LTER) program was estab-
(fCO2) in surface water induce temporal and spatial cal and biological measurements are made at lished in 1990 to study the Antarctic marine ecosystem west of the Antarc-
habitat variability in surface waters west of the Antarc- each location using a Bio-optical Profiling Sys- tic Peninsula, especially habitat variability and response to global climate
tic Peninsula. Geographic surveys of O2, DIC and tem (BOPS; Smith et al. 1984). The shelf break change (Smith et al. 1995).
fCO2 show large interannual and spatial variability is shown by the 1000 meter isobath (solid red
Our component of this multi-disciplinary project, “Microbiology and
line). O2 and DIC surface concentrations from
predicted for polar regions with seasonal ice cover. the Southern offshore area, (designated by
carbon flux,” includes measurements of carbon (C) and oxygen (O) inven-
The magnitude and timing of sea-ice coverage, fluctu- green box on left) and Central onshore area (des- tories (dissolved gases and solutes), C and O fluxes (production, particle
ations in the quantity of Antarctic Circumpolar Deep ignated by green box on right) are compared to export and air-sea gas exchange) and microbial community structure and
winter and spring “ice indices” expressed as ice function.
Water (CDW) upwelled onto the shelf and biological In the ice-dominated Southern Ocean, the seasonal advance and retreat
coverage in km2 for the LTER grid during the win-
production and consumption may explain the inter- ter and spring seasons (Smith et al. 1998). of sea ice may affect both C and O fluxes. Quantifying these fluxes requires
annual and spatial variability that are observed. that we sample the dissimilar ecosystems comprising the Southern Ocean.
Regional Variability
Methods
Oxygen and DIC samples were collected within the Palmer
LTER fixed sampling grid during the austral summer (Jan–Feb)
field seasons of 1993 to 1997 to facilitate both geographical and
interannual comparisons (Figure 1).
Oxygen concentrations were determined in seawater, drawn
into calibrated iodine flasks, by a automated potentiometric
Winkler titration (Carpenter 1965). Precision was typically 0.1%.
Accuracy was determined using CSK KIO3 certified reference
material (Wako Chemical). Oxygen saturation was calculated
using the constants of Weiss (1970) and surface seawater temper-
ature and salinities.
DIC was measured by coulometric determination of extracted
CO2 on stored 300 ml samples fixed with 100 µl of saturated mer-
curic chloride (Johnson et al. 1985). Precision was typically
0.05%. Accuracy was 1 µmol/kg as determined using A. Dickson
Certified Reference Materials (Dickson 1991). For comparison
among stations and years, DIC was normalized to a salinity of Figure 3 CO2 % saturation versus O2 % saturation using
33.5 (N-DIC). data from Figure 2A and 2B. Colors correspond to the sample
An automated underway CO2/O2 measurement system analyzed area shown by the ship track in plot 2C. The blue, green and
yellow points represent measurements from the LTER grid
surface seawater from the ships bow intake utilizing a counter
area while the orange and red points represent measure-
flow rotating disk equilibrator and a LICOR 6262 infrared CO2 ments from coastal inshore locations.
gas analyzer. The system was calibrated with NOAA-CMDL certi-
fied CO2 gas standards. During the 1997 and 1998 field seasons,
underway oxygen concentrations were determined with 4
Endeco oxygen electrodes. The electrodes were calibrated with
oxygen samples taken from the BOPS. Figure 2 Underway system measurements of fCO2 and O2 con-
centrations for the 1997 LTER field season. The colors in plots A
and B correspond to the sample area shown by the ship track in Figure 4 Measured and calculated fCO2 versus Julian day for
plot C. (A) Julian day versus fCO2 (µatm). (B) Julian day versus the LTER 1996 field season. Inset: Calculated versus measured
O2 concentration (µmol/l.) (C) Map showing the ship track of fCO2.The solid line is y=x.
Results the R/V Polar Duke.
Regional Variability
The ratio of O2 to CO2 varies from the air saturated equilibrium
Interannual Variability
state suggesting a combination of processes controlling O2 and
CO2 distributions within onshore to offshore areas (Figures 2
and 3).
A comparison of calculated fCO2 [using constants of Roy et
al. (1993) with the program of Lewis and Wallace (1995)] with
measured fCO2 values showed no significant differences (-6 ±
11 µatm; Figure 4).
Interannual Variability
During the 1993 and 1996 field seasons, supersaturated surface
water predominated throughout the study area (Figure 5). Dur-
ing the 1994 and 1995 field seasons, however, undersaturated
surface water occurred through much of the area (Figure 5).
Relatively low normalized DIC concentrations were wide-
spread during the 1994 field season compared to other years
(Figure 6).
Areas of surface ocean supersaturation (values above atmos-
pheric equilibrium) were found off the shelf, suggesting upwell-
ing as a source of CO2-enriched waters (Figure 7). Areas of Figure 5 Calculated oxygen saturation for the LTER study Figure 6 Salinity normalized DIC for the LTER 1993 to Figure 7 Surface water fCO2 represented as percent satura-
undersaturation (values below atmospheric equilibrium) occur- area in austral summer 1993 to 1997 field seasons (Jan–Feb). 1997 field seasons. The axes are the same as described in Fig- tion relative to the atmosphere for the LTER 1996 to 1998
red in coastal waters and were associated with increases in chlor- The x and y axes represent longitude and latitude, respectively. ure 5. field seasons. Unlike oxygen and DIC measurements, fCO2
ophyll, implying a biological control. Between 1996 and 1998, The z axis represents year. Each colored circle represents a sta- measurements were made with the automated underway CO2
tion location where an oxygen saturation calculation was made. system resulting in greater spatial resolution. The axes are the
supersaturated surface waters encroached onshelf (Figures 2
same as described in Figure 5.
and 7).
Correlation and Processes
Discussion & Conclusions
Figure 8 (left) Mean and
standard deviation of measured
Processes such as upwelling of CDW onto the shelf, parameters for the Central
ice dynamics and biological production and consump- onshore (red line) and South-
tion of organic matter all contribute to the complex ern offs- ore regions (yellow
h
line) for the 1993 to 1996
spatiotemporal variability observed in O2 and carbon
field sea- ons. (A) Normalized
s
pool dynamics. The relative significance of each pro-- DIC in µmol/kg. (B) Oxygen con-
cess in controlling O2, DIC and fCO2 has yet to be centration in µmol/l. (C) Chloro-
determined. phyll mg/m3 (D) Ice indices rep-
resented as ice coverage within
The increased onshelf intrusion of seawaters that the LTER area (Smith et al.
are supersaturated with respect to CO2 between 1996 1998). The yellow line repre-
and 1998 suggests that upwelling of CDW may con- sents the total ice coverage in
the winter and the red line rep-
trol CO2 concentrations offshore. resents the total ice cover dur-
O2 concentrations correlate strongly with the ice ing the spring.
indices, suggesting that ice dynamics are important in
controlling O2 distributions (Figure 8). Within the
Southern offshore region of the LTER grid, higher
O2 concentrations are present during years of lower
chlorophyll concentrations, and visa versa. This sug- References
Carpenter J.H. 1965. Limnology and Oceanography 10, 135–141.
gests that physical controls such as air-sea gas Dickson A.G. 1991. US JGOFS News 3, 4.
exchange may be important in controlling O2 concen- Johnson K.M., King A.E., Sieburth J.McN. 1985. Marine Chemistry 16, 61-82.
Lewis E.R. and Wallace D.W.R. 1995. Data report BNL-61827 informal Brook- aven National National Labora-
h
trations. tory.
Salinity normalized DIC does not correlate with Roy R.N., Roy L.N., Vogel K.M., Porter-Moore C., Pearson T., Good C.E. 1993. Marine Chemistry 42, 249–267.
Smith R.C., Baker K.S., Stammerjohn S. E. 1998. Bioscience 48, 83–93.
O2 or ice indices. Smith R.C., Baker K.S., Fraser W.R., Hofmann E.E., Karl D.M., Klink J.M., Quetin L.B., Prezelin B.B., Ross R.M.,
Trivelpiece W.Z., Vernet M. 1995. Oceanography 8, 77–86.
Smith R.C., Booth C.R., Star J.L. 1984. Applied Optics 23, 2791–2797.
Weiss R.F. 1970. Marine Chemistry 2, 203–215.](https://image.slidesharecdn.com/carrilloposter-111123163546-phpapp02/85/lter-temporal-and-spatial-variability-1-320.jpg)
