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CRUISE REPORT: A16N_2003a
(Updated MAY 2012)




A.   HIGHLIGHTS

A.1.  CRUISE SUMMARY INFORMATION          

      WOCE section designation  A16N_2003a
        Expedition designation  33RO200306_01 
                   (ExpoCodes)  33RO200306_02
               Chief Scientist  JOHN BULLISTER/PMEL
    Co-Chief Scientist Nicolas  GRUBER/UCLA
                         Dates  2003 JUN 04 - 2003 AUG 11
                          Ship  R/V RONALD H. BROWN
                 Ports of call  Reykjavik, Iceland to Natal, Brazil

                                            63°17.58'N
         Geographic boundaries  29°00.00'W             19°59.99'W
                                             6°0.64'S

                      Stations  150
  Floats and drifters deployed  6 ALACE profiling floats, 
                                6 Surface drifters and 
                                3 Carbon Explorer floats
Moorings deployed or recovered  0


                          CONTRIBUTING AUTHORS

   E. Peltola,  R. Wanninkhof, R. Feely, R. Castle,    D. Greeley,
   J.-Z. Zhang, F. Millero,    N.Gruber, J. Bullister, T. Graham


                CHIEF SCIENTIST CONTACT INFORMATION

                   John L. Bullister (NOAA-PMEL)
         7600 Sand Point Way N.E. • Seattle, WA 98115 • USA
               Tel: 206-526-6741 • Fax: 206-526-6744
                 e-mail: John.L.Bullister@noaa.gov

                       Nicolas Gruber (UCLA)
           Institute of Geophysics & Planetary Physics &
                 Department of Atmospheric Sciences
       5853 Slichter Hall • Los Angeles, CA 90095-1567 • USA
               Tel: 310-825-4772 • Fax: 310-206-3051
                   e-mail: ngruber@igpp.ucla.edu




SUMMARY:

A hydrographic survey consisting of a meridional CTD/rosette 
section in the North Atlantic, nominally along 20°W from 63°N to 
6°S was carried out on NOAA ship Ronald H. Brown (NOAA Cruise RB-
03-04) during July-August 2003  The expedition has been assigned 
the ExpoCode 33RO200306_01.  This 2003 section repeated the A16N 
section occupied during the World Ocean Circulation Experiment 
(WOCE) period, hence this cruise is also designated A16N_2003.  
This was also a repeat of a NOAA cruise in 1993, during which a 
full suite of inorganic carbon, hydrographic and CFC measurements 
were made.

This cruise was the first in a decadal series of repeat 
hydrography sections jointly funded by NOAA's Office of Global 
Programs (OGP) and the US National Science Foundation (NSF) as 
part of the CLIVAR/CO2/hydrography/tracer program.  The program 
focuses on the need to monitor inventories of CO2, tracers, heat 
and freshwater and their transports in the ocean.  Earlier 
programs under the World Ocean Circulation Experiment (WOCE) and 
Joint Global Ocean Flux Study (JGOFS) have provided a baseline 
observational field for these parameters.

A total of 150 full water column CTD/rosette stations were 
occupied. Water samples (up to 34 at each station), LADCP, CTD 
and bio-optical data were collected on most casts to within ~20 m 
of the bottom.  Salinity, dissolved oxygen, and nutrient samples 
were analyzed from every bottle sampled.  Other parameters were 
sampled at a lower density, including  a suite of carbon 
parameters (dissolved inorganic carbon-DIC, total alkalinity- 
Talk, pH and partial pressure of CO2- pCO2), chlorofluorocarbons 
(CFCs), dissolved organic carbon (DOC), 3He-tritium, and carbon 
isotopes.  In addition to the CTD/rosette casts, separate trace 
metal casts were made at stations along the section, nominally at 
60 nautical mile spacing. 

Measurements of near surface seawater properties (temperature, 
salinity, and pCO2), as well as atmospheric measurements (CO2, 
CFCs, aerosols) were made along the cruise track.  Six ALACE-type 
profiling floats were deployed along the section, along with 6 
surface drifters and 3 special 'Carbon Explorer' profiling floats 
designed to measure particulate inorganic carbon (PIC). 

This report describes the participants, scientific programs, and 
sampling details.  Additional information on analytical 
methodologies are included in separate reports appended to this 
file.  Further information and copies of the data from this cruise 
can be found at

              http://sts.ucsd.edu/cruise/a16n/hydro/.



                            ACKNOWLEDGMENTS:

The successful completion of the cruise relied on dedicated 
assistance from many individuals on shore and on the expedition.  
Funded investigators in the project and members of the Repeat 
Hydrography Oversight Committee, with Lynne Talley and Richard 
Feely as co-chairs, were instrumental in planning and executing 
the cruise.  Officers and crew of the Ronald H. Brown exhibited a 
high degree of professionalism and assistance to accomplish the 
mission.   

The U.S. CLIVAR/CO2 Repeat Hydrography Program is jointly 
sponsored by the National Science Foundation's Physical and 
Chemical Oceanography Programs, and NOAA's Office of Climate 
Observation, with contributions from the National Aeronautics and 
Space Administration and the Department of Energy.  In particular, 
we wish to thank program managers Eric Itsweire (NSF/OCE), Don 
Rice (NSF/OCE), Mike Johnson (NOAA/OCO), and Kathy Tedesco 
(NOAA/OGP) for their moral and financial support in the effort.



A.2.  INTRODUCTION:

NOAA ship Ronald H. Brown departed Reykjavik Iceland on 19 June 
2003.  There was a port stop in Funchal Madeira from 10-15 July 
2005.  The cruise ended in Natal, Brazil on 11 Aug 2005.  A sea-
going science team from 14 institutions in the U.S. participated 
on the cruise.  Several other science programs were supported with 
no dedicated cruise participants.



PARTICIPATING INSTITUTIONS:

AOML    NOAA-Atlantic Ocean Marine Laboratory
FSU     Florida State University
Hawaii  University of Hawaii
LDEO    Lamont-Doherty Earth Observatory, Columbia University
LBNL    Lawrence-Berkeley National Laboratory
NOAA    National Oceanic and Atmospheric Agency
RSMAS   Rosenstiel School of Marine and Atmospheric Sciences,  
        University of Miami
PMEL    NOAA-Pacific Marine Environmental Laboratory
SIO     Scripps Institution of Oceanography, University of 
        California, San Diego
TAMU    Texas A&M University
UCLA    University of California, Los Angeles
UW      University of Washington
UCB     University of California, Berkeley
UCI     University of California, Irvine
WHOI    Woods Hole Oceanographic Institution



A.3.  CTD/HYDROGRAPHIC MEASUREMENT PROGRAM:

      Chief Scientists:  John Bullister & Nicolas Gruber
      Survey Department: CST Jonathan Shannahoff
      Final Processing:  Kristy McTaggart
      CTD Personnel:     Regina Cesario, Elena Brambilla, Nicole 
                        Lovenduski, Kristy McTaggart

A total of 150 CTD/rosette casts were made, usually to within 20 m 
of the bottom.  Most of the casts were performed with a package 
consisting of a 36-position, 12-liter rosette frame designed at 
PMEL, a 36-place pylon (SBE32) and 34 12-liter 'Bullister' 
bottles.  Two of the 36 bottle positions (positions 34 and 36) on 
the rosette frame were not available because of interference with 
the LADCP instruments mounted on the rosette frame.  Because of 
inclement weather or winch/wire problems, a smaller 24-place 3-
liter foul weather rosette package also designed at PME was 
deployed at 14 stations (Stations 35-42, 102-103, and 142-143).  
Water samples were collected from every bottle for analysis of 
salinity, dissolved oxygen, and nutrients.  The distribution of 
water sample bottles is illustrated in the following figure.

The basic CTD measurements were of pressure, temperature, 
salinity, and dissolved oxygen.  Additional optical sensors were 
attached to the large rosette frame.  Underwater electronic 
components on the 36 position frame consisted of a Sea-Bird 
Electronics (SBE) 9 plus CTD with dual pumps and the following 
sensors: dual temperature (SBE3plus), dual conductivity (SBE4), 
dissolved oxygen (SBE43), transmissometer (Wetlabs SeaStar), 
turbidity (Seapoint Sensors), and PIC (Wetlabs). The other 
underwater electronic components consisted of RDI LADCPs, a Simrad 
or Benthos altimeter, and a pinger. A detailed description of the 
sensors on the two (large and small)  rosette frames is provided 
in the CTD section below.

The CTD was mounted vertically in an SBE CTD frame attached to the 
bottom center of the rosette frame. All SBE4 conductivity and 
SBE3plus temperature sensors and their respective pumps were 
mounted vertically as recommended by SBE.  The entire cage 
assembly was  mounted on the bottom ring of the rosette frame, 
offset from center to accommodate the pylon, and also secured to 
frame struts at the top.  The altimeter was mounted on the inside 
of a support strut adjacent to the bottom frame ring. The 
transmissometer, turbidity and PIC sensors were mounted 
horizontally along the rosette frame adjacent to the CTD.  The 
LADCPs were vertically mounted inside the bottle rings on the 
opposite side of the frame from the CTD. 

The rosette system was suspended from a UNOLS-standard three-
conductor 0.322" electro-mechanical sea cable.  A load cell was 
installed between he rosette frame hanger and the sea cable to 
monitor the CTD/rosette package weight during casts.  The load 
cell data stream was transmitted via the CTD unit and monitored in 
real time in the CTD lab.  

The R/V Brown's forward CTD winch was used during the cruise.  

The deck watch prepared the rosette within 40 minutes prior to 
each cast.  All valves, vents, and lanyards were checked for 
proper orientation. The bottles were cocked and all hardware and 
connections rechecked.  Once stopped on station, the LADCP was 
turned on and syringes were removed from the CTD sensor intake 
ports.  As directed by the deck watch leader, the CTD was powered-
up and the data acquisition system started.  Two stabilizing 
taglines were threaded through rings on the rosette frame.  The 
deck watch leader directed the winch operator to raise the 
package, the squirt boom and rosette were extended outboard, and 
the package quickly lowered into the water.  The tag lines were 
removed and the package was lowered to 10 m.  The CTD console 
operator waited for the CTD sensor pumps to turn on, waited an 
additional 60 seconds for sensors to stabilize, then directed the 
winch operator to bring the package close to the surface, pause 
for typically 10 seconds, and begin the descent.

Each rosette cast was usually lowered to within 20 m of the 
bottom, using the altimeter and pinger to determine a safe 
distance.

On the up cast, the winch operator was directed to stop at each 
bottle trip depth.  The CTD console operator waited 30 seconds 
before tripping a bottle, then an additional 10 seconds after 
receiving the trip confirmation before directing the winch to 
proceed to the next bottle stop.

Sampling depths and the total number of bottles tripped on each 
cast were adjusted depending the overall water depth.  Typically 
all 34 bottles were closed for casts deeper than ~3000 m.  Sample 
spacing was closer in the upper water column, with typically ~20 
bottles closed in the upper 1000 meters of the water column.  The 
bottle depths were staggered to reduce data contouring artifacts 
(see sample distribution figure). 

Recovering the package at the end of the deployment was 
essentially the reverse of launching, with the additional use of 
poles and snap-hooks to attach tag lines for added safety and 
stability.  The rosette was left outside on deck for sampling.  
The bottles and rosette were examined before samples were taken, 
and anything unusual noted on the sample log.

Each bottle on the rosette had a unique serial number. This bottle 
identification was maintained independently of the bottle position 
on the rosette, which was used for sample identification. 

Routine CTD maintenance included soaking the conductivity and DO 
sensors in fresh water between casts to maintain sensor stability.  
Rosette maintenance was performed on a regular basis.  O-rings 
were changed as necessary and bottle maintenance was performed 
each day to insure proper closure and sealing.  Valves were 
inspected for leaks and repaired or replaced as needed.



A.4.   BOTTLE SAMPLING:

A.4.1.  BOTTLE SAMPLING PROCEDURES

A station log sheet was maintained in the CTD lab for each sample 
team to indicate their sampling plans for the upcoming ~10-20 
stations.  This allowed groups which did not sample every station 
fully to better co-ordinate sampling plans with other groups.  
Planned deployments of floats at upcoming stations were also 
entered in this table.

At each station, a sample log sheet was prepared prior to the 
arrival of the case on deck.  Each sampling group filled out a 
column on this log sheet, indicating which rosette bottles were to 
be sampled, and the ID numbers of their individual sample 
containers.  At the end of each rosette deployment, water samples 
were drawn from the bottles in the order listed below.  This log 
also included any comments or anomalous conditions noted about the 
rosette and bottles.  One member of the sampling team was 
designated the "sample cop," whose responsibility was to maintain 
this log sheet, check the correspondence between individual sample 
containers and the rosette bottle as the samples were drawn, and 
insure that sampling progressed in the proper drawing order.

Normal bottle sampling practice included initially pushing in the 
drain valve petcock prior to opening the air vent screw.  The 
release of any water from the petcock indicated an air leak.  This 
observation, together with other diagnostic comments (e.g., 
"lanyard caught in lid," "valve left open") that might later prove 
useful in determining sample integrity, were routinely noted on 
the sample log and are included below.

Once individual samples had been drawn and properly prepared, they 
were distributed for analysis.


SAMPLING AND ANALYSES OF BOTTLE DATA

The order of drawing samples was: CFCs, helium isotopes (3He), 
oxygen (O2), hydrochlorofluorocarbon (HCFCs), pCO2, DIC, pH, TAlk, 
radiocarbon (DI14C), tritium, DOC, particulate inorganic/organic 
carbon (PIC/POC), salinity, and nutrients.  Sampling of the 34 
bottles on the package took about 1.5 hours.  The samples analyzed 
for gases were sampled first and usually drawn within an hour of 
the rosette reaching the deck.  The deepest bottle was sampled 
first and bottles were sampled sequentially to the surface bottle.  
Care was taken to coordinate the sampling to minimize the time 
between the initial opening of each bottle and the completion of 
sample drawing. In most cases, CFCs, 3He, dissolved oxygen, and 
HCFC samples were collected within several minutes of the initial 
opening of each bottle.

Oxygen, nutrient, and salinity samples were taken from all 
bottles.  For the other parameters, not all stations or all 
bottles were sampled.  Full profiles were typically collected at 
every other station for CFCs, DIC, pH, and TAlk, with partial 
sampling for DOC.  The intermediate stations were typically only 
partially sampled for CFCs, DIC, pH,, TAlk. HCFC, PIC/POC.  
Discrete pCO2 profiles were obtained at every two degrees.  3He, 
DI14C, and tritium were sampled at coarser intervals.  A complete 
listing of the samples collected is available at:

 http://whpo.ucsd.edu/data/CO2clivar/atlantic/a16/a16n_2003a/
                           index.htm

To allow direct comparison, CFCs were usually drawn from the same 
bottles as DIC and Talk. 3He and tritium were typically drawn 
from the same bottles as CFCs.  For casts where many parameters 
were sampled, water levels in some of the 12 liter bottles 
occasionally were very low by the time the salinity and nutrients 
were drawn.  This was particularly true for the deepest two 
bottles and the shallowest  two bottles that were often used for 
duplicate sampling for parameters with large water requirements 
such as DIC and TAlk.  

Because of the small volume (~ 3 liters) of the sample bottles on 
the smaller rosette, not all parameters could be drawn from these 
bottles.  On these casts, water for DIC and Talk was collected in 
the same sample bottle to conserve water and some parameters (e.g. 
helium and tritium) were not sampled from the same bottles as the 
carbon parameters.


A.4.2.  PROBLEMS

There were relatively few bottle misfires or leaking bottles on 
the 36 position rosette frame.  Several of the release pins on the 
24 position small volume rosette did not function reliably and a 
number of bottles did not close on these casts.  Sample bottles 
that did not close or bottles that had obvious leaks while on deck 
were noted on the sample log sheets.  Typically, no water samples 
were not drawn from leaky bottles.  Notes made on the sample log 
sheet s concerning bottle/rosette problems are listed below:


Stn  Cast  Bottles   Problem
---  ----  --------  ---------------------------------------------
  1   1    2, 11     leaky air vent screw
  1   1    11        not enough water for salt sample
  2   1    11        leaky air vent screw
  9   1    1-3       winch problem, had to re-lower package after 
                     1- 3tripped.  Did not sample these
  9   1    16        stopcock pushed in
  9   1    22        leaky air vent 
 13   1              Deck was washed with cleaning agent containing 
                     phosphate possible contamination of surface 
                     nutrient samples
 21   1              light rain during sampling
 23   1    4         bottom endcap did not close
 25   1    6         did not close properly
 26   1              rain during sampling
 29   1    12        lanyard trapped under hose clamp
 32   1    1-17      wire spooling problem, re-lowered after closing,  
                     did not sample these bottles  
 33   1    33        lanyard hang up on hose clamp
 35   2    6         leaker (small rosette)
 35   2    1, 9, 24  did not close
 36   1    1,8,9,15  did not close (small rosette)
 37   2    9,19      did not close (small rosette)
 37   2    20        no water for nutrient sample
 38   1    1,9,19    did not close (small package)
 39   1    1,5,9     did not close (small package)
 40   1    5,9       did not close (small package)
 41   1    1,8,9,15  did not close (small package)
 41   2    9,15      did not close (small package)
 42   1    9,15      did not close (small package)

Stn  Cast  Bottles   Problem
---  ----  --------  ---------------------------------------------
 42   1    23        no water for salt, nutrients
 50   1    25        stopcock pushed in
 56   1    1-9       winch problem, had to re-lower package after 
                     1-9 closed
 58   1    1-9       winch problem, had to re-lower package after 
                     1-5 closed
 61   2    9         closed while package still moving
 65   1    11        closed while package still moving
 74   1    35        only enough water to partially fill salt bottle
 76   1    4         bottom cap lanyard broken, possible early closure
 89   1    21        stopcock pushed in
 90   1    13        air vent open
 93   1    12-36     lost communication with package, cast aborted
 99   1    30        lanyard hang up
101   1              wire problems, replaced sheave after this station
102   2    5         did not close (small rosette)
102   2    6         leak around bottom O-ring
102   2    19        stopcock pushed in
103   1    5,8       did not close (small rosette)
103   1    19        stopcock pushed in
110   2    35        no water for nutrient
114   1    33        no water for nutrient; sampled while raining
122   2    33        no water for nutrient, salt
123   1    1         stopcock pushed in
133   1    35        not closed, lanyard hang-up
140   1    15        did not close- pylon problem
142   1    5,9,16    did not close (small rosette)
143   1    8,9,17    did not close (small rosette)
149   1    1         stopcock pushed in


HYDROWIRE AND WINCH PROBLEMS:

On the RB-03-04 cruise, a new hydrowire was provided on the 
forward CTD hydro winch.  Level-wind problems were encountered on 
this winch early on the cruise.  Because the new hydrowire was 
shipped to the R/V Brown already spooled on a drum, there was 
uncertainty if the deeper layers of wire on the drum had been 
spooled under tension, which is essential for proper performance.  
Some time was lost during the up-casts on Leg 2 due to level-wind 
problems and 'nesting' of the wire as it was wound onto the winch, 
and a small number of water samples were compromised because the 
CTD/rosette package had to be re-lowered at depth to correct 
severe level-wind and nesting problems.  Water samples were not 
drawn from these compromised bottles.  Near the end of Leg 2 and 
during Leg 3, the winch operators became proficient in stopping 
the winch as necessary during upcasts and manually adjusting the 
clutch/level-wind mechanism as each layer of wire was spooled on 
the drum.  This reduced these problems significantly, but was 
labor intensive.  

The General Oceanics sheave for the hydrowire was replaced after 
station 101.  For at least several stations prior to its 
replacement, the hydrowire was observed to be pulling strongly to 
one side and wearing a groove into the side of the sheave.  On the 
casts immediately before 101, the sheave began to vibrate 
excessively.  The sheave was turned 180 degrees before station 
101, and another cast was attempted. On the return to deck after 
cast 101, hockles and birdcages were observed in the upper part of 
the wire.  Some un-twisting of the wire strands may also have 
occurred at a significant distance down the wire.  About 500 
meters of hydrowire were cut from the spool and the wire re-
terminated after this cast,.  Since no equivalent replacement for 
this sheave was available on board, a smaller diameter sheave was 
substituted.  Such smaller sheaves may place significantly greater 
stress on the hydrowire.  

Short circuits or wire breaks occurred in 2 of the 3 conducting 
wires in the hydrowire during Leg 3, leaving only 1 conducting 
wire (and the steel armor of the hydrowire) available for the last 
~40 stations on the second leg.  A failure of the last remaining 
conducting wire would have required an unknown amount of hydrowire 
to be cut off, or resorting to use of the other hydrowinch.  


A.4.3.  BOTTLE DATA PROCESSING:

Water samples collected and properties analyzed shipboard were 
managed centrally in a relational database run on a Linux 
workstation. 

The sample log (and any diagnostic comments) was entered into the 
database once sampling was completed.  WOCE/CLIVAR quality flags 
associated with sampled properties were set to indicate that the 
property had been sampled, and sample container identifications 
were noted where appropriate (e.g., oxygen flask number).

Most samples were analyzed on board with the exception of 3He, 
DI14C, tritium, DOC, CDOM, and PIC/POC that were sampled and 
preserved for shore-based analysis.  Descriptions of sampling and 
analysis procedures, as well as the relevant statistics on data 
quantity and quality are included in individual sections below.

The results of individual shipboard analyses were then uploaded 
through the website as results became available.  These results 
included a quality code associated with each measured value and 
followed the coding scheme developed for the World Ocean 
Circulation Experiment (WOCE) Hydrographic Programme (WHP) (Joyce, 
1994).

Various consistency checks and detailed examination of the data 
continued throughout the cruise.  Post cruise data processing and 
quality checking is discussed in the individual sections below.


TRACE METAL CASTS:

In addition to the 150 CTD/rosette casts, separate trace metal 
casts were made at along the section, nominally at 60 mile 
spacing.

Trace metal casts were made at stations:

  4,5,9,10,13,17,19,23,26,28,31,33,35,42,44,46,48,50,53,55,57,5
  9,61,63,65,67,69,70,72,74,76,78,80,82,84,86,88,90,92,94,96,98,
  100,102,104,106,108,110,112,114,116,118,120,122,124,126,129,
  132,135,138,141,142,144,146,148

Because of possible contamination problems in sampling for iron 
and aluminum, these samples were collected using a special trace 
metal clean CTD/rosette, bottles, wire and winch system.  In 
addition to trace metal samples, samples were collected from each 
bottle for the analysis of salinity and nutrients.  The 
CTD/rosette package was deployed off the stern A-Frame using a 
custom built winch with ~1500 m of  Kevlar coated cable provided 
by the trace metal investigators.  Bottles were closed during the 
up-cast without stopping the winch, to minimize possible 
contamination of the samples from the rosette frame and 
instruments.

There were a number of problems with the trace metal winch, 
particularly with its ability to lift the package out of the water 
when the bottles were full.  On a number of casts, member of the 
scientific party and crew manually assisted in pulling on the wire 
to help lift the trace metal rosette package out of the water and 
onto the deck.


A.4.4.  UNDERWAY MEASUREMENTS:

Near surface seawater measurements of temperature, salinity, pCO2 
and ADCP measurements were made continuously along the cruise 
track.  Copies of these data are available in digital format from 
the CCHDO and from the Chief Scientist.  

Weather observations (ship position, cloud cover and type, 
visibility, wind speed and direction, sea state, wave height and 
direction, surface water temperature, atmospheric pressure, and 
wet and dry bulb air temperature) were recorded manually at hourly 
intervals by the bridge and during each hydrocast.  Copies of 
these data log sheets are available from the Chief Scientist.


FLOAT DEPLOYMENT:

     Float Type       Serial# Time   Date (GMT)      Lat     Lon
     ---------------  ------- ----  ------------  -------  -------
     Carbon Explorer   2122   0042  22 June 2005  60°00'N  20°00'W
     Carbon Explorer      1   1822  28 June 2005  47°00'N  20°00'W
     Carbon Explorer      2   1829  28 June 2005  47°00'N  20°00'W
     Drift Buoy       39149   0027  24 July 2005  19°00'N  29°00'W
     Drift Buoy       39148   1409  24 July 2005  18°00'N  29°00'W
     Profiling Float    205   1143  26 July 2005  15°00'N  29°00'W
     Drift Buoy       39152   0300  27 July 2005  14°00'N  29°00'W
     Drift buoy       39150   1752  27 July 2005  13°00'N  29°00'W
     Profiling Float    202   0052  28 July 2005  12°30'N  29°00'W
     Drift buoy       39151   0902  28 July 2005  12°00'N  29°00'W
     Drift buoy       35691   0050  20 July 2005  11°00'N  29°00'W
     Profiling Float    188   1549  29 July 2005  10°00'N  29°00'W
     Profiling Float    189   0957  31 July 2005   7°30'N  27°15'W
     Profiling Float    175   2310   1 Aug  2005   5°00'N  26°00'W
     Profiling Float    209   0901   3 Aug  2005   2°40'N  25°00'W


A.4.5.  SAMPLES PRESERVED FOR SHORE-SIDE ANALYSIS

DOC SAMPLING

Principal Investigator: Dennis Hansell             U. Miami, RSMAS
                        4600 Rickenbacker Causeway
                        Miami, FL 33149
                        dhansell@rsmas.miami.edu
Sampler:                Stacy Brown                U. Miami

Seawater samples were taken directly from the Niskin Bottles into the 60 
ml pre-cleaned bottles for deeper than 200 m. Samples from the up 200 m 
were collected by in-line filtration through a/F filter. All samples 
were kept in frozen before analysis.


14C SAMPLING

Principal Investigator: Ann McNichol               WHOI
Samplers:               John Bullister             NOAA-PMEL
                        Nicolas Gruber             UCLA

Seawater was drawn directly from the Niskin bottles into 500-ml glass 
bottles after about 250 ml overflow of the water. Samples were then 
poisoned with 100 µl saturated HgCl2 solution and sealed by greased 
stoppers. Bottles with samples are kept in cases for shipping back to 
WHOI.



REFERENCE: 

Measuring 14C in Seawater TCO2 by Accelerator Mass Spectrometry, WHOI in 
    WHP Operation and Methods-July, 2003.


HELIUM AND TRITIUM SAMPLING

Principal Investigator: Peter Schlosser
                        Lamont-Doherty Earth Observatory
                        Palisades NY 10964
                        schlosser@ldeo.columbia.edu
Samplers:               Brent Turrin               LDEO (Leg 2)
                        Anthony Dachille           LDEO (Leg 3)

Sampling of helium isotope (3He) and tritium involved separate 
containers for 3He and tritium.  Seawater for 3He analysis was sampled 
into re-useable stainless steel tubes of 90-ml in volume.  Tritium was 
sampled into 1 liter brown glass bottles.  The 3He samples were taken 
first and care was made to rid the vessel of air bubbles by hitting them 
with a stick and opening and closing the two valves at each end of the 
tube.  Tritium was sampled by rinsing the bottles twice and filling with 
water up to the curve at the top of the bottle to allow room to allow 
for thermal expansion.

The He extraction was done on ship on a vacuum extraction system 
supplied by WHOI (W. Jenkins and D. Lott).  



B.   CTD DATA

Chief Scientists:  John Bullister & Nicolas Gruber
Survey Department: CST Jonathan Shannahoff
Final Processing:  Kristy McTaggart
CTD Personnel:     Regina Cesario, Elena Brambilla, Nicole Lovenduski, 
                   Kristy McTaggart

B.1.  ACQUISITION

During this cruise, 150 stations were occupied in the North 
Atlantic from 63N to 5S primary along 20W at 30nm spacing, and 152 
CTDOXY profiles were collected.  All profiles were to within 10m of 
the bottom, ranging from about 200m to nearly 6000m.  

Three underwater package configurations were used during this 
cruise.  The primary package was a new 36-position stainless steel 
frame mounted with 34 12-liter Niskin bottles, Sea-Bird carousel, 
load cell, altimeter, pinger, LADCP, and optical sensors.  The 
Sea-Bird CTD sensors were a 9plus CTD s/n 315; primary TC sensors 
s/n 4193, 1180; secondary TC sensors s/n 1455, 354; and SBE 43 
oxygen sensors s/n 315, 313, or 312.

During bad weather or while testing a deteriorating winch cable, a 
small 24-position stainless steel frame was employed.  This bad 
weather frame was mounted with 24 4-liter Niskin bottles, AOML-
owned Sea-Bird carousel, load cell, altimeter, and pinger.  The 
Sea-Bird CTD sensors were a 9plus CTD s/n 209; primary TC sensors 
s/n 1370, 1434; secondary TC sensors s/n 1460, 1177; and SBE 43 
oxygen sensors s/n 313 or 312.

The third configuration was comprised of the primary package with 
the bad weather CTD and sensors, and used after the primary CTD 
s/n 315 blew the power supply at station 142.  Sea-Bird 
configuration files were named a16n_1.con, a16n_2.con, and 
a16n_3.con, respectively.  N.B., The pre-cruise pressure 
calibration offset for CTD s/n 315 was amended by +1 dbar in 
a16n_1.con.  

Data were acquired at full 24 Hz resolution through a Sea-Bird 
11plus deck unit and the ship's dedicated PC using Seasave 
software version 5.28c.  Analog data were archived onto VCR tapes, 
although likely unrecoverable.  Fortunately, no real-time data 
were lost.  Digital backups were made to Zip disks and CDs.

The discrete sample database, maintained by Frank Delahoyde at 
sea, totals 4824 records.  The only instance of rosette misfire 
identified was during station 119, where two bottles closed at 
1400 dbar; the following 6 bottle closures were offset by one; and 
no sample was collected at 600 dbar.  



B.2.  PROCESSING

The reduction of profile data began with a standard suite of processing 
modules using Sea-Bird Seasoft software DOS version 4.249 in the following 
order:


DATCNV   converts raw data into engineering units and creates a 
         bottle range file. Both down and up casts were processed 
         for scan, elapsed time(s), pressure, t0, t1, c0, c1, and 
         oxygen voltage. Optical sensor data were carried through 
         for casts using the primary package. MARKSCAN was used to 
         skip over scans acquired on deck and while priming the 
         system. 
ALIGNCTD aligns temperature, conductivity, and oxygen measurements 
         in time relative to pressure to ensure that derived 
         parameters are made using measurements from the same 
         parcel of water. Primary conductivity is automatically 
         advanced in the deck unit by 0.073 seconds. On the 
         primary package, the additional alignment of primary 
         sensor s/n 1180 was -0.040 seconds (net alignment 0.033 
         seconds), and the total alignment for secondary sensor 
         s/n 354 was 0.089 seconds. On the bad weather package, 
         the additional alignment of primary sensor s/n 1434 was - 
         0.010 seconds (net alignment 0.063 seconds), and the 
         total alignment for secondary sensor s/n 1177 was 0.057 
         seconds. For the ending package configuration, the 
         additional alignment of primary sensor s/n 1434 was - 
         0.010 seconds (net alignment 0.063 seconds), and the 
         total alignment for secondary sensor s/n 1177 was 0.089 
         seconds as it was then being plumbed with the optical 
         sensors in the primary frame. It was not necessary to 
         align temperature or oxygen.
ROSSUM   averages bottle data over an 8-second interval as 
         specified in the range file, and derives salinity, theta, 
         sigma-theta, and oxygen (µmol/kg). 
WILDEDIT makes two passes through the data in 100 scan bins. The 
         first pass flags points greater than 2 standard 
         deviations; the second pass removes points greater than 
         20 standard deviations from the mean with the flagged 
         points excluded. Data were kept within 100 of the mean 
         (i.e. all data).
FILTER   applies a low pass filter to pressure with a time 
         constant shift) the filter is first run forward through 
         the file and then run backwards through the file. 
         Mistakenly, a time constant of only 0.03 seconds was used 
         for this cruise, of small consequence.
CELLTM   uses a recursive filter to remove conductivity cell 
         thermal mass effects from measured conductivity. In areas 
         with steep temperature gradients the thermal mass 
         correction is on the order of 0.005 PSU. In other areas 
         the correction is negligible. The value used for the 
         thermal anomaly amplitude (alpha) was 0.03. The value 
         used for the thermal anomaly time constant (1/beta) was 
         7.0. Mistakenly, the secondary sensors of either CTD were 
         not corrected for this effect.
LOOPEDIT removes scans associated with pressure slowdowns and 
         reversals. If the CTD velocity is less than 0.25 m/s or 
         the pressure is not greater than the previous maximum 
         scan, the scan is omitted.
BINAVG   averages the data into 1 db bins. Each bin is centered on 
         an integer pressure value, e.g. the 1 db bin averages 
         scans where pressure is between 0.5 db and 1.5 db. There 
         is no surface bin.
DERIVE   uses 1 db averaged pressure, temperature, and conductiv-
         ity to compute salinity, theta, sigma-theta, and dynamic 
         height.
TRANS    converts the data file from binary to ASCII format. 


Package slowdowns and reversals owing to ship roll can move mixed 
water in tow to in front of the CTD sensors and create artificial 
density inversions and other artifacts.  In addition to Seasoft 
module LOOPEDIT, MATLAB program deloop.m computes values of 
density locally referenced between every 1 dbar of pressure to 
compute N^2 and linearly interpolates temperature, conductivity, 
and oxygen voltage over those records where N^2 is less than or 
equal to -1e-5 per s^2.  MATLAB program calctd_1k.m or calctd_2k.m 
or calctd_3k.m applies final calibrations to temperature and 
conductivity, and computes salinity and calibrated oxygen.  
Program cnv_eps1.f  and cnv_eps2.f computes ITS-90 temperature, 
theta, sigma-t, sigma-theta, and dynamic height; creates WOCE 
quality flags, and converts the ASCII data files into NetCDF 
format for PMEL's database.  Program wocelst_ox.F converts the 
NetCDF files into WOCE format for submission to the WHPO, and 
creates WOCE .SUM files, one for each leg of the cruise.



B.3.  SALINITIES

Primary TC data were selected from the primary package.  These 
data were used to calibrate stations 1-34, 43-101, and 104-141.  
Secondary TC data were selected from the bad weather package.  
These data were used to calibrate stations 35-42, 102-103, and 
142-150.  Note that stations 144-150 used bad weather CTD s/n 209 
in the primary package.

Samples were collected by the CTD watchstander.  A duplicate 
sample was collected from the deepest bottle.  Salinity analysis 
was performed by Greg Johnson on leg 1, and Dave Wisegarver on leg 
2.  Analysis was done on the ship's autosalinometer using Ocean 
Scientific ACI2000 interface and IAPSO standard seawater batch 
P143 dated February 2003.  The bath temperature was set to 24C.  
The ambient room temperature should be within 1 degree of the bath 
temperature, preferably cooler.  Samples were left to equilibrate 
in the Autosal lab space for a minimum of 8 hours before analysis.  
The Autosal was standardized once a day.

Sample salinities used to calibrate CTD conductivity sensors were 
obtained from the Data Manager at sea.  However, salinity data 
were re-evaluated post-cruise and a linear drift correction 
between standardizations was applied.  The final data set was 
produced at PMEL in December 2003.  



B.4.  OXYGENS

SBE 43 oxygen sensor s/n 315 
  was used on the primary package for stations 1-60.  It had a 
  noticeable trend from the onset but it wasn't confirmed until 
  sample oxygens were reviewed.  Sensor s/n 315 was swapped out for 
  sensor s/n 313 prior to station 61.  Sea-Bird has suggested that 
  this membrane could've been frozen or torn before the cruise.  
SBE 43 oxygen sensor s/n 313 
  was used first on the bad weather package for stations 35-42 
  before going on the primary package prior to station 61.  Starting 
  at station 94, s/n 313 was not responding well to the new oxygen 
  minimum below the thermocline.  It was swapped out for sensor s/n 
  312 prior to station 122.
SBE 43 oxygen sensor s/n 312 
  was used first on the bad weather package for stations 102-103.  
  It was moved to the primary package prior to station 122 and used 
  for the remainder of the cruise.
  Sample oxygens used to calibrate these sensors were obtained from 
  the Data Manager at sea.  However, oxygen data were re-evaluated 
  post-cruise and the final data set was produced at AOML in 
  September 2004. 



B.5.  BOTTLE DATA

Seasoft module ROSSUM created a bottle data file for each cast.  
These files were appended using program sbecal1k.f for primary 
sensor data or sbecal2k.f for secondary sensor data.  Program 
addsalk3.f matched sample salinities to CTD salinities by 
station/sample number.  MATLAB calibration programs were used to 
determine best fit groupings.  The final results were a second 
order polynomial fit for stations 1-100 using the primary sensor 
pair; a third order polynomial fit for stations 101-141 using the 
primary sensor pair; a linear fit for stations 35-42 and stations 
102-103 using the secondary sensor pair; and a linear fit with a 
station dependent slope for stations 142-150 using the secondary 
sensor pair.


[sta,slope,bias,newbotco,newctdco]=calcos2(stat,cond,pres,botc,2.8,1,100);
                number of points used  2427
               total number of points  2815
              % of points used in fit    86.22
               fit standard deviation     0.001952
                             fit bias     0.0015337094
                        min fit slope     0.99993324
                        max fit slope     0.99997466
[sta,slope,bias,newbotco,newctdco]=calcos3(stat,cond,pres,botc,2.8,101,141);
                number of points used  1039
               total number of points  1312
              % of points used in fit    79.19
               fit standard deviation     0.0018
                             fit bias    -0.004654759
                        min fit slope     1.000081
                        max fit slope     1.0001403
[sta,slope,bias,newbotco,newctdco]=calcos0(stat,cond,pres,botc,2.8,35,42);
                number of points used   184
               total number of points   202
              % of points used in fit    91.09
               fit standard deviation     0.001569
                             fit bias     0.00067359131
                        min fit slope     1.0000342
                        max fit slope     1.0000342
[sta,slope,bias,newbotco,newctdco]=calcos0(stat,cond,pres,botc,2.8,102,103);
                number of points used    42
               total number of points    44
              % of points used in fit    95.45
               fit standard deviation     0.00243
                             fit bias    -0.0086599793
                        min fit slope     1.0003549
                        max fit slope     1.0003549
[sta,slope,bias,newbotco,newctdco]=calcos1(stat,cond,pres,botc,2.8,142,150);
                number of points used   232
               total number of points   279
              % of points used in fit    83.15
               fit standard deviation     0.001669
                             fit bias    -0.0027190403
                        min fit slope     1.0000403
                        max fit slope     1.0000991

Program addoxyk3.f matched sample oxygens to CTD oxygens by 
station/sample number.  Because of sensor hysteresis, MATLAB 
programs matched upcast oxygens to downcast oxygens by sigma-2.  
Coefficients were determined using run_oxygen_cal_1.m and saved in 
final.mat.

Temperature viscous and drift corrections, conductivity 
coefficients, and oxygen coefficients were applied to the bottle 
data file using calclo_k.m.  Quality flags for sample salinities 
were determined using MATLAB program sflag.m. Of the 4676 sample 
salinities, 0.6% were flagged as bad and 1% were flagged as 
questionable.  Final CTD bottle data, a16n_allo.flg, were given 
to John Bullister to incorporate into the master data file.  For 
PMEL's database, individual bottle files for each cast were 
created in NetCDF format using clb_epso.f. 



C.   BOTTLE SAMPLING:

C.1.  Inorganic Nutrients (Phosphate, Nitrate, Nitrite and Silicate)

     Samplers and Analysts: Leg 1  Calvin Mordy
                                   David Wisegarver
                            Leg 2  Charlie Fischer
                                   Jia-Zhong Zhang
     Data Reduction:               Calvin Mordy 

EQUIPMENT AND TECHNIQUES

Concentrations of dissolved nitrite (NO2-), nitrate (NO3-), phosphate 
(PO43-) and silicic acid (H4SiO4) were measured using an automated 
continuous flow analyzer with a segmented flow and colorimetric 
detection.  The four-channel autoanalyzer was customized using 
components from various systems.  The major components were an Alpkem 
301 sampler, one 24 channel Ismatek peristaltic pump and three 
ThermoSeparation monochrometers (for silicic acid, nitrate, and 
nitrite), one Technicon AAII pump and detector (for phosphate), and 
custom software for digitally logging and processing the chromatographs.  
Glass coils and tubing from the Technicon Autoanalyzer II were used for 
analysis of phosphate, and micro-coils from Alpkem were used for the 
other three analyses.  Pump tubes were changed 4 times during the 
expedition, although some of the tubes were changed more frequently as 
part of troubleshooting.


CHEMISTRY

NITRITE 
Nitrite was determined by diazotizing with sulfanilamide and coupling 
with N-1 naphthyl ethylenediamine dihydrochloride to form an azo dye. 
The color produced is measured at 540 nm (Zhang et al., 1997a).  
Samples for nitrate analysis were passed through a cadmium column, which 
reduced nitrate to nitrite. Total nitrite, mostly from reduction of 
nitrate with a small amount of nitrite present in the original samples, 
was then determined as described above.  Nitrate concentrations in 
seawater samples were calculated by difference.

PHOSPHATE 
Phosphate in the samples was determined by reacting with molybdenum (VI) 
in an acidic medium to form a phosphomolybdate complex. This complex was 
subsequently reduced with hydrazine at a temperature of 55°C to form 
phosphomolybdenum blue (Zhang et al., 2001). An AAII detector with an 
880 nm filter was used to measure the absorbance during the cruise.

SILICIC ACID 
Silicic acid was analyzed by reacting with molybdate in acidic solution 
to form ß-molybdosilicic acid. The ß-molybdosilicic acid was then 
reduced by ascorbic acid to form molybdenum blue (Zhang et al., 1997b).  
The absorbance of the molybdenum blue was measured at 660 nm.  


SAMPLING AND STANDARDS

Nutrient protocols closely followed the methods of Gordon et al. (1993).  
Samples were drawn in 40 ml HDPE Boston Round sample bottles that had 
been stored in 10% HCl and rinsed 4-5 times with sample before filling.  
Samples were usually analyzed 2-3 hours after sampling.  A replicate was 
always drawn from the deep bottle for analysis with samples from the 
subsequent station for comparison.  All samples were brought to room 
temperature prior to analysis.  A separate analytical run was conducted 
at each station (except for the most shallow stations). The sequence of 
a typical analytical run for a station was 1) blanks, 2) working 
standards, 3) the working standard from the previous station, 4) deep 
water from the previous station, 5) samples analyzed from deep to 
surface, 6) replicate analysis of the four deepest samples and problem 
samples (if any), 7) working standards, and 8) blanks.  The blanks were 
deionized water, and the standards were simply a "zero" standard of Low 
Nutrient Seawater (LNSW), and a high standard of spiked LNSW.  Linearity 
of the autoanalyzer was checked every ten days, and corrections for non-
linearity were applied to the phosphate data.

The high standard was made from the addition of 1 ml of primary nitrite 
standard and 20 ml of a secondary mixed standard (containing silicic 
acid, nitrate, and phosphate) in 500 ml of Low Nutrient Sea Water using 
pre-calibrated Eppendorf pipettes and volumetric flasks. 

Dry standards were pre-weighed at PMEL, and dissolved to prepare primary 
standards at sea.  Silicic acid (Na2SiF6, >98%) and nitrate (KNO3, 
99.99%) were from Aldrich, phosphate (KH2PO4, 99.99%) and nitrite (NaNO2, 
98.2%) were from Baker.  The secondary mixed standard was prepared by 
additions of the nitrate and phosphate primary standards to the silicic 
acid primary standard in deionized water.

After each run, the electronic chromatograph was scrutinized to ensure 
proper selection of individual peak heights.  The peak height data was 
inserted into Microsoft Excel worksheets and the concentrations were 
calculated after factoring the baseline drift, carryover corrections, 
refractive index, and standard drift.  Quality control plots were 
maintained of the baseline, matrix, carryover, standard factor, old 
standard, and station-to-station variability of the deep water 
replicate.

Nutrient concentrations were reported to the shipboard data manager in 
micromole per liter.  Measurements were made in a temperature-controlled 
bioanalytical laboratory (20 ± 2°C), and the laboratory temperature 
during analysis was reported to facilitate unit conversion to a 
micromole per kg basis.

PROBLEMS

During the cruise, several detectors had to be replaced.  During the 
first 25 stations, the data acquisition system was not working, and the 
peaks were read from chart recorders.   

After installation of Lachat Cd Column at Station 84, the NO3 carryover 
correction immediately increased from about 1% to 3%, followed by a 
steady increase to about 6% at Station 135, and then an exponential 
increase to about 14% at Station 150.  Carryover corrections were 
substantial for samples collected in the nutricline, and corrections for 
stations 149 and 150 were closely examined.  The first of the deep water 
replicates analyzed at the end of the run always had the largest 
carryover correction.  This "dummy" deep sample (bottle 1) was used to 
wash out the previous low nutrient surface sample before analysis of 
bottles 2, 3 and 4.  The carryover correction for the dummies from 
Stations 149 and 150 were ~4 µM, and this brought the concentrations to 
within 0.2 µM of the initial bottle 1 measurement.  Although 
substantial, this suggests that the correction was appropriate and the 
error in the correction was minimal.  Samples of greatest concern were 
at the base of the mixed layer (i.e. Sta. 149, bottle 31) where 
carryover corrections of 1.0 and 0.8 (stations 149 and 150 respectively) 
were applied to give concentrations of 0.0 and 0.1 µM - the same as 
observed for the upper 3 bottles.  (Stations were measured deep to 
shallow; therefore, samples at the top of the nutricline have the 
largest relative carryover correction.)  A check of the bottle 
temperature and salinity data suggests that these samples were indeed 
from the upper mixed layer. 

Another problem was a dramatic (~30%) drop in the nitrite standard 
factor from Station 84 to Station 111.  The standard factor immediately 
recovered after making a new nitrite primary standard.  The nitrite 
standard has been known to decay with time, especially if not stored in 
the refrigerator.  The standard concentration of nitrite was 
recalculated for these stations based on comparisons of the decaying 
standard factors with standard factors from Stations 25-83 and 112-150.

NUMBER OF SAMPLES, REPLICATES AND PRECISION

A replicate sample was almost always drawn from the deepest bottle, and 
most replicate analyses were conducted on the four deepest bottles.  A 
few replicate analyses were conducted for samples in the upper water.  
The precision of phosphate, silicic acid and nitrate was within 1% of 
full scale.

                  |           | Silicic  |          |
                  | Phosphate | Acid     | Nitrate  | Nitrite
                  |-----------|----------|----------|-------
# of Samples      | 5368      | 5369     | 5369     | 5369
# of Replicates   |  499      |  500     |  490     |  n/a
AVG Standard      |    0.006  |    0.064 |    0.062 |  n/a
    Deviation (µM)|           |          |          |
% Deviation       |    0.5%   |    0.5%  |    0.3%  |  n/a



REFERENCES 

Gordon, L. I., Jennings Jr., J.C., Ross, A.A. and Krest, J.M. (1993) A 
    suggested protocol for continuous automated analysis of seawater 
    nutrients (phosphate, nitrate, nitrite and silicic acid) in the 
    WOCE Hydrographic program and the Joint Global Ocean Fluxes Study, 

WOCE Operations Manual, vol. 3: The Observational Programme, 
    Section 3.2: WOCE Hydrographic Programme, Part 3.1.3: WHP 
    Operations and Methods. WHP Office Report WHPO 91-1; WOCE Report 
    No. 68/91. November, 1994, Revision 1, Woods Hole, Mass., USA, 52 
    loose-leaf pages. 

Zhang, J-Z., P. B. Ortner and C. Fischer, (1997a) Determination of 
    nitrite and nitrate in estuarine and coastal waters by gas 
    segmented continuous flow colorimetric analysis. EPA's manual " 
    Methods for the determination of Chemical Substances in Marine and 
    Estuarine Environmental Matrices - 2nd Edition". EPA/600/R-97/072, 
    September 1997. 

Zhang, J-Z., and G. A. Berberian, (1997b) Determination of dissolved 
    silicate in estuarine and coastal waters by gas segmented 
    continuous flow colorimetric analysis. EPA's manual " Methods for 
    the determination of Chemical Substances in Marine and Estuarine 
    Environmental Matrices - 2nd Edition". EPA/600/R-97/072, September 
    1997.

Zhang, J-Z., C. Fischer and P. B. Ortner, (2001) Continuous flow 
    analysis of phosphate in natural waters using hydrazine as a 
    reductant, International Journal of Environmental Analytical 
    Chemistry, 80(1): 61-73.



C.2.  CHLOROFLUOROCARBON (CFC) MEASUREMENTS

     Principal Investigators: John L. Bullister, NOAA-PMEL
                              John.L.Bullister@noaa.gov
                              Mark J. Warner, University of Washington
                              mwarner@ocean.washington.edu

     Samplers and Analysts:   Mark J. Warner, University of Washington
                              Eric Wisegarver, University of Washington
                              esw@u.washington.edu

Samples for the analysis of dissolved CFC-11, CFC-12 and CFC-113 were 
drawn from ~2,421 of the ~4,923 water samples collected during the 
expedition. Specially-designed 12-liter 'Bullister' sample bottles were 
used on the cruise to reduce CFC contamination.  These bottles have the 
same outer diameter as standard 10 liter Niskin bottles, but use a 
modified end-cap design to minimize the contact of the water sample with 
the end-cap O-rings after closing.  The O-rings used in these water 
sample bottles were vacuum-baked prior to the first station.  Stainless 
steel springs covered with a nylon powder coat were substituted for the 
internal elastic tubing provided with standard Niskin bottles.  When 
taken, water samples for CFC analysis were the first samples drawn from 
the 12-liter bottles.  Care was taken to coordinate the sampling of CFCs 
with other samples to minimize the time between the initial opening of 
each bottle and the completion of sample drawing. In most cases, 
dissolved oxygen, 3He, and HCFC samples were collected within several 
minutes of the initial opening of each bottle.  To minimize contact with 
air, the CFC samples were drawn directly through the stopcocks of the 
12-liter bottles into 100 ml precision glass syringes equipped with two-
way metal stopcocks.  The syringes were immersed in a holding tank of 
clean surface seawater until analyzed.

For air sampling, a ~100 m length of 3/8" OD Dekaron tubing was run from 
the main laboratory to the bow of the ship.  A flow of air was drawn 
through this line into the main laboratory using an Air Cadet pump.  The 
air was compressed in the pump, with the downstream pressure held at 
~1.5 atm. Using a backpressure regulator.  A tee allowed a flow (100 cc 
min-1) of the compressed air to be directed to the gas sample valves of 
the CFC analytical system, while the bulk flow of the air (>7000 cc min-
1) was vented through the backpressure regulator.  Air samples were only 
analyzed when the relative wind direction was within 60° of the bow of 
the ship to reduce the possibility of shipboard contamination.  The pump 
was run continuously to insure that the air inlet lines and pump were 
thoroughly flushed. Analysis of ~ 190 bow air samples was performed 
along the cruise track. At each location, replicate measurements were 
made to increase the precision.

Concentrations of CFC-11 and CFC-12 in air samples, seawater, and gas 
standards were measured by shipboard electron capture gas chromatography 
(EC-GC) using techniques modified from those described by Bullister and 
Weiss (1988). For seawater analyses, water was transferred from a glass 
syringe to a fixed volume chamber (~30 ml).  The contents of the chamber 
were then injected into a glass-sparging chamber.  The dissolved gases 
in the seawater sample were extracted by passing a supply of CFC-free 
purge gas through the sparging chamber for a period of 4 minutes at ~70 
ml min-1. Water vapor was removed from the purge gas during passage 
through an 18 cm long, 3/8" diameter glass tube packed with the 
desiccant magnesium perchlorate.  The sample gases were concentrated on 
a cold-trap consisting of a 1/8" OD stainless steel tube with a ~10 cm 
section packed tightly with Porapak N (60-80 mesh), held at ~ -20°C in a 
cryogenic bath.  After 4 minutes of purging, the trap was isolated, and 
the trap was heated electrically to ~100°C.  The sample gases held in 
the trap were then injected onto a precolumn (~25 cm of 1/8" O.D. 
stainless steel tubing packed with 80-100 mesh Porasil C, held at 70°C) 
for the initial separation of CFC-12, CFC-11, and CFC-113 from later 
eluting compounds. After these CFCs had passed from the pre-column into 
the main analytical column (~183 cm of 1/8" OD stainless steel tubing 
packed with Carbograph 1AC, 80-100 mesh, held at 70°C) of the GC (a 
Shimadzu Mini-2 gas chromatograph with ECD)

The analytical system was calibrated frequently, using a standard gas of 
known CFC composition.  Gas sample loops of known volume were thoroughly 
flushed with standard gas and injected into the system. The temperature 
and pressure was recorded so that the amount of gas injected could be 
calculated. The procedures used to transfer the standard gas to the 
trap, precolumn, main chromatographic column, and EC detector were 
similar to those used for analyzing water samples.  Two sizes of gas 
sample loops were used.  Multiple injections of these loop volumes could 
be made to allow the system to be calibrated over a relatively wide 
range of concentrations. Air samples and system blanks (injections of 
loops of CFC-free gas) were injected and analyzed in a similar manner.  
The typical analysis time for seawater, air, standard or blank samples 
was ~11 minutes.

Concentrations of the CFCs in air, seawater samples, and gas standards 
are reported relative to the SIO98 calibration scale (Cunnold et. Al., 
2000).  Concentrations in air and standard gas are reported in units of 
mole fraction CFC in dry gas, and are typically in the parts per 
trillion (ppt) range.  Dissolved CFC concentrations are given in units 
of picomoles per kilogram seawater (pmol kg-1).  CFC concentrations in 
air and seawater samples were determined by fitting their 
chromatographic peak areas to multi-point calibration curves, generated 
by injecting multiple sample loops of gas from a working standard (PMEL 
cylinder 34603) into the analytical instrument.  The response of the 
detector to the range of moles of CFC passing through the detector 
remained relatively constant during the cruise. Full-range calibration 
curves were run at intervals of 14 days during the cruise.  These were 
supplemented with occasional injections of multiple aliquots of the 
standard gas at more frequent time intervals.  Single injections of a 
fixed volume of standard gas at one atmosphere were run much more 
frequently (at intervals of ~90 minutes) to monitor short-term changes 
in detector sensitivity. 

The efficiency of the purging process was evaluated periodically by re-
stripping high concentration surface water samples and comparing the 
residual concentrations to initial values. These re-strip values were 
approximately 0.8% for CFC-11, 0.2% for CFC-12 and 0.0% for CFC-113.  
Corrections for the efficiency were  applied to the final data set.

On this expedition, based on the analysis of ~100 duplicate samples, we 
estimate precisions (1 standard deviation) of 1% or 0.004 pmol kg-1 
(whichever is greater) for dissolved CFC-11, 1% or 0.004 pmol kg-1 for 
CFC-12 measurements and 2% or 0.009 pmol kg-1 for CFC-113

A small number of water samples had anomalously high CFC concentrations 
relative to adjacent samples.  These samples occurred sporadically 
during the cruise and were not clearly associated with other features in 
the water column (e.g., anomalous dissolved oxygen, salinity, or 
temperature features).  This suggests that these samples were probably 
contaminated with CFCs during the sampling or analysis processes.  
Measured concentrations for these anomalous samples are included in the 
preliminary data, but are given a quality flag value of either 3 
(questionable measurement) or 4 (bad measurement). A quality flag of 5 
was assigned to samples which were drawn from the rosette but never 
analyzed due to a variety of reasons (e.g., leaking stopcock, plunger 
jammed in syringe barrel). A total of  35 analyses of CFC-11, 24 
analyses of CFC-12 and 5 analyses of CFC-113 were assigned a quality 
flag of 3.  A total of 16 analyses of CFC-11, 13 analyses of CFC-12 and 
17 analysis of CFC-113 , were assigned a quality flag of 4.



REFERENCES

Bullister, J.L., and R.F. Weiss, 1988:  Determination of CC13F and CC12F2 
    seawater and air.  Deep-Sea Res., v. 25, pp. 839-853.

Prinn, R.G., R.F. Weiss, P.J. Fraser, P.G. Simmonds, D.M. Cunnold, F.N. 
    Alyea, S. O'Doherty, P. Salameh, B.R. Miller, J. Huang, R.H.J. 
    Wang, D.E. Hartley, C. Harth, L.P. Steele, G. Sturrock, P.M. 
    Midgley, and A. McCulloch, 2000:  A history of chemically and 
    radiatively important gases in air deduced from ALE/GAGE/ AGAGE.  
    J. Geophys. Res., v. 105, pp. 17,751-17,792.


A16N_2003a AIR MEASUREMENTS

                DATE     TIME   CFC-11  CFC-12  CFC-113
              YYYYMMDD   HHMM   (ppt)   (ppt)   (ppt)
              --------   ----   ------  ------  -------
              20030619   0829   254.0   534.2   79.4
              20030619   0841   254.1   533.1   78.9
              20030619   0853   253.3   532.7   78.9
              20030619   0905   253.1   532.4   78.8
              20030619   0917   252.7   532.6   78.8
              20030619   1825   252.2   527.4   78.6
              20030619   1837   251.5   528.9   77.9
              20030619   1849   252.6   528.6   78.3
              20030619   1901   252.5   528.2   78.3
              20030619   1913   251.4   528.3   78.6
              20030620   0121   251.8   526.8   78.9
              20030620   0133   251.6   527.0   77.2
              20030620   0145   250.8   525.6   79.0
              20030620   0157   251.1   527.4   78.3
              20030620   0209   251.2   527.3   78.5
              20030620   1458   250.1   514.4   76.2
              20030620   1510   250.7   514.6   76.3
              20030620   1522   250.4   513.2   75.7
              20030623   0730   251.8   511.6   75.0
              20030623   0742   250.2   511.8   75.1
              20030623   0754   252.1   512.2   75.9
              20030623   0806   250.2   511.0   75.9
              20030626   0352   253.1   540.7   81.8
              20030626   0404   253.8   541.0   81.5
              20030626   0416   253.4   539.9   80.8
              20030626   0428   253.9   539.7   81.5
              20030627   0456   253.1   541.7   80.2
              20030627   0508   252.8   541.8   80.4
              20030627   0520   252.2   541.0   79.8
              20030627   0532   252.3   540.8   80.4
              20030628   0702   251.7   541.1   80.7
              20030628   0714   252.5   539.9   81.4
              20030628   0726   250.8   539.0   81.2
              20030628   0738   251.7   540.7   81.4
              20030629   0026   251.5   540.4   81.3
              20030629   0038   249.8   540.9   82.6
              20030629   0050   250.0   540.0   79.8
              20030629   0102   252.3   543.0   80.3
              20030629   1000   251.0   545.6   82.5
              20030629   1012   252.4   542.6   82.2
              20030629   1024   252.9   542.9   81.1
              20030629   1036   252.9   547.1   81.5
              20030629   1048   252.7   543.1   80.9
              20030630   0007   251.9   543.2   80.5
              20030630   0019   253.1   543.9   80.9

A16N_2003a AIR MEASUREMENTS (Continued)

                DATE     TIME   CFC-11  CFC-12  CFC-113
              YYYYMMDD   HHMM   (ppt)   (ppt)   (ppt)
              --------   ----   ------  ------  -------
              20030630   0031   252.4   540.2   81.3
              20030630   0043   251.8   544.1   81.1
              20030630   0055   252.9   542.3   80.0
              20030630   1206   252.4   543.2   80.9
              20030630   1218   251.9   541.4   80.9
              20030630   1230   251.8   539.6   80.3
              20030630   1242   251.9   541.7   80.4
              20030702   0410   252.2   543.5   80.6
              20030702   0422   252.4   544.7   81.1
              20030702   0434   253.4   543.8   81.0
              20030702   0446   253.5   541.9   80.5
              20030703   0718   255.1   545.5   81.2
              20030703   0730   254.7   546.6   81.2
              20030703   0742   253.6   546.6   81.1
              20030703   0754   254.4   545.9   80.7
              20030703   02233  254.1   545.8   79.5
              20030703   2245   253.6   545.3   80.2
              20030703   2257   254.2   545.6   80.6
              20030703   2309   254.5   545.1   80.4
              20030703   2321   253.8   543.6   80.4
              20030704   1656   253.6   544.5   80.2
              20030704   1708   252.9   544.1   81.0
              20030704   1720   252.8   543.7   81.0
              20030704   1732   253.5   544.3   80.8
              20030705   0911   253.3   543.9   80.8
              20030705   0923   253.7   542.8   80.7
              20030705   0935   254.0   543.5   80.4
              20030705   0947   253.5   543.9   80.6
              20030706   0052   254.4   542.8   80.9
              20030706   0104   252.8   540.7   79.6
              20030706   0116   252.3   540.8   80.2
              20030706   0128   253.8   542.8   80.7
              20030706   0140   253.1   540.6   80.2
              20030707   0751   253.9   541.2   80.4
              20030707   0803   253.9   544.1   80.4
              20030707   0815   253.0   543.8   81.0
              20030707   0827   253.8   542.3   80.4
              20030708   1428   254.7   545.3   81.4
              20030708   1440   253.3   542.0   80.7
              20030708   1452   252.8   544.0   82.4
              20030708   1504   253.2   541.2   80.8
              20030709   2215   252.2   541.2   79.8
              20030709   2227   251.5   541.5   79.3
              20030709   2239   252.3   544.1   79.4
              20030709   2251   251.5   543.8   80.1

A16N_2003a AIR MEASUREMENTS (Continued)

                DATE     TIME   CFC-11  CFC-12  CFC-113
              YYYYMMDD   HHMM   (ppt)   (ppt)   (ppt)
              --------   ----   ------  ------  -------
              20030719   1020   250.8   541.0   80.3
              20030719   1032   251.5   541.8   81.2
              20030719   1044   253.3   540.2   80.5
              20030719   1056   252.8   543.0   80.7
              20030720   0053   253.2   541.6   80.3
              20030720   0105   252.6   541.5   81.1
              20030720   0117   251.4   542.3   80.9
              20030720   0129   252.5   542.2   80.8
              20030720   0141   253.1   540.6   79.8
              20030721   0644   250.7   542.7   80.4
              20030721   0656   251.6   543.5   80.7
              20030721   0708   251.4   543.3   81.4
              20030721   0720   249.9   542.3   81.0
              20030721   2214   251.2   542.3   81.4
              20030721   2226   251.5   540.9   80.7
              20030721   2238   250.4   541.9   81.0
              20030721   2250   252.2   540.8   80.6
              20030721   2302   250.3   542.4   81.6
              20030722   1417   252.7   541.6   80.3
              20030722   1429   251.7   540.3   81.0
              20030722   1441   253.3   539.6   80.4
              20030722   1453   252.4   542.0   80.3
              20030723   2158   250.6   541.5   81.2
              20030723   2210   253.1   540.3   80.1
              20030723   2222   252.5   542.7   81.7
              20030723   2234   252.0   542.8   81.0
              20030723   2246   253.7   541.7   81.1
              20030725   0253   251.3   542.2   81.1
              20030725   0305   252.0   541.8   81.7
              20030725   0317   253.7   541.6   81.0
              20030725   0329   252.2   541.5   81.6
              20030725   0341   254.3   541.4   81.0
              20030728   0715   251.1   543.8   81.0
              20030728   0727   249.9   546.0   81.3
              20030728   0739   250.0   545.6   81.8
              20030728   0751   250.2   544.7   81.2
              20030728   2248   251.6   543.5   81.7
              20030728   2300   249.9   540.5   81.6
              20030728   2312   250.4   540.8   81.4
              20030728   2324   251.6   541.4   80.3
              20030730   0229   251.4   540.2   81.1
              20030730   0241   252.8   540.3   80.9
              20030730   0253   250.0   541.5   81.2
              20030730   0305   251.0   541.2   80.7
              20030731   0017   252.7   541.2   81.0

A16N_2003a AIR MEASUREMENTS (Continued)

                DATE     TIME   CFC-11  CFC-12  CFC-113
              YYYYMMDD   HHMM   (ppt)   (ppt)   (ppt)
              --------   ----   ------  ------  -------
              20030731   0029   250.7   541.8   82.1
              20030731   0041   250.8   541.5   81.8
              20030731   0053   252.0   540.3   81.5
              20030731   1703   252.4   540.2   81.2
              20030731   1715   251.5   540.4   81.7
              20030731   1727   249.6   540.1   80.9
              20030731   1739   249.2   540.2   81.3
              20030731   1751   250.3   539.8   80.8
              20030801   2133   249.9   540.5   81.8
              20030801   2145   250.9   540.6   81.4
              20030801   2157   250.1   541.2   80.0
              20030801   2209   250.1   544.1   80.8
              20030801   2221   250.3   539.9   81.2
              20030803   0350   250.7   541.2   81.9
              20030803   0402   250.7   539.1   79.9
              20030803   0414   250.7   540.7   81.3
              20030803   0426   251.7   540.4   80.5
              20030803   1833   250.6   542.1   81.5
              20030803   1845   252.1   541.9   80.4
              20030803   1857   251.2   542.7   81.1
              20030803   1909   252.0   539.3   80.1
              20030804   1020   252.0   539.9   81.5
              20030804   1032   251.7   540.9   80.9
              20030804   1044   251.4   540.8   81.0
              20030804   1056   252.7   541.0   80.9
              20030805   0235   251.7   543.3   81.0
              20030805   0247   251.2   543.1   81.6
              20030805   0259   252.4   541.4   81.5
              20030805   0311   250.4   541.8   81.8
              20030806   1418   251.7   541.0   80.2
              20030806   1442   251.2   539.9   81.7
              20030806   1454   251.6   538.6   80.1
              20030807   0446   249.3   539.4   80.8
              20030807   0458   252.1   540.7   80.5
              20030807   0510   249.5   540.1   80.6
              20030807   0522   249.6   538.3   80.2
              20030808   0445   252.7   541.0   80.0
              20030808   0457   250.8   541.0   81.2
              20030808   0509   250.6   540.7   80.3
              20030808   0521   249.5   540.8   80.5
              20030808   1749   250.9   541.3   81.0
              20030808   1801   252.1   541.3   81.4
              20030808   1813   251.6   541.1   80.1
              20030808   1825   250.7   539.4   81.5







C.3.  CO2 STUDIES ON A REPEAT HYDROGRAPHY CRUISE IN THE ATLANTIC OCEAN: 
               CO2 CLIVAR SECTION A16N_2003a DURING JUNE-AUGUST, 2003
                  E. Peltola, R. Wanninkhof, R. Feely, R. Castle, 
                  D. Greeley, J.-Z. Zhang, F. Millero, N. Gruber, 
                  J. Bullister and T. Graham [AOML]


Notice:  Mention of a commercial company or product does not con-
         stitute an endorsement by NOAA/AOML.  Use of information 
         from this publication concerning proprietary products or 
         the tests of such  products for publicity or advertising 
         purposes is not authorized.



                                ABSTRACT

This report presents methods, analytical and quality control procedures 
performed during A16N cruise, which took place from June 4 to August 11, 
2003 aboard the NOAA Ship RONALD H. BROWN under auspices of the National 
Oceanic and Atmospheric Administration (NOAA). The first hydrographic 
leg (June 19-July 10) was from Reykjavik to Funchal, Madeira along the 
20˚ W meridian and the second leg (July 15-August 11) continued 
operations from Funchal to Natal, Brazil on a track southward and ending 
at 6˚ S, 25˚ W. The research was the first in a decadal series of repeat 
hydrography sections jointly funded by NOAA-OGP and NSF-OCE as part of 
the CLIVAR/CO2/hydrography/tracer program. Samples were taken from up to 
34 depths at 150 stations.

The data presented in this report includes the analyses of water samples 
for: dissolved inorganic carbon (DIC), fugacity of CO2 (fCO2), Total 
Alkalinity (TA),  pH, nitrate (NO3), nitrite (NO2), phosphate (PO4), 
silicate (SiO4) and dissolved oxygen (O2).  



C.3.1.  INTRODUCTION

The A16N_2003a cruise from Reykjavik, Iceland to Natal, Brazil was the 
first in a series of repeat hydrography cruises to measure decadal 
changes in circulation, heat and fresh water budgets, and carbon 
inventory in the ocean.  The cruises repeat a sub-set of the World Ocean 
Circulation Experiment/World Hydrographic Program (WOCE/WHP) lines 
occupied in each major ocean basin in the 1990ties. 

The program is driven by the need to monitor the changing patterns of 
carbon dioxide (CO2) in the ocean and provide the necessary data to 
support continuing model development that will lead to improve 
forecasting skill for oceans and global climate. The WOCE/JGOFS survey 
during the 1990s has provided a full depth, baseline data set against 
which to measure future changes. By integrating the scientific needs of 
programs requiring measurement of the full water column, major synergies 
and cost savings are achieved. These measurements are of importance both 
for major research programs, such as CLIVAR and the U.S. GCRP Carbon 
Cycle Science Program (CCSP), and for operational activities such as 
GOOS and GCOS.  As outlined in the program documentation one component 
of a global observing system for the physical climate/CO2 system should 
include periodic observations of hydrographic variables, CO2 system 
parameters and other tracers. The large-scale observation component of 
the CCSP has a need for systematic observations of the invasion of 
anthropogenic carbon in the ocean superimposed on a variable natural 
background.  The five topic areas that the CO2/CLIVAR repeat hydrography 
program addresses are:

  A. Carbon system studies 
  B. Heat and freshwater storage and flux studies 
  C. Deep and shallow water mass and ventilation studies 
  D. Calibration of autonomous sensors 
  E. Data for model calibration 

Further descriptions of the repeat hydrography program can be found at: 

                         http://ushydro.ucsd.edu/

Details of the A16N_2003a cruise can be found in the cruise instructions 
posted at the website of PMEL: 

                    http://www.pmel.noaa.gov/CO2/a16n/

and the repeat hydrography website: 

                         http://ushydro.ucsd.edu/

The latter website also serves the full dataset from the cruise. The 
A16N_2003a cruise involved efforts of a dozen investigators whose names 
and project are listed in Table 1.  The cruise was executed  under 
leadership of Dr. John Bullister who served as chief scientist and Dr. 
Niki Gruber who was co-chief scientist.  A full list of personnel on the 
cruise is given in Table 2.  A list of participating institutions is in 
Table 3.

The cruise consisted of a transit leg from Charleston to Reykjavik on 
which limited surface water observations were taken. Surface water pCO2 
measurements for the transit and the hydrography legs can be found at 
www.aoml.noaa.gov/ocd/gcc. The first hydrographic leg was from Reykjavik 
to Funchal, Madeira along the 20° W meridian and the second leg 
continued operations from Funchal to Natal, Brazil on a track southward 
and ending at 6° S, 25° W (see Figure 1).

This data report focuses on the measurement of dissolved inorganic 
carbon (DIC), fugacity of CO2 (fCO2), Total Alkalinity (TA), pH, nitrate 
(NO3), nitrite (NO2), phosphate (PO4), silicate (SiO4) and dissolved 
oxygen (O2).  

Methodology, instrumentation and standardization of these parameters 
improved significantly during the WOCE/JGOFS era.  Notable developments 
include release of manuals detailing the analytical methods and 
operating protocols (DOE, 1994; http://cdiac.esd.ornl.gov/oceans 
/handbook.html).  Certified Reference Materials (CRM) are now available 
for DIC and TA, which are run interspersed with samples to determine 
calibration offsets.  On this cruise the TA values were adjusted 
accounting for the small difference between the CRMs run at sea and the 
certified value determined at SIO. For DIC there were problems with the 
gas loop calibrations attributed to inaccurate temperature sensors.  The 
reference materials were therefore used as primary calibration for both 
DIC and TA..

Instrumentation improved as well in the last decade.  Alkalinity 
measurements can be done with better precision through automation and 
close checks of the response of electrodes.  Burettes are independently 
calibrated, and the preparation of titrant (hydrochloric acid) undergoes 
improved quality control and standardization (Millero et al., 1998).  
Measurement of pH is now done at extreme precision with 
spectrophotometric methods (Byrne and Breland, 1989). The DIC 
measurements are done by coulometry, a precise integrative method.  
During the A16_2003a cruise we utilized two single operator multi-
parameter metabolic analyzers (SOMMAs) (Johnson et al., 1999) for 
analyses, which facilitated a sample throughput of up to 80 samples per 
day.  The fCO2 measurements were done with an equilibration system 
described in Wanninkhof and Thoning, (1993).  For this cruise we changed 
the data reduction and calculation routines. Comparison of data with a 
cruise along a similar transect in 1993 shows a appreciable bias between 
results that is detailed in the section describing the pCO2 analyses.  
Oxygen measurements were performed by Winkler titrations (Carpenter, 
1965) with photometric endpoint detection (Friederich et al., 1984).  
The titrator worked well but there were issues with errors in bottle 
volumes and problems with pipettes used to generate standard curves.  
Extensive post-cruise trouble shooting and bottle volume re-
determination were necessary to reduce the data. 

The data underwent carefully quality assurance and quality control 
(QA/QC) both during the cruise and post-cruise.  Precision of 
measurements was determined from duplicate sampling and comparison of 
deep-water data where little variability is expected.  Outliers in the 
data were flagged based on several methods utilizing prior knowledge of 
the trends and known relationships between parameters.  Depth profiles 
for each parameter were scrutinized for outliers.  When deviations were 
observed, it was assessed if other parameters showed deviations.  
Inorganic carbon system parameters were linked through physical chemical 
properties and by knowledge of two of the four parameters, the other two 
can be calculated provided silicate, phosphate, temperature and salinity 
of the sample are known.  These so-called over-determinations or 
internal consistency calculations were used to assess the difference 
between calculated and measured values.  When the difference exceeded 10 
µmol kg-1 for the measured TA and the TA calculated from DIC and pH or 
fCO2, the three parameters were scrutinized and compared with other 
methods to assess if the datum should be labeled as questionable.  Other 
techniques described in detail below include regional multi-linear 
regressions (MLR) between the inorganic carbon parameters and physical 
and chemical parameters known to correlate with them (for instance DIC = 
f(T, S, AOU, Si, PO4)). Again the differences between measured and 
calculated parameters are inspected.  Finally the parameters were 
plotted against latitude for narrow depth intervals.  Since changes 
along depth horizons are usually gradual, anomalies can be easily 
spotted and flagged.

This report describes the analytical procedures, calculations, and 
assessment of precision for DIC, TA, fCO2, and pH.  This is followed by 
a description of the QA/QC methods based on internal consistency of 
these parameters and the MLR technique.  The final section describes the 
procedures for measurement of nutrients and oxygen, and details the 
issues 


C.3.2.  DATA COLLECTION AND ANALYTICAL METHODS

C.3.2.1.  TOTAL DISSOLVED INORGANIC CARBON (DIC)

The DIC analytical equipment was set up in a seagoing laboratory van. 
The analysis was done by coulometry with two analytical systems (AOML-1 
and AOML-2) used simultaneously on the cruise.  Each system consisted of 
a coulometer (UIC, Inc.) coupled with a SOMMA (Single Operator 
Multiparameter Metabolic Analyzer) inlet system developed by Kenneth 
Johnson (Johnson et al., 1985, 1987, 1993; Johnson, 1992) formerly 
of Brookhaven National Laboratory (BNL).  In the coulometric analysis of 
DIC, all carbonate species are converted to CO2 (gas) by addition of 
excess hydrogen ion (acid) to the seawater sample, and the evolved CO2 
gas is swept into the titration cell of the coulometer with compressed 
nitrogen, where it reacts quantitatively with a proprietary reagent 
based on ethanolamine to generate hydrogen ions.  These are subsequently 
titrated with coulometrically generated OH-. CO2 is thus measured by 
integrating the total charge required to achieve this.

The coulometers were calibrated by injecting aliquots of pure CO2 
(99.995%) by means of an 8-port valve outfitted with two sample loops 
that had been calibrated by Kelly Brown, CCN Consulting (Wilke, 1993). 
However, due to large temperature variation the calibration factors 
obtained from gas loop measurements were of poor quality. Instead of 
using an average of the small and large loop values, we used a constant 
value for each analyzer throughout the entire cruise. The constant 
calibration value used for AOML-1 was 1.00532 and for AOML-2 1.00650. 
The CO2 gas volumes bracketed the amount of CO2 extracted from the water 
samples for the two AOML systems.  All DIC values were corrected for 
dilution by 0.2 ml of HgCl2 used for sample preservation. The total 
water volume of the sample bottles was 540 ml. The correction factor 
used for dilution was 1.00037. A correction was also applied for the 
offset from the Certified Reference Material (CRM) Batch 59, supplied by 
Dr. A. Dickson of Scripps Institution of Oceanography (SIO). This 
correction was applied for each cell using the CRM value obtained in the 
beginning of the cell. To check the stability of the coulometer and 
coulometer solutions, the CRMs were measured at the beginning, middle, 
and end of each coulometer cell solution. The coulometer cell solution 
was replaced after 25 mg of carbon was titrated, typically after 9-12 
hours of continuous use.  Sample titration times were 9-16 minutes.

Samples were drawn from the "Niskin" bottles into cleaned, precombusted 
540-ml Pyrex bottles using Tygon tubing according to procedures outlined 
in the Handbook of Methods for CO2 Analysis (DOE, 1994). Bottles were 
rinsed once and filled from the bottom, overflowing half a volume. Care 
was taken not to entrain any bubbles. The tube was pinched off and 
withdrawn, creating a 5-ml headspace, and 0.2 ml of saturated HgCl2 
solution was added as a preservative. The sample bottles were sealed 
with glass stoppers lightly covered with Apiezon-L grease, and were 
stored at room temperature for a maximum of 12 hours prior to analysis.

Replicate seawater samples were taken from the surface, 1000 m, and 
bottom "Niskin" sample bottles and run at different times during the 
cell.  The first replicate of the surface water was used at the start of 
the cell with fresh coulometer solution, the second surface replicate 
and the first one of the 1000 replicates were run in the middle of the 
cell after about 12 mg of C were titrated. The second one of the 1000 m 
replicates and the first one of the bottom replicates were run at the 
end of the cell after about 25 mg of C were titrated, while the second 
one of the bottom replicate samples was run using a new coulometer cell 
solution, see. No systematic difference between the replicates was 
observed.  The trends do not suggest any systematic dependency of 
results with amount of carbon titrated for a particular cell. The 
results of the duplicate samples have been presented in Figure 2, and 
Table 4 and 5.

Calculations

Calculation of the amount of CO2 injected was according to the 
Department of Energy (DOE) CO2  handbook [DOE, 1994].  
The concentration of CO2 ([CO2]) in the samples was determined according 
to:
                            (Counts-Blank Run Time)* K µmol/count
      [CO2] = Cal. Factor * -------------------------------------
                             pipette volume * density of sample

where Cal factor is the calibration factor that were fixed for this 
cruise because of malfunctioning of gas loops, "Counts" is the 
instrument reading at the end of the analysis, "Blank" is the 
counts/minute determined from blank runs performed at least once for 
each cell of the solution, "Run Time" is the length of coulometric 
titration (in minutes), and K is the conversion factor from counts to 
µmol which is dependent on the slope and intercept relation between 
instrument response and charge.  For a unit with Ecal slope of 1 and 
intercept of 0, the constant is 2.0728 * 10-4.

The blank values for AOML1 were in the range of 12.0-33.3 counts/min 
with an average value of 19.6 counts/min and a standard deviation of 6.8 
counts/min. For AOML2 they were in the range of 12.0-30.0 counts/min 
with an average value of 21.7 counts/min and a standard deviation of 6.1 
counts/min.

The pipette volume was determined by taking aliquots at known 
temperature of distilled water from the volumes prior to the cruise.  
The weights with the appropriate densities were used to determine the 
volume of the pipettes (AOML1: 28.726 cm3 @ 19.96°C, AOML2: 22.623 cm3 @ 
22.63°C).  

Calculation of pipette volumes, density, and final CO2 concentration 
were performed according to procedures outlined in the DOE CO2 handbook 
(DOE, 1994).


C.3.2.2.  FUGACITY OF CO2 (FCO2) 

Instrumentation

The fugacity of CO2 was measured on the A16N_2003a cruise at a constant 
temperature of 20°C by equilibrating a 500-ml water aliquot in a 
volumetric flask with a closed headspace. The headspace is circulated 
through a non-dispersive infrared detector that measures both CO2 and 
H2O levels. The analytical instrumentation is detailed in Wanninkhof and 
Thoning (1993) and is the same as the setup used in the N.Atl-93 cruise 
that occupied the same cruise line in 1993 (Castle et al., 1998). 

The  system is patterned after that of   Chipman et al. (1993) with 
modifications as presented in Wanninkhof and Thoning (1993).  In short, 
in the system a 500-ml water sample is equilibrated at ambient pressure 
with an 80-ml headspace in a thermostatted volumetric flask. The 
headspace is circulated through a non-dispersive infrared analyzer, 
NDIR, LICOR model 6262. Upon equilibration the circulation flow is 
stopped and 30 readings of H2O content and CO2 content in the cell are 
taken over a 30-second interval and averaged.  The system is a dual 
channel system where one equilibration occurs while circulating through 
the NDIR and a second flask is equilibrated offline. Once the first 
sample is analyzed the second flask is switched in line with the NDIR 
and the residual air in the NDIR is equilibrated with the second flask 
content. The second equilibration phase through the NDIR takes less time 
as a large part of the headspace already is equilibrated offline.  The 
two-channel configuration decreases the total analysis time to about 20 
minutes for two samples. 

The system is calibrated after every eight samples with six gaseous 
standards traceable to the manometrically determined values of C. D. 
Keeling of Scripps Institute of Oceanography.  The mole fractions of the 
standards used during the A16N2003a cruise were:

                    Tank number  mole fraction
                    -----------  -------------
                      CA05989      378.7 ppm
                      CA05980      792.5 ppm
                      CA05984     1036.9 ppm
                      CA05940     1533.7 ppm
                      CA05988      593.6 ppm
                      CA05998      205.1 ppm

The standards are also used as the headspace gas for the equilibration.  
Since the mole fractions of the gases in the headspace prior to 
equilibration are known, the small perturbation of the fCO2 in the water 
during the equilibration process can quantitatively be accounted for. 
The headspace gas is selected such that it is close the anticipated 
water value thereby minimizing the correction.

Data Reduction

The calculation of the fCO2 involves several steps including the 
conversion of the NDIR output to an equivalent dried mole fraction of 
CO2, the correction for the perturbation of the fCO2 in water by 
equilibration, and the small adjustment from the measurement temperature 
to 20°C. For the reduction of the A16N_2003a fCO2 we made an important 
adjustment in procedures. On previous cruises, the calibration of the 
samples that were run at 100% water vapor pressure (@ 20°C) to the 
standards that are dry was done through an empirical algorithms created 
by running standards both wet and dry.  For this cruise we relied on the 
internal correction from wet to dry mole fraction of CO2 provided by the 
LI-COR 6262. This change is based on testing by our group and other 
investigators that showed that the correction provided by the instrument 
is of high quality and subject to less uncertainty than our empirical 
corrections.  Since this is a fundamental change in our procedures we 
describe the old and new routine in detail below including comparison of 
the results.  

The correction from detector output to (dry) mole fraction of CO2, XCO2 
in the headspace was previously done by measuring the voltage output of 
the CO2 and H2O channel.  An empirical algorithm between dry standards 
and standards saturated with water vapor at 20°C was created of the 
form: 

    MVCO2(dry) = MVCO2 (wet) + A + B*MVCO2(wet) + C*(MVCO2(wet))2

Where MV is the millivolt output of the CO2 channel and MVCO2 (wet) is 
the milli-volt value measured for the equilibrated headspace of the 
sample.  From this algorithm the (water saturated) headspace gas is 
corrected to the dry state such that the samples can be directly related 
to the standard.  The next step is the convert the MVCO2(dry) of the 
sample to a XCO2 by creating a curve of MVCO2(dry) vs. XCO2 using the 
standards preceding and following the samples.  For each sample the 
three standards closest to the samples are selected and a second-order 
polynomial was created of MVCO2 vs. XCO2 by averaging the appropriate 
standards preceding and following the sample. The second- order 
polynomial is then used to calculate the XCO2 of the sample.

Following this step the fCO2 in the headspace is calculated according 
to:
                        fCO2 = XCO2 (1-pH2O)*0.9966

Where pH2O is the water vapor pressure @ 20°C (= 0.0226 atm) and 0.9966 
is the conversion factor from pCO2 to fCO2 @ 20°C.

The next step is the correction for change in the fCO2 in the water 
sample due to exchange of CO2 with the headspace during equilibration.  
This step is accomplished by using the mass balance criteria that the 
total amount of carbon in the headspace and water is conserved and by 
using the fact that the TA remains unchanged during equilibration.  The 
DIC of the sample (determined independently) and the headspace gas 
concentration prior to equilibration along with the volume of water and 
headspace are used to calculate the total amount of carbon in the 
system.  From the change in headspace  CO2 before versus after 
equilibration the change the DIC in the water can then be determined.  
From this change and the TA (calculated from DIC and fCO2 after 
equilibration), the fCO2 in the water before equilibration can then be 
determined.  

The final step is to correct the fCO2 from analysis temperature to 20°C.  
The water samples are always equilibrated within 0.1°C of 20°C such that 
this correction is less than 0.4% of the value.  The correction for 
perturbation of the fCO2 in the water during equilibration and the 
temperature correction to 20°C are performed using the carbonate 
dissociation constants and the temperature dependence of the constants 
and the calculation routines described in (Peng et al., 1987)

For A16N_2003a the correction from the moist gas of the sample to an 
equivalent dry concentration was performed utilizing the internal 
correction routine built into the Li-6262 analyzer.  This internal 
algorithm has been extensively checked by others and our tests showed 
that the correction was robust as well.  The important advantage of this 
internal correction is that in our previous data reductions we assumed 
that the algorithm between wet and dry created in laboratory tests 
before the cruise or after the cruise does not change appreciably over 
time.  This has proven not always to be the case. Secondly, the water 
vapor level measured during the standard runs can be appreciable despite 
absence of water vapor in the compressed gas standards since it takes a 
long time for the water vapor introduced by the equilibration of the 
samples to be flushed from the system.  Therefore we see a decreasing 
trend of water vapor level when the six samples are run consecutively 
(see Figure 3).

The modified data reduction routine uses the XCO2(dry) calculated by the 
detector for both standards and samples. A second-order polynomial fit 
is created between the actual mole fraction of CO2 in the standard and 
the instrument value.  This standardization accounts instrument drifts 
over time.  The detector was zeroed and spanned for CO2 every day while 
the water vapor channel was spanned right before the first leg and 
before the second leg.  Standardizing the water vapor channel is 
difficult because of the "stickiness" of the water vapor leading to lags 
and very slow response times.  A polynomial is created for the three 
standards closest to the sample by averaging the pertinent standards 
before and after the sample.  The other steps of correcting for small 
temperature deviations of the water bath from 20°C and correction to 
fCO2 prior to equilibration are identical to the procedures outlined 
above.

The new correction routine results in small differences in values for 
calculated fCO2 compared to the previous data reduction routine.  Table 
6 shows a comparison for station 45.  The values using the new 
reduction are systematically about 2 µatm lower than the old reduction 
method.  The table also gives the results of two different water vapor 
correction algorithms.  One empirical correction was established before 
the cruise and one determined from running wet vs. dry standards after 
the cruise.  The results show differences in the range from 7 to 17 
µatm.

Quality Control

During the cruise a total of 1515 Niskin samples were analyzed for fCO2, 
compared to 2500 DIC samples.  This was because only one full-time and a 
part-time operator were available for the work while two full-time 
analysts were involved in DIC analysis.  A summary of the analysis 
statistics is given in Table 7.

The precision of the results is based on comparison of duplicate values 
and is estimated to be 2 µatm or 0.3% based on the results in Table 
8. There is no apparent trend in imprecision with depth or absolute 
concentration when comparing absolute difference.  The relative (%) 
difference is slightly higher for lower fCO2 values found near the 
surface.   

Deep-water comparison with the 1993 cruise (NAtl-93) and crossover with 
     1999 cruise (24N).

The A16N_2003a cruise overlapped or intersected with two previous 
cruises that were sampled by our group.  The NAtl-93 cruise (Castle et 
al., 1998) followed the same track and was occupied during the summer of 
1993  but it was run from South to North.  A 24-bottle rosette was used 
such that fewer depth samples were obtained and the spacing of the 
stations was nominal 1 degree compared to 1/2 degree spacing on the 2003 
occupation.

The 24N-98 cruise was run in February and intersected the A16N_2003a 
cruise near 24° N, 26.5° W.  In the comparison we make the assumption 
that changes in deep water are negligible over the time period. The 
crossover with the 24 N cruise is shown in Figure 4. The fCO2 shows a 
consistent offset with the 2003 data being about 18 µatm higher than the 
1998 data.  For the comparison with the 1993 data we looked at the deep 
water offset in the deep water for stations spaced about 5 degrees apart 
(Figure 5).  Again a systematic bias is observed with the 2003 data 
being higher. The magnitude of the bias however is about 10 µatm.  The 
cause of these offsets is disconcerting and attributed to the water 
vapor correction. However, the exact reason or possible corrections is 
not readily apparent.

The surface water fCO2 levels are measured with a different system in 
underway mode  near sea surface temperature and offer an independent 
assessment of agreement of fCO2 values.  However, the temperature 
correction has some uncertainties which complicate the comparison.  For 
the comparison the fCO2(20) values are corrected to  SST as determined 
by the thermosalinograph using the empirical correction of ∂fCO2/∂T = 
0.0423°C-1 and by using the temperature dependence of the dissociation 
constant and using the thermodynamic equations. The results are shown in 
Figure 6 and show average differences of:

       -3.30 ± 4.9 µatm (n=76) for fCO2(UW)-fCO2(disc)Mehr  and
       -6.66 ± 4.1 µatm (n=76) for fCO2(UW)-fCO2(disc)4.23%.

In case of  fCO2(UW)- fCO2(disc)Mehr, the fCO2(20)  are normalized to sea 
surface temperature using the Mehrbach constants as refit by Dickson and 
Millero.  For fCO2(UW)-fCO2(disc)4.23%., the fCO2(20) are normalized to 
SST  using the empirical relationship of 0.0423°C-1.  Again our 
temperature corrected discrete data are on average higher than the 
underway measurements.  The differences CO2(UW)-fCO2(disc)Mehr and 
fCO2(UW)-fCO2(disc)4.23%  are plotted against temperature in Figure 7.  
There is a slight trend with temperature for the adjustments using the 
Mehrbach constants.  Also, near 20°C when the adjustment is small the 
comparison shows that the discrete data is systematically higher. For 
the range from 18 to 22°C the difference is -5.1 ± 4.9µatm (n=76) and -
6.7 ± 4.1 µatm (n=76) for fCO2(UW)-fCO2(disc)Mehr and fCO2(UW)-
fCO2(disc)4.23% very similar to the average difference over the entire 
temperature range suggesting that the systematic offset is not 
attributable to the temperature correction alone.


C.3.2.3.  TOTAL ALKALINITY (TA)

Seawater samples were drawn from the "Niskin" bottles with a 40-cm 
length of silicon tubing.  One end of the tubing was fit over the 
petcock of the "Niskin" bottle and the other end was inserted into the 
bottom of a 500-ml Corning glass-stoppered sample bottle.  The sample 
bottle was rinsed three times with approximately 300 ml of seawater.  
The sample bottle was slowly filled from the bottom.  Once filled, the 
sample bottles were kept in a constant water bath at 25°C for half-hour 
before analysis.  

The titration system used to determine TA consisted of a Metrohm 665 
Dosimat titrator and an Orion 720A pH meter controlled by a personal 
computer (Millero et al., 1993).  The acid titrant, in a water-jacketed 
burette, and the seawater sample, in a water-jacketed cell, were kept at 
25±0.1°C with a Neslab constant-temperature bath.  The Plexiglas water-
jacketed cells were similar to those used by Bradshaw et al. (1988), 
except that a larger volume (200 ml) was used to increase the precision.  
The cells had fill and drain valves with zero dead-volume to increase 
the reproducibility of the cell volume. 

The HCl solutions used throughout the cruise were made, standardized, 
and stored in 500 cm3 glass bottles in the laboratory for use at sea.  
The 0.23202 M HCl solutions were made from 1 M Mallinckrodt standard 
solutions in 0.45 M NaCl to yield an ionic strength equivalent to that 
of average seawater (~0.7 M).  The acid was standardized using a 
coulometric technique by the Univ. of Miami and by Dr. Dickson of 
Scripps Institution of Oceanography (SIO).  The two standardization 
techniques agreed to +/-0.0001 N. 

The volume of HCl delivered to the cell is traditionally assumed to have 
a small uncertainty (Dickson, 1981) and is equated with the digital 
output of the titrator.  Calibrations of the Dosimat burettes with Milli 
Q water at 25°C indicated that the systems deliver 3.000 ml (the value 
for a titration of seawater) to a precision of 0.0004 ml.  This 
uncertainty resulted in an error of 0.4 µmol/kg in TA. 

The titrators were calibrated in the laboratory before the cruise. 
Certified standard Reference Material (CRM) Batch 59 prepared by Dr. 
Dickson was used at sea to monitor the performance of the titrators. All 
TA data have been corrected based on CRM values for each cell and each 
leg. (Millero et al, 2000), see Table 9.


C.3.2.4.  pH

Seawater samples were drawn from the "Niskin" bottles with a 20-cm 
length of silicon tubing.  One end of the tubing was fit over the 
petcock of the "Niskin" bottle and the other end was attached over the 
opening of a 10-cm glass spectrophotometric cell.  The 
spectrophotometric cell was rinsed three to four times with a total 
volume of approximately 200 ml of seawater; the Teflon endcaps were also 
rinsed and then used to seal a sample of seawater in the glass cell.  
While drawing the sample, care was taken to make sure that no air 
bubbles were trapped within the cell.  The sample cells were kept in a 
waterbath at 20°C for a half an hour before analysis.

Seawater pH was measured using the spectrophotometric procedure (Byrne, 
1987) and the indicator calibration of Clayton and Byrne (1993).  The 
indicator was an 8.0-mM solution of m-cresol purple sodium salt 
(C21H17O5Na) in MilliQ water. 

The absorbance measurements were made using a Varian Cary 2200 
spectrophotometer.  The temperature was controlled to a constant 
temperature of 25°C with an Endocal RTE 8DD refrigerated circulating 
temperature bath that regulates the temperature to ± 0.01°C.  The 
temperature was measured using a Guildline 9540 digital platinum 
resistance thermometer.


C.3.2.5.  OXYGEN

Method 

The analytical method for dissolved oxygen in seawater during A16N_2003a 
cruise was based on automated Winkler titration by Williams and 
Jenkinson (1982) and modified by Friederich et al. (1991).  Dissolved 
oxygen samples were withdrawn from 10-L Niskin bottles to 145-ml Pyrex 
brand iodine flasks (Corning 5400, Corning, New York, USA). The exact 
volume of each flask at room temperature had been gravimetrically 
calibrated with its ground glass stopper following standard procedures 
(DOE, 1994; WHP Operations and methods, 1991). One ml of manganese 
chloride reagent and one ml of alkaline iodide reagent were added to 
each sample in the iodine flasks and its stopper was placed in the 
bottle neck. The bottles were shaken vigorously for about one minute to 
completely fix oxygen with manganese hydroxide. In this method, 
dissolved oxygen in the sample reacts with manganese hydroxide to form 
Mn(OH)3 precipitate. Particulate Mn(OH)3 dissolve upon the acidification 
and resulting Mn3+ oxidize iodide to iodine in acidic solution. The 
liberated iodine complex with excess iodide forming I3¯ and the latter is 
titrated with a sodium thiosulfate solution that is standardized by a 
primary standard potassium iodate. The complex I3¯ has a maximum 
absorbance at 352 nm and change in absorbance of I3¯ at 352 nm is used to 
detect the end point.  A custom-build automated oxygen titrator with MS 
DOS interfacing software was used to determine dissolved oxygen 
concentrations in the samples.

A total of 5011 seawater samples were taken from 150 stations and 
analyze for dissolved oxygen concentrations. At the beginning of cruise, 
a test CTD cast was made by sampling 20 Niskin bottles from same depth 
(170 m). Analysis of these samples was listed in Table 10 and indicate a 
precision of 0.3 µmole/L. Throughout the cruise duplicate samples 
from same Niskin bottle were collected at each station to estimate the 
precision of overall measurement (sampling and analysis). Analyses of 
300 replicate samples listed in Table 11 indicated that the precision of 
shipboard automated Winkler titration is 0.29 including all outliers and 
0.24 µmole/L excluding the outliers. Analysis of outliers indicated 
that most outliers in duplicate analysis were due to errors in the 
volumes of oxygen bottles if it is not a problem with Niskin bottles or 
sampling error. The outliers in vertical profiles of oxygen were also 
used to identify the bottles that might have errors in volumes. Total of 
33 sample bottles were recalibrated and 11 of them had volume errors 
greater than 0.3 ml (Table 12). This accounts about 5% of sample 
bottles used during the A16N cruise. The volumes of such identified 
questionable oxygen bottles were recalibrated after the cruise and 
dissolved oxygen concentrations were recalculated for those samples 
using correct volumes.

The primary iodate standard solution was prepared from high purity 
reagent grade KIO3 (Mallinckrodt, USA), pre-dried in an oven at 110_C 
for overnight and cooled in a desiccator before weighing. The 
thiosulfate solution was prepared from reagent grade Na2S2O3  5H2O 
(Mallinckrodt, USA). During the cruise, total of 25 bottles of 
thiosulfate solutions (1 liter each) were consumed for oxygen analyses. 
Each new bottle of thiosulfate solution was first standardized by the 
primary standard KIO3 solution before using it for sample titration. 
Standardizations of the thiosulfate solutions were performed by 
titration of known amounts of KIO3 solution (usually 2, 4, 6, and 8 ml). 
Regression analysis of four titration points generates a slope (factor) 
and an intercept (blank) from which sample concentration are calculated. 
Extending KIO3 solution to 20 ml produced essentially the same 
calibration curve as shown in the thiosulfate bottle 21 in Table 13. 
Each bottle of thiosulfate usually lasts for 2 to 3 days of sample 
titration. The thiosulfate bottle 24 had replicate standardization. The 
thiosulfate bottle 19 was standardized at the beginning and the end of 
its life span to check its stability during storage. All the replicate 
analyses produced acceptable results within uncertainty of 
standardization as shown in Table 13. It should be pointed out that at 
beginning of cruise there are several standardizations with lower slopes 
and larger intercepts as shown in Figure 8. These were attributed to 
malfunction of titration system used during that period. When system is 
functioning properly it produced slopes within 1% of the theoretical 
value of 24.818 and intercepts less than ± 0.01 as shown in most part of 
cruise in Figure 8.

At the beginning of leg 2 (from stations 72 to 79) a problematic 
automatic pipette was used to deliver the KIO3 standard solution for 
standardization of thiosulfate solution in bottle 14. An unusually high 
slope was observed and this pipette was not used in subsequent analyses. 
Shipboard and post cruise comparison indicated that there is an error in 
volume delivery of this automatic pipette. Dissolved oxygen 
concentrations from station 72 to 79 have been corrected for errors in 
volume delivery of iodate solution by this automatic pipette used in the 
standardization of thiosulfate solution. A correction factor (1.0153) 
was estimated based on post-cruise recalibration of the automatic 
pipette as shown in Table 14 and was applied to data from station 72 to 
79. 

Since the Dosimat titrators have demonstrated high precision and 
accuracy (0.05 and 0.2% at delivery of 10ml solution, respectively) in 
volume delivery of titrants, we recommend use a Dosimat or similar 
positive displacement burette to quantitatively dispense the iodate 
standard solution in the future cruises. This procedure can improve the 
accuracy of shipboard oxygen analysis.




                            ACKNOWLEDGMENTS

The dedication and assistance of the officers and crew of the NOAA Ship 
RONALD H. BROWN is gratefully appreciated and hereby acknowledged. This 
research was supported by the Climate Observation and Services Panel of 
NOAA. We wish to acknowledge the COSP program manager Mike Johnson for 
supporting the field program.  The CO2 CLIVAR repeat hydrography program 
is a joint effort between NOAA and NSF-OCE. Eric Itsweire of NSF was 
instrumental in forming the program.




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TABLE 1:  Principal Investigators

PROJECT                     NAME                  INSTITUTION
--------------------------  --------------------  -----------
CTD                         Gregory Johnson       PMEL
Salinity                    Gregory Johnson       PMEL
CTD/O2                      Gregory Johnson       PMEL
Chlorofluorocarbons (CFCs)  John Bullister        PMEL
Chlorofluorocarbons (CFCs)  Mark Warner           UW
HCFs                        Shari Yvon-Lewis      AOML
Total CO2(DIC), pCO2        Richard Feely         PMEL
Total CO2(DIC), pCO2        Richard Wanninkhof    AOML
Nutrients                   Calvin Mordy          PMEL
Nutrients                   Jia-Zhong Zhang       AOML
Dissolved Oxygen            Jia-Zhong Zhang       AOML
Helium/tritium              Peter Schlosser       LDEO
Total Alkalinity            Frank Millero         Miami
pH                          Frank Millero         Miami
Trace Metals                Christopher Measures  Hawaii
Trace Metals                William Landing       FSU
Aerosols                    William Landing       FSU
ADCP                        Eric Firing           Hawaii
ALACE Float deployment      Breck Owens           WHOI
ALACE Float deployment      Silvia Garzoli        AOML
PIC/POC                     Jim Bishop            LBNL
DOC                         Dennis Hansell        Miami
13-C, 14-C                  Ann McNichol          WHOI
Alkyl Nitrate               Eric Saltzman         UCI
Bathymetry                  Ship personnel
Underway thermosalinograph  Ship personnel

    

TABLE 2:  Cruise Personnel 
                                                                Leg
Position           Name                Institution   Country  0  1  2
------------------ ------------------- ------------- -------  -  -  -
Chief Scientist    John Bullister      PMEL          US          *  *
Co-Chief Scientist Nicolas Gruber      UCLA          Swiss       *  *
Data Manager       Frank Delahoyde     SIO           US          *  *
Grad Student       Nicole Lovenduski   UCLA          US             *
Grad Student       Elena Brambilla     SIO           Italy       *
Grad Student       Regina Cesario      UW            US          *
CTD Data Processor Kristene McTaggart  PMEL          US          *  *
ET                 Douglas Anderson    AOML          US          *
ET                 David Bitterman     AOML          US             *
LADCP              Julia Hummon        UH            US          *  *
Salinity           Gregory Johnson     PMEL          US          *
Salinity           David Wisegarver    PMEL          US             *
O2                 George Berberian    AOML          US          *  *
Nutrients          Jia-Zhong Zhang     AOML          US             *
Nutrients          David Wisegarver    PMEL          US          *
Nutrients          Charles Fischer     AOML          US             *
Nutrients          Calvin Mordy        UW-JISAO/PMEL US          *
CFC                Mark Warner         UW            US          *  *
CFC                Eric Wisegarver     PMEL          US          *  *
Helium/Tritium                         LDEO                      *  *
HCFC               Shari Yvon-Lewis    AOML                      *  *
Alkalinity & pH    Xiaorong Zhu        UM            China       *  *
Alkalinity & pH    Taylor Graham       UM            US       *  *
Alkalinity & pH    Mike Trapp          UM            US             *
Alkalinity & pH    Vanessa Koehler     UM            US       *  *  *
Alkalinity & pH    William Hiscock     UM            US       *  *
Alkalinity & pH    David Sergio Valdes UM            Mexico         *
Alkalinity & pH    Denis Pierrot       UM            France   *
DIC1               Esa Peltola         AOML          US          *  *
DIC2               Robert Castle       AOML          US          *  *
pCO2               Dana Greeley        PMEL          US          *  *
pCO2               Kevin Sullivan      UM-CIMAS/AOML US       *
Trace Metal        Chris Measures      UH            Chile       *  *
Trace Metal        Rodrigo Torres      WHOI          US       *  *  *
Trace Metal        Matt Brown          UH                     *
Aerosol            William Landing     FSU           US       *  *  *
Aerosol            Clifton Buck        FSU           US       *  *  *
Aerosol            Erik Kvaleberg      FSU           Norway   *
Aerosol            Anthony Arguez      FSU           US       *
POC/PIC            Jim Bishop          LBNL          US          *
POC                Alexey Mishonov     TAMU          Ukraine     *
DOC                Stacy Brown         UM            US          *
Alkyl Nitrate      Elizabeth Dahl      UCI
CIRIMS-IR-SST      Trina Litchendorf   UW            US       *

The Chief Survey Technician aboard the R/V Ronald Brown for the cruise was Jonathan Shannahoff.



TABLE 3: PARTICIPATING INSTITUTIONS

         AOML     NOAA, ATLANTIC OCEANOGRAPHIC & METEOROLOGICAL LABORATORY
                  4301 Rickenbacker Causeway
                  Miami, FL 33149-1098
         FSU      FLORIDA STATE UNIV. DEPARTMENT OF OCEANOGRAPHY
                  0102 OSB, West Call Street
                  Tallahassee, FL 32306
         LBNL     EO LAWRENCE BERKELEY NATIONAL LABORATORY
                  1 Cyclotron Road
                  Berkeley, California 94720
         LDEO     THE LAMONT-DOHERTY EARTH OBSERVATORY 
                  61 Route 9W
                  Palisades, NY 10964-1000
         PMEL     NOAA, PACIFIC MARINE ENVIRONMENTAL LABORATORY
                  7600 Sand Point Way NE
                  Seattle, WA 98115-0070
         SIO      SCRIPPS INSTITUTION OF OCEANOGRAPHY
                  8602 La Jolla Shores Drive
                  La Jolla, CA. 92037
         TAMU     TEXAS A&M UNIV., DEPARTMENT OF OCEANOGRAPHY
                  College Station 
                  TX 77843-3146
         UCI      UNIV. OF CALIFORNIA, IRVINE, EARTH SYSTEM SCIENCE
                  Irvine, CA 92697-3100
         UCLA     UNIV. OF CALIFORNIA, INSTITUTE OF GEOPHYSICS AND 
                  Planetary Physics & Dept. of Atmospheric Sci
                  5853 Slichter Hall,
                  Los Angeles, CA 90095-1567
         UCSD     UNIV. OF CALIFORNIA, SAN DIEGO
                  9500 Gilman Drive
                  La Jolla, CA 92093 - 0214
         UH       UNIV. OF HAWAII, DEPARTMENT OF OCEANOGRAPHY,
                  Univ. of Hawaii at Manoa
                  1000 Pope Rd, Marine Sci. Bldg, 
                  Honolulu, HI 96822
         UM       UNIV. OF MIAMI
                  4301 Rickenbacker Causeway,
                  Miami, Florida 33149
         UM-CIMAS UNIV. OF MIAMI/COOPERATIVE INSTITUTE FOR
                  Marine and Atmospheric Studies
                  4301 Rickenbacker Causeway,
                  Miami, Florida 33149
         UW       UNIV. OF WASHINGTON
                  Box 357940, Seattle,
                  WA 98195-7940
         UW-JISAO UNIV. OF WASHINGTON/JOINT INSTITUTE FOR
                  STUDY OF THE ATMOSPHERE AND OCEAN
                  Box 357940, Seattle,
                  WA 98195-7940
         WHOI     WOODS HOLE OCEANOGRAPHIC INSTITUTION
                  Co-op Building, MS #16
                  Woods Hole, MA 02543



TABLE 4: Dissolved Inorganic Carbon Duplicate Statistics

                        Duplicate Statistics:

        |   BB   |  BM   |   ME  |  BE  |   DC  |  DI  |BEBE|  MM  |  EE  |Deleted
--------|--------|-------|-------|------|-------|------|----|------|------|-------
Avg:    |   0.8  |  1.3  |  1.2  | 1.3  |  1.4  | 0.7  | -  | 1.3  | 1.0  | 
Stdev:  |   0.80 |  0.94 |  0.57 | 1.27 |  0.86 | 0.42 | -  | 1.01 | 0.30 |  
Number: |  94    | 39    | 13    | 8    | 56    | 3    | 0  | 6    | 3    |  64
Total:  | 286    |       |       |      |       |      |    |      |      |
                          
         BB    The duplicate samples were measured back-to-back    
         BM    One duplicate was measured in the beginning and the other 
               one in the end of the cell
         ME    One duplicate was measured in the middle and the other one 
               in the end of the cell
         BE    One duplicate was measured in the beginning and the other 
               one in the end of the cell
         DC    The duplicates were run on a same instrument, but on 
               different cells  
         DI    The duplicates were run on different instruments      
         BEBE  Both duplicates were measured in the beginning of the cell, 
               but not back-to-back
         MM    Both duplicates were measured in the middle of the cell, but 
               not back-to-back
         EE    Both duplicates were measured in the end of the cell, but 
               not back-to-back



TABLE 5:  Dissolved Inorganic Carbon (DIC) Duplicates

                                  Pres      DIC
                Stn  Cast  Btl    (db)    µmol/kg    Stdev
                ---  ----  ---    -----   -------    -----
                  1    1     1      200    2145.9    0.38
                  1    1    11        2    2099.3    1.71
                  2    1     1      553    2157.6    0.36
                  2    1    18        2    2105.8    0.86
                  3    1     1    1,009    2157.6    1.23
                  5    1     1    1,816    2161.5    0.81
                  5    1     8    1,000    2157.2    1.23
                  6    1    29        2    2085.1    1.11
                  7    1    29        2    2079.5    0.15
                  8    1    30        2    2068.8    0.52
                 10    1    32        2    2064.4    0.16
                 11    1    12    1,051    2168.3    0.72
                 11    1    33        3    2064.7    1.19
                 12    1    32        2    2062.6    0.25
                 13    1    33        2    2063.3    0.86
                 15    1     1    1,647    2161.9    0.50
                 15    1    27        2    2090.1    0.60
                 16    1     1    1,168    2172.1    0.70
                 17    1    21        2    2082.7    0.87
                 19    1     1    1,464    2159.3    1.70
                 21    1    26        9    2088.8    0.54
                 22    1    25        6    2083.1    0.17
                 23    1     1    1,418    2160.7    0.05
                 24    1    31        3    2088.7    0.04
                 25    1     1    2,706    2190.1    0.41
                 25    1    26      125    2128.7    0.03
                 25    1    32        2    2080.1    1.84
                 26    1    33        3    2090.8    0.22
                 27    1     1    3,812    2203.2    0.18
                 27    1    13    1,050    2166.7    0.80
                 29    1    14    1,100    2172.0    0.51
                 29    1    35       20    2086.3    1.75
                 30    1    33        2    2082.2    0.74
                 31    1     1    4,472    2204.0    1.60
                 31    1    13    1,050    2180.3    0.49
                 32    1    35        2    2075.3    0.98
                 33    1     1    4,482    2201.4    0.27
                 33    1    14    1,002    2177.5    0.49
                 34    1    33        3    2072.3    0.60
                 36    1    24        8    2079.6    0.34
                 41    1    20    1,001    2180.5    0.13
                 41    2    24        4    2069.7    0.50
                 42    1    23       25    2070.1    0.05
                 43    1     1    4,066    2197.4    0.75
                 43    1    14    1,003    2182.1    1.45
                 43    1    35        4    2070.2    0.25

TABLE 5:  Dissolved Inorganic Carbon (DIC) Duplicates (Continued)

                                  Pres      DIC
                Stn  Cast  Btl    (db)    µmol/kg    Stdev
                ---  ----  ---    -----   -------    -----
                 44    2    32        3    2067.4    0.03
                 45    1     1    5,240    2200.0    0.53
                 45    1    14    1,001    2184.3    1.73
                 45    1    35        3    2067.2    0.68
                 46    1    33        3    2067.6    2.01
                 47    1     1    2,458    2169.3    1.26
                 47    1    10    1,049    2192.6    1.47
                 47    1    31        3    2068.4    0.28
                 48    2    30        3    2070.7    0.49
                 49    1     1    4,775    2197.9    1.64
                 51    1    15    1,046    2190.3    0.05
                 51    1    35        3    2069.7    2.05
                 52    1     1    4,734    2198.0    1.72
                 52    1    33        4    2069.9    0.91
                 53    1     1    4,826    2201.0    1.04
                 53    1    14      900    2179.3    1.10
                 53    1    32       19    2066.9    0.53
                 54    1    35        3    2068.2    1.82
                 55    2     1    5,218    2200.6    0.14
                 55    2    17      950    2189.1    0.43
                 55    2    30       92    2099.1    0.25
                 55    2    35        4    2085.9    0.29
                 57    2     1    3,875    2196.1    0.64
                 57    2    35        4    2086.4    0.60
                 58    1    35        4    2092.6    2.11
                 59    1    15    1,051    2194.2    1.71
                 59    1    35        3    2090.1    1.04
                 60    1    33        3    2089.6    0.32
                 61    2     1    5,215    2201.5    0.26
                 61    2    17      992    2185.1    0.81
                 61    2    35        4    2085.9    0.67
                 62    1    35        3    2095.4    0.30
                 63    2     1    5,319    2200.1    0.71
                 63    2    14    1,051    2190.1    0.01
                 63    2    35        3    2107.4    0.93
                 64    1    35        4    2094.4    1.43
                 65    1     1    5,343    2198.8    0.36
                 65    1    33        3    2109.3    1.39
                 66    1    35        3    2105.5    0.78
                 67    2     1    5,252    2200.5    0.72
                 67    2    17      951    2190.2    1.62
                 67    2    35        4    2104.1    1.84
                 68    1    17      942    2186.7    1.25
                 68    1    35        3    2108.3    0.62
                 69    1     1    5,317    2199.7    2.33
                 69    1    14    1,002    2187.6    0.54
                 69    1    35        4    2101.5    0.27
                 70    1    33        3    2103.2    0.02
                 71    1     1    5,332    2199.4    0.99
                 71    1    17      951    2186.6    0.59
                 71    1    35        3    2103.0    0.17
                 72    2     1    5,332    2198.1    0.41
                 72    2    17      950    2188.8    0.57

TABLE 5:  Dissolved Inorganic Carbon (DIC) Duplicates (Continued)

                                  Pres      DIC
                Stn  Cast  Btl    (db)    µmol/kg    Stdev
                ---  ----  ---    -----   -------    -----
                 72    2    31       65    2095.3    0.92
                 72    2    35        3    2109.7    1.77
                 74    1     1    5,275    2199.4    1.87
                 74    1    14    1,000    2191.4    0.40
                 74    1    35        4    2111.0    1.54
                 75    1    35        3    2111.9    0.63
                 76    1     1    5,306    2198.7    0.80
                 76    1    13    1,050    2197.3    1.86
                 76    1    35        4    2112.4    0.05
                 78    2     1    5,329    2193.8    1.01
                 78    2    35        3    2103.6    0.05
                 79    1    35        3    2109.9    0.55
                 80    1    14    1,000    2196.4    0.57
                 80    1    35        3    2108.1    0.17
                 81    1    35        4    2096.7    0.65
                 82    2     1    5,491    2201.1    0.17
                 82    2    17      949    2195.7    0.52
                 82    2    35        4    2100.5    0.04
                 83    1    35        4    2101.6    0.36
                 84    1     1    5,551    2202.9    0.88
                 84    1    17      950    2205.3    0.90
                 84    1    35        4    2102.1    1.65
                 85    1    35        4    2097.5    1.73
                 86    1    35        3    2100.1    0.09
                 87    1    35        4    2082.8    0.56
                 88    2     1    5,528    2201.2    0.34
                 88    2    17      949    2209.3    0.59
                 88    2    35        4    2086.0    1.88
                 89    1    35        3    2083.5    0.72
                 90    1     1    5,125    2198.7    1.31
                 90    1    14    1,000    2209.0    2.12
                 91    1    35        3    2065.0    0.53
                 92    1     1    4,874    2201.0    1.05
                 92    1    12    1,050    2208.2    1.57
                 92    1    35        4    2064.0    2.10
                 94    2     1    4,632    2200.6    0.55
                 94    2    33        3    2062.8    0.29
                 95    1    35        4    2064.9    0.47
                 96    1     1    4,612    2202.5    2.00
                 96    1    15      950    2216.7    1.24
                 96    1    35        3    2055.3    0.08
                 97    1    33        3    2063.7    0.82
                 98    2    13    1,000    2211.4    0.77
                 98    2    33        4    2035.1    0.49
                100    2     1    3,892    2203.1    0.68
                100    2    12    1,050    2220.2    0.19
                100    2    33        4    2048.2    0.14
                101    1    35        3    2035.8    0.09
                104    2     1    5,534    2207.5    1.41
                104    2    20      548    2240.9    0.10
                104    2    35        3    2040.4    0.24
                105    1    35        3    2025.6    0.54

TABLE 5:  Dissolved Inorganic Carbon (DIC) Duplicates (Continued)

                                  Pres      DIC
                Stn  Cast  Btl    (db)    µmol/kg    Stdev
                ---  ----  ---    -----   -------    -----
                106    2     1    5,796    2198.2    1.94
                106    2    35        4    2026.5    0.21
                107    1    35        3    2013.5    0.20
                108    1     1    5,798    2199.3    0.69
                108    1    15      749    2238.0    1.96
                108    1    35        3    2018.2    0.69
                109    1    35        3    2028.2    0.04
                110    2     1    6,071    2198.1    0.24
                110    2    35        3    2026.0    0.03
                111    1    35        3    2019.1    0.93
                112    1     1    5,446    2201.7    0.23
                112    1    17      950    2226.5    0.64
                112    1    35        3    2004.8    1.92
                113    1    35        3    1977.0    0.73
                114    1     1    5,296    2205.2    0.96
                114    1    14    1,001    2223.8    0.60
                114    1    33       20    1978.5    0.50
                116    2     1    5,162    2206.6    2.36
                116    2    20      424    2226.5    0.18
                116    2    35        3    1955.0    0.01
                117    1    35        4    1953.3    0.52
                118    2     1    4,422    2193.1    2.31
                118    2    13    1,000    2224.7    0.83
                118    2    33        3    1954.8    0.18
                119    1    35        3    1951.9    0.11
                120    1     1    4,358    2193.9    1.04
                120    1    20      449    2238.3    0.26
                120    1    35        4    1944.9    1.08
                121    1    35        3    1948.3    0.28
                122    2     1    4,577    2197.4    0.16
                122    2    13    1,051    2217.4    0.93
                122    2    33       10    1986.5    0.30
                123    1    35        4    1987.8    1.40
                124    1     1    4,088    2195.7    0.12
                124    1    35        3    1987.2    0.63
                125    1    35        3    1986.0    0.96
                126    2    18      550    2218.4    1.62
                126    2    33       10    1986.7    0.26
                127    1    35        3    1989.8    0.16
                128    1     1    3,803    2191.6    0.97
                129    1     1    3,932    2194.4    2.15
                129    1    13      999    2217.2    0.09
                129    1    35        4    1987.8    2.23
                130    1    35        3    1995.2    0.45
                131    1     1    3,678    2191.5    1.51
                132    1     1    3,358    2186.2    1.64
                132    1    12    1,052    2212.8    0.68
                132    1    33        3    2038.5    1.27
                133    1    33       19    2042.0    0.33
                134    1    35        4    2043.1    0.28
                135    1     1    3,231    2185.0    1.00
                135    1    12    1,000    2216.5    0.06
                135    1    33        4    2044.8    0.15

TABLE 5:  Dissolved Inorganic Carbon (DIC) Duplicates (Continued)

                                  Pres      DIC
                Stn  Cast  Btl    (db)    µmol/kg    Stdev
                ---  ----  ---    -----   -------    -----
                136    1    32        3    2044.9    0.02
                137    1    33        3    2048.5    1.54
                138    2     1    3,187    2182.0    0.95
                138    2    11    1,049    2214.8    1.10
                138    2    32        3    2049.6    0.21
                141    1     1    5,019    2257.0    1.09
                141    1    15    1,000    2216.5    0.56
                141    1    35        3    2040.2    0.80
                144    2     1    5,410    2257.3    0.23
                144    2    14    1,050    2215.4    0.10
                144    2    35        3    2037.1    0.59
                146    1    17    1,000    2215.3    0.21
                146    1    35        4    2024.2    2.17
                148    2     1    5,807    2255.9    0.61
                148    2    17      950    2215.0    1.66
                148    2    35        4    2017.4    0.31
                150    1    18    1,000    2214.9    0.72
                150    1    35        4    2020.1    0.58



TABLE 6: Comparison of results of different water vapor correction routines

         Key   Lat           fCO2(20)  fCO2(20)  fCO2(20)
         field (N) pressure  (final)   (cruise)  (newH2O)
         ----- --- --------  --------  --------  --------
         45101  43  5239.7    762.9     765.80    745.8
         45102  43  4994.3    765.7     768.80    748.5
         45103  43  4499.7    769.5     771.45    751.7
         45104  43  3983.9    768.5     770.30    751.8
         45106  43  3001.5    758.4     760.50    742.1
         45108  43  2000.5    755.2     756.60    738.6
         45109  43  1800.0    761.4     762.90    745.3
         45111  43  1401.5    746.0     747.80    729.8
         45112  43  1200.0    728.4     730.10    712.9
         45114  43  1001.0    724.1     725.70    708.1
         45115  43   900.3    728.7     730.40    713.2
         45116  43   800.7    712.4     714.00    696.6
         45117  43   699.6    712.3     713.80    696.9
         45118  43   601.3    687.2     689.00    672.7
         45119  43   501.0    635.2     637.20    621.3
         45121  43   401.1    576.8     578.60    563.8
         45123  43   299.7    556.3     557.90    543.4
         45125  43   201.0    510.7     512.10    499.1
         45127  43   151.0    507.8     509.00    495.7
         45129  43    99.7    494.1     495.30    482.3
         45130  43    79.6    486.6     487.80    474.8
         45131  43    60.0    482.2     483.40    471.7
         45132  43    39.5    450.7     451.80    440.2
         45133  43    19.9    381.9     384.20    374.2
         45135  43     3.4    374.7     375.30    365.6

         fCO2(20)(final)
           final data reduction using the detector XCO2 (dry) output
         fCO2(20)(cruise)
           data reduction on cruise using an empirical water vapor  
           correction 
         fCO2(20)(new H2O)
           data reduction in Jan 2004 using an empirical water vapor  
           correction that was determined post-cruise
 


TABLE 7: Analysis statistics for fCO2(20)
 
         Total number of stations                                150
         Total number of stations sampled for fCO2 (full depth)   67
         Total number of Niskin bottles tripped                 4823
         Total number of Niskin bottles sampled for fCO2        1522
         Number of duplicates                                    140
         Number of bad values                                      6
         Number of questionable values                            48



TABLE 8: Table OF  pCO2 duplicate values

                          Dif.
         Key             (µatm)              #
         number   Depth    %    Dif.  Ave.  samps  Comment
         ------  ------  ------ ---   ----- -----  --------------------
           1101   200.1   4.4   0.7   644     2    B
           1111     2     4     0.8   503.1   2    B
           5108   999.7   5     0.7   718.9   2    B
           9112  1199.8   4.8   0.6   781     2    B
           9133    20.5   0.4   0.1   435.8   2    C
          10131    19.8   0.3   0.1   409.0   4    A & B, 4 bottles
          13105  2101     4.6   0.6   758     2    B
          17103   799.7   4.2   0.6   749.6   2    B
          18125     3.1   2.5   0.6   453.45  2    B
          25106  1700.4   0     0.0   770.8   2    C
          25107  1500.5               770.8   1    B, 1 dup bad 
          26135     2.3   3.6   0.8   453.2   2    B
          28235     2.2               424.4   1    B, 1 dup bad 
          33102  4000.4   1.7   0.2   775.15  2    B
          33135     2.5               384     1    B, 1 dup bad 
          41121   893.9   2.8   0.4   737.9   2    C
          43105  3000.8   1.3   0.2   760.15  2    B
          45103  4499.7   1.8   0.2   769.5   2    B
          45125   201     0.8   0.2   510.7   2    B
          45133    19.9   3.2   0.8   381.9   2    B
          47103  1999.7   4.2   0.6   751.2   2    B
          47113   748.8   3.5   0.5   707.85  2    B
          49111  1199.7   2.2   0.3   701.3   2    B
          49126   149.4               507.7   1    B, 1 dup bad  
          49132    20.3   3.9   1.0   371.75  2    B
          51113  1457.1   0.5   0.1   750.05  2    B
          51135     2.9   2.9   0.8   356.8   2    B
          52133     3.6               358.9   1    B, 1 dup bad 
          53112  1099.9   2.5   0.3   715.4   2    B
          53120   400.3   6.4   1.1   571.9   2    B
          54104  4304.7   0.5   0.1   762.5   2    B
          54111  1437.6   2.5   0.3   715.4   4    A & B, 2 bottles dup 
          54135     2.8               357.3   1    B, 1 dup bad 
          56133     3.2   3.3   0.9   359.7   2    B
          57205  2492.3   3.3   0.4   745.0   2    B
          57221   398.7   1.4   0.2   597.1   2    B
          61204  4297.4   1.9   0.2   763.2   2    B
          61215  1300.5   2.9   0.4   740.4   2    B
          61230   100.7   1.6   0.4   409.8   2    B
          63202  4999.8   1.7   0.2   765.4   2    B
          63214  1050.6   1.4   0.2   725.8   2    B
          65102  5001.8   2.4   0.3   765.4   2    B
          65108  2000.5   3.8   0.5   735     2    B
          65114  1099.3   0.6   0.1   766.9   2    B
          67203  4707.3   3.4   0.4   770     2    B
          67216  1100.5   1.5   0.2   729.1   2    B
          67218   800     3.3   0.5   732.2   2    B
          69104  4000.4   2.5   0.3   765.3   2    B
          69106  2999.5   0     0.0   757.1   2    B
          69112  1199.3   2.7   0.4   739.3   2    B
          71107  3349.7               761.5   1    B, 1 dup bad 
          71110  2650.8   1.8   0.2   751     2    B
          71113  1750     0     0.0   731.2   2    B
          72207  3549.7   0.3   0.0   760.5   2    B
          72210  2650.2   0.2   0.0   750.8   2    B
          72213  1749     1     0.1   733.7   2    B
          74103  4500.1   0.1   0.0   766.4   2    B

TABLE 8: Table OF  pCO2 duplicate values (Continued)

                          Dif.
         Key             (µatm)              #
         number   Depth    %    Dif.  Ave.  samps  Comment
         ------  ------  ------ ---   ----- -----  --------------------
          74107  2500.1   4.6   0.6   752.2   2    B
          75135     3.2   0.9   0.3   331.3   2    B
          76103  4244.4               760.2   1    B, 1 dup bad 
          76107  2248.6   1.9   0.3   749.4   2    B
          76110  1499.2   1.2   0.2   764.5   2    B
          78202  5000     3.4   0.4   765.1   2    B
          78206  2998.9   0.3   0.0   755.9   2    B
          80102  4150     7.1   0.9   758.3   2    B
          80106  2949.8   0.3   0.0   755.1   2    B
          80110  1750.6   0.8   0.1   762.8   2    B
          80126   190     0.3   0.1   420.1   2    B
          82203  4747.8   1.3   0.2   766.4   2    B
          82207  3549     0     0.0   761.6   2    B
          84102  5299.6   2     0.3   770.5   2    B
          84106  3799.5   0.6   0.1   768.1   2    B
          84112  1899.2   0.6   0.1   765     2    B
          84116  1099.9   0.4   0.0   897.9   2    B
          86101  5611.2   1.8   0.2   766.1   2    B
          86105  4399.6   2.1   0.3   765.6   2    B
          88204  4449.5   0.3   0.0   766.5   2    B
          88206  3849     1.7   0.2   763.0   2    B
          88217   949.2   1.9   0.2  1002.1   2    B
          90105  3499.8   3.9   0.5   761.6   3    A & B
          90115   898.3   3.3   0.3  1078.4   2    B
          94203  4002     0.4   0.1   764.8   2    B
          94206  2499.6   0.9   0.1   764.45  2    B
          94215   799.2              1151.3   1    B, 1 dup bad 
          96103  4150.3   0.7   0.1   766.95  2    B
          96106  3250.3   0.9   0.1   765.55  2    B
          98203  3997.9               770.4   1    B, 1 dup bad 
          98205  2996.7               757.4   1    B, 1 dup bad 
         100204  2797.3               756.4   1    B, 1 dup bad 
         100206  2200     0.4   0.1   762.5   2    B
         100214   849.5   3.7   0.3  1183.9   2    B
         104205  4147.9   2.1   0.3   779.15  2    B
         104207  3548.8   1.8   0.2   760.9   2    B
         104213  1748.6   0.8   0.1   791.7   2    B
         106206  3998.4   0.6   0.1   777     2    B
         106209  2798.8   1.8   0.2   757.5   2    B
         108112  1299.2   2.6   0.3   947.7   2    B
         108135     2.7   2.3   0.8   285.25  2    B
         110205  4400.3   1.2   0.2   777.9   2    B
         110212  1899.9   1.8   0.2   763.4   2    B
         110226   199.4   8.3   0.8  1048.7   2    B
         112105  4148     0.4   0.1   770.6   2    B
         112120   550.1   1.6   0.1  1433     2    B
         112133    14.5   1.6   0.6   277.8   2    B
         114103  4500.9   3.2   0.4   776.2   2    B
         114110  1600.6   0     0.0   804.7   2    B
         116203  4249.5   0.4   0.1   776.1   2    B
         116207  2249.5   0.7   0.1   755.3   2    B
         116216   749.2   2.8   0.2  1336.6   2    B
         118203  3999.4   3.9   0.5   771.6   2    B
 
TABLE 8: Table OF  pCO2 duplicate values (Continued)
  
                          Dif.
         Key             (µatm)              #
         number   Depth    %    Dif.  Ave.  samps  Comment
         ------  ------  ------ ---   ----- -----  --------------------
         118211  1199.5   5     0.5  1053.1   2    B
         118224   199.6   5.2   0.6   873.7   2    B
         118233     3.2   0.6   0.2   252.3   2    C
         118235     3.1   1.6   0.6   252.6   2    B
         120103  3599.9   0.4   0.1   775     2    B
         120108  2000                 767.1   1    B, 1 dup bad 
         120129    99.3   0     0.0   596.1   2    B
         122204  2999.6   0.2   0.0   769.8   2    B
         122212  1149.3   2.9   0.3  1037.1   2    B
         124105  2401.5   1.7   0.2   760.0   2    B
         124123   300.6   2.2   0.2  1099.6   2    B
         126203  3398.7   0     0.0   774.1   2    B
         126208  1899.2   0     0.0   758.3   2    B
         126225   185.5   3     0.4   855.2   2    B
         129103  3098.8   2.7   0.4   770.75  2    B
         129133    19.6   0.7   0.3   267.05  2    B
         130116   747.7   0.7   0.1  1177.2   2    B
         130125   184.6   5     0.6   815.6   2    B
         130129    90.4   6     0.8   756.8   2    B
         131113  1049.3   1     0.1  1090.7   2    A & B,1 dup bad 
         132103  2900.3   0.8   0.1   768.2   2    B
         132115   750.7   2.5   0.2  1185.1   2    B
         132130    50.4   0.4   0.1   323.4   2    B
         133133    19.1   1.1   0.4   313.3   2    B
         135105  1899.3   1.6   0.2   757.4   2    B
         135114   799.4   0.2   0.0  1177.5   2    B
         135128    79.6   1.5   0.4   419.25  2    B
         138203  2599.7   2.4   0.3   765.1   2    B
         138207  1599.3   0.9   0.1   780.0   2    B
         138231    10     0.2   0.1   318.7   2    B
         141104  3999.6   1.5   0.2   799.75  2    B
         141114  1199.6              1016.4   1    B, 1 dup bad 
         141126   219.8   2.2   0.2   933.8   2    B
         144203  4599.9   2.1   0.2   962.55  2    B
         144209  1899.6   0     0.0   750.2   2    B
         146103  4898.9   5.5   0.6   993.05  2    B
         146110  2800     0.7   0.1   764.85  2    B
         146126   199.8   0     0.0   910.2   2    B
         148203  4998.7   2.3   0.2  1001.15  2    B
         148220   548.4   3.8   0.3  1238.8   2    B
         150133    25.7   1.1   0.4   293.15  2    B
         -------------------------------------------
              Average     2.0   0.3     
              Stdev       1.7   0.3     
    
         Values were labeled questionable or bad based on the quality 
         control procedures listed below.  
              A = from same sample bottle
              B = from same Niskin
              C = from different Niskins sampled at same depth



TABLE 9: Total Alkalinity (TA) Certified Reference Material Measurements
         (DIC and pH values have been calculated from TA titrations)

                                                      pH (total scale)  Total
                          TA µmol/kg    DIC kg/kg         @ 25°C        Runs
         ---------------  ------------  ------------  ----------------  -----
         LEG 1
           System 1       2222.2 ± 3.6  2015.0 ± 3.7  7.891 ± 0.007     15
           System 2       2224.2 ± 3.2  2017.7 ± 3.4  7.893 ± 0.007     17
         LEG 2
           System 1       2222.5 ± 4.5  2012.1 ± 2.4  7.895 ± 0.009     16
           System 2       2222.9 ± 3.8  2016.1 ± 4.1  7.890 ± 0.009     15
           Manual Sys     2217.2 ± 2.1  2013.4 ± 0.5  7.888 ± 0.006      3
         
         BOTH LEGS
           System 1       2222.4 ± 3.8  2013.6 ± 3.4  7.891 ± 0.011     33
           System 2       2223.6 ± 3.5  2017.0 ± 3.8  7.891 ± 0.008     30
           Manual Sys     2217.2 ± 2.1  2013.4 ± 0.5  7.888 ± 0.006      3
         
         ALL SYSTEMS      2222.7 ± 3.6  2015.2 ± 3.5  7.891 ± 0.009     66
         
         CERTIFIED VALUES
           CRM Batch 59   2220.98       2007.1        7.895a
                                                      7.9674 ± 0.0005b  19
           TRIS                                       8.0855 ± 0.0003a  19
         
         CORRECTION FACTOR
           LEG 1
             System 1        0.9994        0.9961     0.004    
             System 2        0.9980        0.9947     0.002    
           LEG 2
             System 1        0.9988        0.9975     0.000    
             System 2        0.9991        0.9958     0.005    
             Manual Sys      1.0017        0.9969     0.007    



TABLE 10: Replicate analyses of dissolved oxygen concentration from the 
          test CTD cast

                                Niskin  Depth
                         Stn    Bottle   (m)     DO (µm)
                         ----   ------  -----    -------
                         test      1     170     277.2
                         test      2     170     277.2
                         test      3     170     276.9
                         test      4     170     277.1
                         test      5     170     276.8
                         test      6     170     276.8
                         test      7     170     277.1
                         test      8     170     276.8
                         test      9     170     276.7
                         test     10     170     277.4
                         test     11     170     277.6
                         test     12     170     274.5*
                         test     13     170     277.9
                         test     14     170     277.2
                         test     15     170     277.3
                         test     16     170     276.8
                         test     17     170     277.4
                         test     18     170     276.9
                         test     19     170     277
                         test     20     170     276.8
                         ------------------------------
                         Average                 277.1
                         STDV                      0.03

  * Outlier in replicate analyses not included in the average and 
    possibly due to errors in bottle volumes or sampling.



TABLE 11: Replicate analyses of dissolved oxygen concentration 
          (µmol/L) by Winkler titration from same Niskin bottle or 
          different bottles at same depth

           Station  Sample  Replicate 1  Replicate 2  Replicate 3  Replicate 4
           -------  ------  -----------  -----------  -----------  -----------
              1       1        276.1        266.8*       
              1       4        279.1        279.4        
              1       8        266.7        289.2        
              1      11        297.2        296.1        
              2       2        262.8        262.2        
              2      18        297.2        302.7*       297.4
              4       1        287.1        161.1*       
              5       4        277.3        266.3*       
              5      25        276.2*       279.9        
              6       1        302.1*       288.1        
              6      12        245.4        245.3        
              7       8        250.4        249.9        
              7      14        269.9*       261.1        
             10       6        286.6        286        
             10      32        306.3        306.8        
             11       4        286.2        286.5        
             11      35        307.6        308.3        307.6
             12      23        273.1        273.4        
             14       3        277.5        278        
             14      32        275.1        275.6        
             15       7        232.4        232.1        
             15   "27, 28"     274.3        275.6        
             16       2        241.1        241.6        
             16      24        279.8        279.9        
             19       4        264          264.5        
             19   "26, 27"     274.6        281.7*       
             20       4        231.1*       227.4        
             20      17        258          257.8        
             21   "25, 26"     275.5        275.1        
             24       7        265.7        265.1        
             24      25        259          259.3        
             25       5        284.3        284.3        
             25      20        241          241   
             25      28        263.8        264.4   
             26   "33, 35"     268.3        267.9   
             28       2        243.7        244.2   
             30       9        275.6        276.6   
             30      31        271.9        271.7   
             32      27        194          194.2   
             34   "33, 35"     269.6        270.2   
             40       1        270.2*       246.5   
             43       6        268.8        268.6   
             43      17        196.5        192.9   
             44       7        263.9        264.1   
             45       2        247          246.9   
             45      35        248.7        249.4   
             46      10        208.2        208.4   
             47       7        229.7        229.9   
             47   "31, 32"     247.1        247        
             49      33        240          239.8        

TABLE 11: Replicate analyses of dissolved oxygen concentration 
          (µmol/L) by Winkler titration from same Niskin bottle or 
          different bottles at same depth (continued)

           Station  Sample  Replicate 1  Replicate 2  Replicate 3  Replicate 4
           -------  ------  -----------  -----------  -----------  -----------
             51      15        195.5        195.9        
             51      32        278.3        278.6        
             52      11        200.4        200.1        
             52      32        240.2        240.4        
             53   "33, 35"     237.9        237.7        
             54      14        190.1        191.5        
             54      31        261.4        261.4        
             55       7        251.2        250.6        
             55      31        260          259.9        
             57       6        264.9        265.4        
             57      33        238.1        237.8        
             60       1        250.9        250.8        250.8
             60      13        218.7        216.1        216.9
             60      29        236          235.5        235.4
             60   "11,5.0"     248.1        247.7        246.3        247.3
             61       1        258.9        253.3*            
             61       2        253.1        251.7             
             61       5        251.7        252          252.6     
             61       7        252.9        253.1             
             62       1        250.9        251             
             62       3        251          250.8             
             62       5        250.8        250.7             
             62       7        251          251.5             
             63       8        261          260.9        261.5     
             63      13        190.1        190.1        190     
             63      17        187.9        187.6        187.9     
             63      24        212.6        212.8        212.5     
             63      29        234.3*       240          241.6     
             63      33        242.3        242.2             
             64       4        251.4        250.8             
             64      12        186.8        182.4*       
             64      30        237.6        237.8        
             65       1        251.1        251        
             65       4        251.8        251.6        
             65      17        170.6        170.6        
             66       3        251.6        251.4        
             66       9        247.4        246.8        
             66      15        181.1        181          180.8
             66      28        228.2        228.8        
             67       7        251.2        250.8        251.1
             67      20        191.6        191.5        191.6
             68       1        251.6        251.8        
             68       3        251.6        251.9        
             68       7        251.3        251.5        
             68      16        189.5        189.7        
             68      25        209.5        209.4        
             68      33        226.2        226.1   
             69       1        251.1        251.3   
             69       3        251.5        251.3   
             69       5        250.9        250.6   

TABLE 11: Replicate analyses of dissolved oxygen concentration 
          (µmol/L) by Winkler titration from same Niskin bottle or 
          different bottles at same depth (continued)

           Station  Sample  Replicate 1  Replicate 2  Replicate 3  Replicate 4
           -------  ------  -----------  -----------  -----------  -----------
             69      16        180.9        181.3   
             69      33        229.8        229.8   
             70       9        246.1        245.8   
             70      22        213.5        213.1   
             70   "12,3.0"     192.2        191.3   
             71       1        251.6        251.9   
             71       5        251.4        251.6   
             71      18        169.8        170   
             71      30        242.8        242.9   
             72      12        246.3        246   
             72      28        217          217.1   
             73       1        246.5        246.6   
             73       3        246.9        246.6   
             73       5        245.9        246.2   
             73      16        161.8        162.4   
             73      33        213.8        213.8   
             74       1        246.1        246.3   
             74       4        247.3        247   
             74      17        171.6        171.6   
             74      21        195.4        195   
             74      33        214          214.1   
             74      35        213.6        213.8   
             75       1        246.4        246.4   
             75       5        246.9        246.6   
             76       1        246.6        246.7   
             76       4        247          246.8   
             76      18        182.5        182.3   
             77       1        247.3        246.4   
             77       5        246.8        247   
             77      23        197.8        197.4   
             78       4        246.4        246.8   
             78      10        214.2        214.4   
             79       1        246.3        246.8   
             79       5        246.1        246   
             79      18        154*         158.2   
             79      33        212.7        212.5   
             80       3        249.2        249.3   
             80      14        161.4        161.1   
             80      32        229.9        229.7   
             81       1        249.3        249.6   
             81       2        249.6        249.8   
             82       2        249.8        249.6   
             82      28        213          212.6   
             83       1        249.3        249   
             83       5        249.3        248.9   
             83      18        132.2        132.2   
             84       3        238.4*       249.3   
             84      15        181.4        181.6   
             85       1        248.6        249.2   
             85       2        248.8        249.2   

TABLE 11: Replicate analyses of dissolved oxygen concentration 
          (µmol/L) by Winkler titration from same Niskin bottle or 
          different bottles at same depth (continued)

           Station  Sample  Replicate 1  Replicate 2  Replicate 3  Replicate 4
           -------  ------  -----------  -----------  -----------  -----------
             86       1        249.7        248.8   
             86       5        249.2        248.8   
             86      19        131.2        130.8   
             87       1        254.6        254.2   
             87      19        130          130.3   
             88       1        254.5        254   
             88      16        173          172.8   
             89       1        253.8        253.5   
             89       3        252.3        253.8   
             89       5        252.2        251.9   
             89      16        133          131.7   
             90       2        253.3        253.8   
             90      18        116.2        115.7   
             91       1        252.9        252.4   
             91      18         94.70        95.20    
             92       1        251.9        251.8   
             92       2        251.7        252   
             92      18        110.9        110.3   
             92      33        215.7        215.8   
             94       2        249          249.3   
             94      14        117.9        117.5   
             95       1        256.4*       245.3   
             95       6        243.2        243.4   
             95      23         74.00        73.90    
             96       2        243.5        243.2   
             96      22         70.50        70.80    
             96      32        220.8        220.2   
             97       2        246.8        246.9   
             97      18         93.20        96*   
             98       2        245.9        249.2*   
             98      19         81.00        80.60    
             98      32        209          209   
             99       2        248.1        248   
             99      21         94.80        95.00    
             99      23         94.00        93.90    
            100       2        250.5        250.7   
            100      22         76.50        76.20    
            100      32        211.2        211   
            101       1        250.9        251.2   
            101      19         71.60        71.60    
            104       2        252          251.9   
            104      23         72.90        72.90    
            104      33        206.7        206.7        
            105       1        253.1        253.3        
            105       4        250.1        249.9        
            105      25         79.30        79.70         
            106       2        253.9        253.6        
            106      22         59.50        59.50         
            106      33        206.8        206.6        
            107       1        252          252.2        

TABLE 11: Replicate analyses of dissolved oxygen concentration 
          (µmol/L) by Winkler titration from same Niskin bottle or 
          different bottles at same depth (continued)

           Station  Sample  Replicate 1  Replicate 2  Replicate 3  Replicate 4
           -------  ------  -----------  -----------  -----------  -----------
            107      18         70.30        70.20         
            107      32        206.6        206.2        
            108       2        253.4        254.2        
            108      21         51.00        51.20         
            108      32        211.6        211.8        
            109       2        254.1        254.4        254.2
            109      14        225.3        225.5        
            109      22         50.40        51.70         
            110       2        254.4        254.5   
            110      21         51.40        51.00    
            111       4        250.7        250.8   
            111      24         67.70        67.50    
            111      30         83.30        83.70    
            112       4        253.6        254.5   
            112      24         96.20        96.40    
            112      32        179.8        179.9   
            113       5        254.3        254   
            113      17         92.70        92.70    
            113      23         89.60        89.50    
            114       6        255.5        255.9   
            114      25        102.3        102.1   
            114      32        186.4        186.5   
            115       1        249          249.2   
            115      21         64.60        64.50    
            115      33        205.5        205.2   
            116       2        252.1        252.2   
            116      20         77.60        77.30    
            116      32        207.9        207.8   
            117       4        259.6        259.9   
            117      22         63.70        63.00    
            118       2        257          257.1   
            118      19         62.60        62.20    
            118      33        206.8        206.9   
            119       1        254.8        254.7   
            119      22         55.60        55.40    
            119      35        206.6        206.9   
            120       4        254.8        255.1   
            120      24        140          140.3   
            120      33        205.4        205.1   
            121       3        255.2        255.1   
            121      19         70.00        69.90    
            121      33        206.7        206.5   
            122       2        255.4        255.3   
            122      18         87.80        87.60    
            122      33        209.1        209   
            123       1        252          252   
            123      17        131.6        131.8   
            123      29        155.3        155.1   
            124       3        255.6        256   
            124      28        137.2        137.4   

TABLE 11: Replicate analyses of dissolved oxygen concentration 
          (µmol/L) by Winkler titration from same Niskin bottle or 
          different bottles at same depth (continued)

           Station  Sample  Replicate 1  Replicate 2  Replicate 3  Replicate 4
           -------  ------  -----------  -----------  -----------  -----------
            124      30        205.5        205.8   
            125       1        253          253.4   
            125      19        112.8        113.8   
            125      35        255          254.7   
            126       4        256.2        256.3   
            126      13        160.7        161   
            126      26         98.70        98.10    
            127       4        257          257.4   
            127      28         99.40        98.90    
            127      33        209.2        209.1   
            128       2        259.3        259.1   
            128      16        153.7        153.9   
            128      28         96.70        96.30    
            129       3        255          255   
            129      19        136.7        136.9   
            129      32        207.2        207.5   
            130       1        253.6        253.4   
            130      35        213.5        213.2   
            131       3        257.6        258   
            131      26        108.5        108.7   
            131      33        212.3        212.4   
            132       4        253.6        253.3   
            132      19        121.5        121   
            132      28        132.5        132.5   
            133       1        261.2        261   
            133      23        105.4        105.3   
            133      32        204.6        204.8   
            134       1        257.9        257.7   
            134      23         96.80        96.60    
            134      35        210.5        210.3   
            135       6        245.9        245.9   
            135      20        116.9        116.6   
            135      33        208.8        208.8   
            136       1        256.6        256.2   
            136       8        229.2        229.6   
            136      26        175.7        175.5   
            137       2        256.9        257.2   
            137      24        113.4        113.3   
            137      32        209.3        209.5   
            138       2        255.8        256   
            138      20         83.20        83.00    
            138      31        208.9        209.1   
            139       2        232.5        232.2   
            139      23         95.80        95.60    
            140       3        240.9        241.2   
            140      23         70.10        70.30    
            140      31        207.3        207.5   
            141       3        236.2        236.3   
            141      15        166.4        166.7   
            141      32        209.1        209.2   

TABLE 11: Replicate analyses of dissolved oxygen concentration 
          (µmol/L) by Winkler titration from same Niskin bottle or 
          different bottles at same depth (continued)

           Station  Sample  Replicate 1  Replicate 2  Replicate 3  Replicate 4
           -------  ------  -----------  -----------  -----------  -----------
            143      13        158.7        158.9   
            144       2        230.2        230.3   
            144      15        158.9        158.8   
            144      31        169.2        169.5   
            145       1        228          228.1   
            145      23        104.3        104.7   
            145      35        212.9        212.7   
            146       4        234.1        234.3   
            146      16        174.5        174.3   
            146      25        101.8        101.9   
            147       4        233.2        233.6   
            147      28        106.3        106.3   
            147      33        209.7        209.7   
            148       1        228.6        229.2   
            148      23         90.70        90.60    
            148      33        210.3        210   
            149       2        228.9        228.6   
            149      24         86.50        86.20    
            149      35        208.4        208.4   
            150       3        231.1        231.2   
            150      24         85.90        86.20    
            150      31        205.6        205.6   



TABLE 12:  After cruise recalibration of the volumes (cm3) 
           of the oxygen bottles

                    Old         New
           Bottle  Volume      Volume    Difference
           ------  -------     -------   ----------
             1     145.853     145.610    -0.243
             2     145.200     145.209     0.009
             3     145.318     149.967     4.649
             4     143.917     143.908    -0.009
             5     139.471     138.748    -0.723
             6     145.464     145.470     0.006
             7     145.443     145.441    -0.002
             8     152.778     152.796     0.018
             9     142.276     146.019     3.743
            10     145.662     145.666     0.004
            11     143.687     143.643    -0.044
            12     145.292     147.003     1.711
            13     142.335     142.307    -0.028
            14     141.151     145.220     4.069
            15     145.456     145.507     0.051
            16     145.908     145.897    -0.011
            17     145.645     145.644    -0.001
            18     144.759     144.734    -0.025
            19     142.898     142.913     0.015
            20     143.300     143.310     0.010
            21     146.299     141.180    -5.119
            22     144.406     147.777     3.371
            23     145.704     148.320     2.616
            24     141.570     152.070    10.500
            25     145.085     145.109     0.024
            26     145.599     145.606     0.007
            27     147.751     146.772    -0.979
            28     144.469     144.459    -0.010
            29     147.404     147.396    -0.008
            30     146.101     146.131     0.030
            31     146.039     146.004    -0.035
            32     145.111     145.152     0.041
            33     145.501     145.501     0.000
            34     146.663     146.678     0.015
            35     143.309     143.347     0.038
            36     147.371     147.429     0.058
            37     146.290     150.489     4.199
            38     140.623     144.152     3.529
            39     146.959     151.425     4.466
            40     144.179     144.183     0.004
            41     139.747     141.192     1.445
            42     143.726     150.186     6.460
            43     146.369     146.369     0.000
            44     142.137     142.137     0.000
            45     142.478     142.478     0.000
            46     143.805     143.805     0.000
            47     143.494     143.500     0.006
            48     145.665     142.890    -2.775
            49     144.254     144.254     0.000
            50     145.715     141.225    -4.490
            51     147.807     147.809     0.002
            52     146.055     146.055     0.000
            53     143.431     143.431     0.000
            54     143.347     145.342     1.995
            55     144.658     144.715     0.057
            56     146.009     146.032     0.023
            57     142.607     144.083     1.476
            58     145.371     145.372     0.001
            59     144.344     144.343    -0.001
            60     145.292     145.244    -0.048
            61     146.185     146.159    -0.026
            62     142.781     142.786     0.005
            63     144.319     144.307    -0.012
            64     144.039     144.042     0.003
            65     145.311     149.630     4.319
            66     144.080     144.153     0.073
            67     143.908     143.892    -0.016
            68     137.386     146.368     8.982

TABLE 12:  After cruise recalibration of the volumes (cm3) 
           of the oxygen bottles (continued)

                    Old         New
           Bottle  Volume      Volume    Difference
           ------  -------     -------   ----------
            69     145.505     145.539     0.034
            70     143.273     143.276     0.003
            71     146.396     146.377    -0.019
            72     145.602     145.555    -0.047
            73     145.019     145.027     0.008
            74     146.627     146.634     0.007
            75     144.237     144.236    -0.001
            76     144.935     144.856    -0.079
            77     146.540     146.552     0.012
            78     143.597     143.551    -0.046
            79     142.704     148.421     5.717
            80     146.607     145.227    -1.380
            81     147.842     147.813    -0.029
            82     145.624     145.493    -0.131
            83     149.920     143.503    -6.417
            84     149.503     142.045    -7.458
            85     143.718     143.666    -0.052
            86     145.641     145.552    -0.089
            87     143.796     143.654    -0.142
            88     140.322     140.321    -0.001
            89     138.752     138.633    -0.119
            90     138.785     138.658    -0.127
            91     145.587     142.249    -3.338
            92     144.516     142.404    -2.112
            93     151.851     149.504    -2.347
            94     145.714     145.720     0.006
            95     149.465     149.364    -0.101
            96     151.184     148.882    -2.302
            97     144.609     144.592    -0.017
            98     152.251     152.200    -0.051
            99     144.545     144.552     0.007
           100     147.346     147.187    -0.159
           101     139.500     139.479    -0.021
           102     149.319     149.298    -0.021
           103     147.485     147.484    -0.001
           104     138.295     138.310     0.015
           105     139.030     139.035     0.005
           106     144.610     144.606    -0.004
           107     148.793     148.778    -0.015
           108     146.952     146.951    -0.001
           109     149.911     149.928     0.017
           110     146.285     142.968    -3.317
           111     149.657     141.784    -7.873
           112     142.400     143.215     0.815
           113     143.206     143.217     0.011
           114     139.272     139.267    -0.005
           115     139.648     139.631    -0.017
           116     141.125     141.138     0.013
           117     141.218     142.124     0.906
           118     147.477     147.484     0.007
           119     148.834     148.847     0.013
           120     147.002     147.023     0.021
           121     144.803     144.080    -0.723
           122     141.945     141.949     0.004
           123     143.415     143.134    -0.281
           124     145.482     144.116    -1.366
           125     145.685     145.706     0.021
           126     144.523     144.527     0.004
           127     145.756     145.780     0.024
           128     140.523     140.521    -0.002
           129     143.820     143.811    -0.009
           130     145.730     138.828    -6.902
           131     145.849     145.855     0.006
           132     145.156     145.146    -0.010
           133     145.696     145.673    -0.023
           134     143.807     143.807     0.000
           135     148.692     148.692     0.000
           136     141.083     141.083     0.000
           137     143.675     143.675     0.000

TABLE 12:  After cruise recalibration of the volumes (cm3) 
           of the oxygen bottles (continued)

                    Old         New
           Bottle  Volume      Volume    Difference
           ------  -------     -------   ----------
           138     145.247     145.247     0.000
           139     144.459     144.459     0.000
           140     143.336     143.336     0.000
           141     143.962     143.971     0.009
           142     144.590     142.608    -1.982
           143     145.759     145.776     0.017
           144     137.683     145.339     7.656
           145     145.356     145.346    -0.010
           146     142.249     142.273     0.024
           147     145.810     145.800    -0.010
           148     144.984     144.954    -0.030
           149     146.996     146.998     0.002
           150     145.100     145.094    -0.006
           151     142.395     142.369    -0.026
           152     144.586     144.983     0.397
           153     147.093     147.102     0.009
           154     145.219     142.119    -3.100
           155     150.067     150.055    -0.012
           156     138.514     143.383     4.869
           157     148.070     144.191    -3.879
           158     145.740     145.788     0.048
           159     143.852     143.853     0.001
           160     145.975     145.999     0.024
           161     144.786     144.785    -0.001
           162     144.560     144.304    -0.256
           163     146.144     146.096    -0.048
           164     144.518     144.296    -0.222
           165     144.623     144.514    -0.109
           166     141.617     141.524    -0.093
           167     144.192     144.162    -0.030
           168     145.917     145.651    -0.266
           169     145.682     145.604    -0.078
           170     146.535     146.342    -0.193
           171     139.221     139.144    -0.077
           172     150.611     150.569    -0.042
           173     145.165     145.101    -0.064
           174     145.379     145.303    -0.076
           175     144.814     144.744    -0.070
           176     141.770     141.687    -0.083
           177     143.827     143.722    -0.105
           178     145.031     144.941    -0.090
           179     145.668     143.528    -2.140
           180     147.606     147.524    -0.082



TABLE 13: Shipboard standardization of thiosulfate solution during 
          A16N_2003a cruise

 THIO   STANDARD  STARTING  ENDING
BOTTLE    FILE    STATION   STATION  INTERCEPT  SLOPE   REMARKS
------  --------  --------  -------  ---------  ------  -----------------
   1       2          1         4     -0.004    24.743  
   2       6          4         8      0.1515   24.585  
   3       7          7        15      0.1155   23.87   
   4       9         16        18      0.0885   24.635  
   5      10         19        23      0.1117   24.312  
   6      11         24        29      0.05     24.96   
   7      15         30        37      0.143    24.495  
   8      16         37        46      0.1255   24.135  
   9      17         46        50      0.0405   24.845  
  10      18         51        58      0.0072   24.988  
  11      21         59        61      0.0042   25.075  
  12      22         62        65     -0.0015   25.005  
  13      23         66        71     -0.0025   24.87   
  14      24         72        79     -0.01     25.355  Digital Pipette
  15      25         80        86     -0.0007   24.97   
  16      26         87        92      0.008    24.755  
  17      27         93        97      0.002    24.735  
  18      30         98        98      0.0045   24.92   
  19      30G        98       106      0.0057   24.873  
  19                                   0.001    24.89   End of the Bottle
  20      31G       107       115      0.002    24.88   
  21                                   0.0096   24.719  5-20ml KIO3
  21      32G       116       123      0.0043   24.747  2-16ml KIO3
  22      33G       124       131      0.0056   24.757  
  23      35G       132       140      0.0097   24.753  
  24      36G       141       148      0.0063   24.682  
  24                                   0.009    24.685  Repeat
  25      37G       149       150      0.007    24.697  
  25      38                           0.007    24.678  
  25      39                           0.0039   24.649  
-------------------------------------------------------------------------
AVERAGE                                0.03015  24.7421



TABLE 14: Post cruise comparison of volume delivery of a manual and 
          the problematic automatic pipette used for stations 
          72-79 by standardization of KIO3 solution with same batch 
          Na2S2O3 solution. The correction of 1.01531 was applied 
          to all samples in this station range.

                AUTOMATIC          MANUAL
RUN  FACTOR     INTERCEPT    R2    FACTOR    INTERCEPT    R2      RATIO
---  ---------  ---------  ------  --------  ---------  ------  --------
 1   25.050     -0.0023    1.0000  24.577     0.0127    1.0000  
 2   25.035     -0.0008    1.0000  24.690     0.0057    1.0000  
 3   25.017     -0.0005    1.0000  24.685     0.0040    1.0000  
 4   25.205     -0.0052    1.0000  24.673     0.0050    1.0000  
 5   25.067      0.0012    1.0000  24.687     0.0063    1.0000  
 6   24.990      0.0022    1.0000  24.690     0.0070    1.0000  
 7   25.112     -0.0030    1.0000  24.670     0.0065    1.0000  
 8   25.047      0.0030    1.0000  24.700     0.0060    1.0000  
 9   25.290     -0.0063    1.0000  24.685     0.0075    1.0000  
10   24.910      0.0040    1.0000  24.658     0.0075    1.0000  
11   24.861      0.0050    1.0000  24.697     0.0065    1.0000  
12                                 24.693     0.0083    1.0000  
---  ---------  ---------  ------  --------  ---------  ------  --------
AVG  25.05309   -0.0002            24.67542   0.0069            1.015306
STD   0.120788   0.0037             0.03323   0.0022     
RSD   0.5%                          0.1%        





APPENDIX

         WOCE QUALITY FLAG DEFINITIONS FOR WATER BOTTLES.

         Flag  Definition
         ----  --------------------------------------
          1    Bottle information unavailable
          2    No problems noted
          3    Leaking
          4    Did not trip correctly
          5    Not reported
          7    Unknown problem
          9    Samples not drawn from this bottle


         WOCE WATER QUALITY FLAG DEFINITIONS.

         Flag  Definition
         ----  --------------------------------------
          1    Sample drawn but analysis not received
          2    Acceptable measurement
          3    Questionable measurement
          4    Bad measurement
          5    Not reported
          6    Mean of replicate measurements
          9    Sample not drawn for measurement
         




DATA PROCESSING NOTES


DATA      CONTACT    DATA TYPE      DATA STATUS SUMMARY
--------  ---------  -------------  --------------------------------------------
04/01/03  Swift      CTD/BTL        List of cruise parameters
          Here is the current parameter list for the 2003 A16N son-of-WOCE 
          cruise.

          Kristin Sanborn of ODF gave me the list. She has been working with Bob 
          Williams on preparations for the bottle data processing on that 
          cruise. Of course some of the water samples generate many individual 
          parameters. An asterisk after a value indicates it comes from the CTD 
          computer. An f before a value indicates it's a flag.

          stnnbr     castno       
          btlnbr     (bottle serial number)   sampno   (niskin number + castno*100)
          lat        (decimal degrees)        lon      (decimal degrees)
          year*      month*   day*            hour*    min*     
          second*    (decimal seconds)        ctdprs*  ctdsal*  fctdsal    
          ctdtmp*    ctdoxy*  fctdoxy         trans*   (Bishop tranmissometer)  
          pic*       (Bishop particulate inorganic carbon)
          scatter*   (Bishop scatter meter)   sigma0*  theta*
          cfc11      fcfc11                   cfc12    fcfc12    
          cfc13      fcfc13                   ccl4     fccl4
          hcfc22     (AOML HCFC-22)           fhcfc22
          ch3cl      (methyl chloride)        fch3cl       
          ch3br      (methyl bromide)         fch3br
          aomlcfc11  (AOML cfc-11)            faomlcfc11
          hcfc141b   (AOML HCFC-141b)         fhcfc141b
          ch3i       (methyl iodide)          fch3i
          aomlcfc13  (AOML cfc13)             faomlcfc13
          aomlccl4   (AOML ccl4)              faomlccl4       
          tcarbn     ftcarbn
          pco2       fpco2       nitrat       fnitrat       nitrit       fnitrit
          phspht     fphspht     silcat       fsilcat       oxygen       foxygen
          hel3       fhel3       tritum       ftritum       alkali       falkali
          ph         fph         doc          fdoc          don          fdon
          
          There appear to be two different CFC groups working at the same time 
          on A16N, each apparently drawing their own samples.
			
08/27/03  Bullister  CTD/BTL/SUM    Raw shipboard prelim data available via ftp
          You have my permission to obtain the data from Frank and post them
          at the website.  You should include the caveats that these data are
          the raw shipboard version, are still preliminary and will be updated.

09/04/03  Bullister  DOC            Submitted
          This is from John Bullister and is the project instructions 
          document for A16N_2003a (Ron Brown). It's the closest thing that 
          he had to cruise docs, but he's working on a preliminary post-
          cruise report.  When he completes the work-in-progress, we should 
          replace the new doc with the one he's working on now.
                    

09/08/03  McTaggart  CTD            Submitted available on NOAA ftp site  
          A16N preliminary CTD data files in WOCE format are ready for you on 
          our FTP site:  ftp.pmel.noaa.gov under /ctd/woce/a16n.



DATA      CONTACT    DATA TYPE      DATA STATUS SUMMARY
--------  ---------  -------------  --------------------------------------------
09/08/03  Diggs      CTD            Data retrieved from NOAA ftp site
          I have received your files and am checking them over.  

09/10/03  Delahoyde  BTL/SUM         BTL Parameters Submitted:
            BTLNBR  CTDRAW  CTDPRS  CTDTMP  CTDSAL  CTDOXY  THETA   SALNTY  
            OXYGEN  SILCAT  NITRAT  NITRIT  PHSPHT  CFC-11  CFC-12  CFC113  
            TCO2    TALK    PH      PCO2
            
          These data were provided by:
          
          PARAMETER/PROGRAM   | NAME                  | EMAIL ADDRESS
          --------------------|-----------------------|-----------------------------
          Chief Scientist     | John Bullister/PMEL   | bullister@pmel.noaa.gov   
          CTDO/S/O2/nutrients | Greg Johnson/PMEL     | gjohnson@pmel.noaa.gov
          Nutrients           | Calvin Mordy/PMEL     | mordy@pmel.noaa.gov
                              | Jia-Zhong Zhang/AOML  | zhang@aoml.noaa.gov
          Total CO2(DIC),PCO2 | Dick Feely/PMEL       | feely@pmel.noaa.gov 
                              | Rik Wanninkhof/AOML   | rik.wanninkhof@noaa.gov
          CFC                 | John Bullister/PMEL   | bullister@pmel.noaa.gov
          CFC                 | Mark Warner/UW        | mwarner@ocean.washington.edu  
          HCFs                | Shari Yvon-Lewis/AOML | syvon@aoml.noaa.gov
          He/Tr               | Peter Schlosser/LDEO  | peters@ldeo.columbia.edu
          14C/13C             | Ann McNichol/WHOI     | amcnichol@whoi.edu     
          
          The data included in these files are preliminary, and are subject 
          to final calibration and processing. They have made available for 
          public access as soon as possible following their collection. 
          Users should maintain caution in their interpretation and use. 
          Following American Geophysical Union recommendations, the data 
          should be cited as: "data provider(s), cruise name or cruise ID, 
          data file name(s), CLIVAR and Carbon Hydrographic Data Office, La 
          Jolla, CA, USA, and data file date." For further information, 
          please contact one of the parties listed above or whpo@ucsd.edu. 
          Users are also requested to acknowledge the NSF/NOAA-funded U.S. 
          Repeat Hydrography Program in publications resulting from their use.
                    
          A16N water property codes for WOCE ".sum" file "PROPERTIES" column:
          
                Water           Water           Water           Water 
          Code  Property  Code  Property  Code  Property  Code  Property 
          ----  --------  ----  --------  ----  --------  ----  --------
             1  Salinity     8  CFC-12      25  PCO2       101  PIC
             2  O2           9  Tritium     26  PH         102  Al
             3  SIO3        10  He          27  CFC-113    103  Fe
             4  NO3         12  del14C      32  DON        104  AlkNO3
             5  NO2         13  del13C      40  POC        105  Carbohydrates
             6  PO4         23  TCO2        43  DOC        106  CDOM
             7  CFC-11      24  TALK       100  HCFCs      



DATA      CONTACT    DATA TYPE      DATA STATUS SUMMARY
--------  ---------  -------------  --------------------------------------------
09/26/03  McTaggart  CTD            Submitted
          There is a file for you on our anonymous FTP site, ftp.pmel.noaa.gov, 
          under /ctd/woce/a16n.  It's called a16n_allo.clb and it is the 
          preliminary calibrated discrete CTD measurements and associated sample 
          salinities and oxygens.
                  
          In generating this file, I found an error I had made in applying 
          the preliminary calibrations to the profile data.  The .ctd files 
          now on our FTP site are correct and should be downloaded again.  I 
          apologize for this oversight.  And I changed the expocode in the 
          header to be a 13-character string instead of a 12-character 
          string as it is on the WHPO website (e.g. suffix '_01' instead of '_1').
                    
09/29/03  Diggs      CTD            Website Updated  CTD submitted and online
          CTD data recalibrated.  Updated versions of the ctd and ctd-
          exchange on website.  
                    
10/03/03  Johnson    CTD/BTL        Defined ctd/nuts/O2 PIs
          For A16N please keep me (Gregory Johnson) as PI for CTD/O2 and S, but 
          Mordy & Zhang for nutrients, and Zhang for bottle O2.
			
10/20/03  Diggs      CTD/SUM/BTL    Website Updated with Formatted files
          CTD, SUM, BTL available along with Exchange formatted versions on 
          WHPO website.
                    
10/22/03  Diggs      CTD/BTL        Website Updated; Citation added to files
          Repackaged all zip files (WOCE CTD, Exchange CTD, and WOCE Bottle 
          w/ SUM) with new citation files per request from Talley and 
          Swift).
                    
10/29/03  Diggs      SUM/CTD/BTL    Updated archive citations
          Updated all citations (00_README files) embedded in each zip 
          archive as well as the Exchange formatted bottle file. Bottle 
          Exchange updated to reflect accurate ExpoCodes for each station 
          from updated summary file.
          
10/30/03  Kappa      DOC            Cruise Report PDF & ASCII versions Updated
          • added links from TOC to text in PDF version
          • made a text version
          • added these WHPO-SIO Data Processing Notes
          
11/03/03  Coartney   Cruise Report  Website Updated; New PDF & ASCII docs online

01/30/04  Diggs      CTD/BTL/SUM    Website Updated; line identifiers changed
          Corrected all cruise line identifiers to A16N (from A16N_2003A) as per 
          Jim Swift's request.
			
02/20/04  Kappa      Cruise Report  Updated PDF & ASCII versions made
			
06/11/04  Diggs      CTD            Website Updated; missing files added
          A transmission error occurred from PMEL to SIO, resulting in only 80 
          files being at the WHPO. Alison MacDonald from WHOI noticed the 
          problem. I re-ftp'd the files, format checked them, convert them to 
          Exchange, and put all of the ftp files back on the website. All checks 
          out.
			


DATA      CONTACT    DATA TYPE      DATA STATUS SUMMARY
--------  ---------  -------------  --------------------------------------------
10/27/04  Hansell    DOC/TDN       Submitted data & sampling procedures report
          The data disposition is: Public  
          The file format is:      Plain Text (ASCII) 
          The archive type is:     NONE - Individual File 
          The data type(s) is:     Bottle Data (hyd)
            • Dissolved Organic Carbon 
            • Total Dissolved Nitrogen for A16N2003 Line 
            • Documentation     
          The file contains these water sample identifiers:
            • Cast Number (CASTNO)
            • Station Number (STATNO)
            • Bottle Number (BTLNBR)
            • Sample Number (SAMPNO)
          HANSELL, DENNIS would like the following action(s) taken on the data: 
            • Merge Data
            • Place Data Online 

12/10/04  Kozyr      Cruise Report  Submitted CO2 report
          I am attaching here 3 files with reports on measured carbon fields. 
          You will have to decide what and how much information you need for 
          cruise report.

12/10/04  Kozyr      CO2            Submitted  TCARBN, TALK, pH, and pCO2
          I have just submitted the final TCARBN, TALK, pH, and pCO2 data for 
          A16_2003 cruise for merging into the hydrographic data file. Could you 
          with the new numbers. Please, let me know if you have any questions 
          regarding the data. 

12/10/04  Kozyr      CO2            Submitted
          This is information regarding line A16N_2003
               ExpoCode:      33RO200306_01 33RO200306_02
               Cruise Date:   2003/06/19 - 2003/08/11
               From:          KOZYR, ALEX
               Email address: kozyra@ornl.gov
               Institution:   CDIAC/ORNL
               Country:       USA
          
          The file:  
               a16n_2003_carbn_final.txt - 308958 bytes
          has been saved as:
               20041210.063700_KOZYR_A16N_2003_a16n_2003_carbn_final.txt
          in the directory:  
               20041210.063700_KOZYR_A16N_2003
          The data disposition is:
               Public  
          The bottle file has the following parameters:
               TCARBN, TALK, PCO2, PH
          The file format is:
               WOCE Format (ASCII) 
          The archive type is:
               NONE - Individual File 
          The data type(s) is:
               Bottle Data (hyd)
          The file contains these water sample identifiers:
               Cast Number (CASTNO)
               Station Number (STATNO)
               Bottle Number (BTLNBR)
               Sample Number (SAMPNO)
          KOZYR, ALEX would like the following action(s) taken on the data:
               Merge Data
          Any additional notes are:
               This is the final bottle TCARBN, TALK, pH, and pCO2 data. I have 
               merged these numbers from two  different files I received from 
               PMEL and AOML CO2 measurement groups. New quality flags were 
               assigned according to QA-QC work. Please let me know if you need 
               more information on these data.



DATA      CONTACT    DATA TYPE      DATA STATUS SUMMARY
--------  ---------  -------------  --------------------------------------------
12/10/04  Anderson   CO2            Website Updated OnLine
          Copied files submitted by A. Kozyr from INCOMING to     
            .../a16n_2003a/original_data/20041210_KOZYR_A16N_2003.
            These files contain updated TCARBN, TALK, PCO2, and PH.
          I will merge into online file.
      
12/17/04  Bullister  Cruise Report  Submitted Final cruise report  
      
12/29/04  Mordy      NUTs           Submitted by Calvin Mordy  
            Date:    Wed, 29 Dec 2004 13:44:00 -0800 (PST)
            From:    WHPO Website <http@odf.ucsd.edu>
            To:      Calvin.W.Mordy@noaa.gov, jrweir@odf.ucsd.edu, whpo@ucsd.edu
            Subject: WHPO DATA A16N: BOT from MORDY

          This is information regarding line: A16N
                     ExpoCode:      33RO200306_01 _02
                     Cruise Date:   2003/06/04 - 2003/08/11
                     From:          MORDY, CALVIN
                     Email address: Calvin.W.Mordy@noaa.gov
                     Institution:   NOAA/PMEL
                     Country:       USA
          
          The file:  A16N-Apr14nuts-submitted.xls - 1207296 bytes
              has been saved as:  20041229.134359_MORDY_A16N_A16N-Apr14nuts-
              submitted.xls in the directory:  20041229.134359_MORDY_A16N
          The data disposition is:
              Public  
          The bottle file has the following parameters:
              SILCAT, NITRAT, NITRIT, PHSPHT
          The file format is:
              MS Excel (Binary) 
          The archive type is:
              NONE - Individual File 
          The data type(s) is:
              Bottle Data (hyd)
          The file contains these water sample identifiers:
              Cast Number (CASTNO)
              Station Number (STATNO)
              Bottle Number (BTLNBR)
          MORDY, CALVIN would like the following action(s) taken on the data:
              Merge Data
              Place Data Online
              Update Parameters
          Any additional notes are:
              Data are provided in µmole/l and µmole/kg.  The lab temperature 
              and the CTD bottle salts that were used in the unit conversion 
              are also provided.
          
      
12/30/04  Bullister  Cruise Report  Submitted Oxygen Data Report  
          The cruise we did was A16N_2003 (not p16n_2003).
          I forwarded Jim Swift's directive (see next message) to all the 
              investigators on A16N_2003 last February, advising them to forward 
              data and documentation directly to the CCHDO-WHPO.  I'll send out 
              another reminder.
          In addition to the carbon data and documentation, I have copies here 
              of the revised CTD and bottle salinity data from Kristy McTaggart, 
              revised CFC data from our group, revised oxygen data (and documen-
              tation) from Z. Zhang, and revised nutrient data from Calvin 
              Mordy.  I can send you these individual files as attachments to 
              the next message.
          I have merged all of these revised data files into Frank Delahoyde's 
              A16n2003 shipboard file to create a master data file in the .sea 
              format. I can also sent this to you.
          Unfortunately, I am heading out tomorrow for the A16S cruise and can't 
              do much more before I leave.  I will have all the a16n2003 data 
              with me on the cruise and should be able to answer questions by e-
              mail.
          My address should be:
              john.bullister.atsea@rbnems.ronbrown.omao.noaa.gov
      


DATA      CONTACT    DATA TYPE      DATA STATUS SUMMARY
--------  ---------  -------------  --------------------------------------------
01/18/05  Anderson   CO2            Website Updated, data OnLine 
          ...File  Jan. 18, 2005
          a16n_2003a  33RO200306_01  
          Merged the carbon data  (TCO2, TALK, PH, and PCO2) sent by A. Kozyr 
              Dec. 10, 2004 re his email below into online file.  Made new 
              exchange and NetCDF files.  

          Date:      Fri, 14 Jan 2005 14:18:05 -0500
          From:      Alexander Kozyr <kozyra@ornl.gov>
          Subject:   A22_2003 Alkalinity data
          To:        Sarilee Anderson <sarilee@minerva.ucsd.edu>

          Thank you very much Sarilee. Did you make a new exchange file as well?
          Could you check A16N_2003a files? I've sent the final carbon-related 
              data (TCARBN (or TCO2), ALKALI, pH, and pCO2) for this section on 
              12/10/2004 to WHPO but did not see any changes in your files. When 
              you merge these data, please make sure that you merge all four 
              parameters, because from the first look it seems like TCARBN and 
              pH are the same, but in reality we PIs changed some numbers and 
              flags for both.
			
02/14/05  Kappa      Cruise Report  Replaced "Cruise Instructions"
          The bulk of this cruise report was submitted by Alex Kozyr on 
          12/10/04.  It includes sections on:
              • TCARBN
              • Fugacity of CO2
              • ALKALI
              • pH
              • Nutrients
              • Oxygen
              • Figures
              • Tables
          Both the PDF and ASCII cruise reports also contain the WHPO/CCHDO 
          summary pages, and these Data Processing Notes.  Figures are found 
          only in the PDF version.  The PDF version also has links from text to 
          figures and tables, PDF bookmarks and PDF thumbnails.
           
03/10/05  McTaggart  CTD            Submitted Data Processing Report
          Attached is the CTD documentation file I gave to John Bullister
          along with the CTD bottle data last November.  He said it was 
          incorporated into a document with oxygens and nutrients etc. and
          submitted to WHPO.

03/15/05  Kappa      CTD            Added CTD Data Processing report

05/19/05  Locarnini  CTD            Data Update: oxy values corrected
          Please, notice that all CTD dissolved oxygen values for 33RO200306, 
          STNNBR 018, CASTNO 1, are equal to 0.0 (Zero) and have a Quality Flag 
          equal to 2 (Two).

06/21/05  Anderson   TOC/TDN        Data, Exchange, and NetCDF files online
          a16n_2003a  33RO200306_01 and 33RO200306_02 
            Merged the DOC (dissolved organic carbon) and TDN (total dissolved 
            nitrogen) submitted by Dennis Hansell on Oct. 27, 2004.
          Many values of -9.00 had flag of 2 or 3, I changed the flags for 
            values of -9.00 to 9. 
          There was one level that was not in the online file and therefore was 
            not merged, see below.
              STNNBR  CASTNO  SAMPNO  BTLNBR    DOC   DOCF     TDN   TDNF 
                                               kg/kg          kg/kg    
               150      1       1       1      39.51   2      33.66    2 
          Made new exchange and NetCDF files.          Sarilee Anderson 



DATE      CONTACT    DATA TYPE      DATA STATUS SUMMARY
--------  ---------  -------------  --------------------------------------------
08/29/05  Kozyr      DOC/TDN        Submitted Final Data
          I tried to submit some files to CCHDO through your web site, but it 
          would not work, it would ask me to complete the form, but form was 
          completely completed :-) and I did not know what it wanted from me. 
            So, the attached file is the final and public DOC and TDN data 
          measured during the A16N_2003a cruise (33RO200306_01_02). Could you 
          please merge these data and their quality flags into the main 
          hydrographic files. Please, let me know when the updated files will be 
          available online.

09/06/05  Anderson   DOC/TDN        Data Online; No exchange file yet
Merged the final DOC and TDN data submitted by Alex Kozyr (see B. Key 
            8/26/05 email) into the online file. No apparent problems. 
          Was not able to make the exchange file Program needs to be  modified 
            to accept DOC and TDN. 

09/22/05  Bullister  Cruise Report  Submitted cruise report and cfc report

09/22/05  Bullister  BTL            Submitted updated BTL files
          I was the Chief Scientist on the repeat hydrography cruise A16N_2003a 
            (Cruise ExpoCode 33RO200306_01).
          I did a quick check to compare the shipboard data file from A16N_2003a 
            to the files currently at the web site:
          http://whpo.ucsd.edu/data/CO2clivar/atlantic/a16/a16n_2003a/index.htm
          I think the bottle hydro values (ctdprs, ctdtmp, ctdsal, salnty, 
            ctdoxy, fctdsal, fsalnty, fctdoxy), dissolved oxygen, nutrients, and 
            CFCs have not been updated from the shipboard versions.
          Last year I asked the individual PI's to send their updated A16N_2003a 
            data to the CCHDO office directly, as per Jim Swift's instructions. 
            I also sent copies I had of the updated hydro, oxygen, nutrient and  
            CFC data to the office some time ago I think it is important to get 
            the updated versions of the data merged into your web site files
          In the next message I will attach the following files:
            a16n_allo.flg
              (revised bottle file of ctdprs, ctdtmp, ctdsal, salnty, ctdoxy, 
              fctdsal, fsalnty, fctdoxy data, prepared by Kristy McTaggart at 
              PMEL)
            A16NBottleOxygenFinal_may21_2004.xls
              (Excel spreadsheet of revised oxygen data, from Jia-Zhong Zhang at 
              AOML; data are in per liter units)
            A16NBottleOxygenFinal_may21_2004working.txt.sent to WOCE*
              (ASCII version of oxygen data I extracted from above Excel 
              spreadsheet.  I changed 5 oxygen flags in this file; data are in 
              per liter units).
            A16nuts-apr14.xls   
              (Excel spreadsheet of revised nutrient data from Calvin Mordy at 
              PMEL; data are in per liter units)
            A16nuts-apr14working.txt
              (ASCII version of revised nutrient data I extracted from above 
              spreadsheet; data are in per liter units)
            a16n2003_cfc.dat
              (ASCII listing of revised CFC data from John Bullister; data are 
              in per kg units)
            flag changes
              (a file describing the flag changes I applied to the master bottle 
              data file I keep here at PMEL.  These mostly change the parameter 
              flags for samples where the fbtlnbr is 3, 4 or 9)
          I would be extremely grateful if you could let me know that you have 
            received these files, if you have any questions or comments on the 
            files, and when the data have been merged into the web site version 
            of the A16N_2003a data set



DATE      CONTACT    DATA TYPE      DATA STATUS SUMMARY
--------  ---------  -------------  --------------------------------------------
09/23/05  Locarnini  CTDOXY         Update Needed
          Please, notice that all CTD dissolved oxygen values for 33RO200306, 
          STNNBR 018, CASTNO 1, are equal to 0.0 (Zero) and have a Quality Flag 
          equal to 2 (Two).

09/23/05  Anderson   CTDOXY         Data values corrected as per Locarnini
           • Station 18 oxygens were all 0.0, but the Q flag was 2
           • I changed the flags to 9 for all oxygens
           • Made new zip file with corrected sta. 18, and made a new exchange file
           • I was unable to make a NetCDF file at this time
					
09/26/05  Mordy      Cruise Report  Submitted nutrients report
          Here is a more informative version of the A16N cruise report for 
          nutrients.  
					
10/12/05  Kappa      Cruise Report   Doc Update
          Added new Chi Sci, PI reports:
           • New cruise report contains 
           • John Bullister's cruise summary, OXY and CFC reports, 
           • Mordy's nutrients report, 
           • K. McTaggart's CTD report, and 
           • NOAA/PMEL CO2 report; as well as 
           • CCHDO data processing notes.
					
10/27/05  Bullister  BTL             Final Data Submitted
          Updates prelim data files, see 9/22/05	
					
10/28/05  Bishop     XMISS           Data availability: 1/2006
          I am responsible for the data and it's final workup. There were 
          significant data dropouts in records during A16N.  FYI, results from 
          A16S should be available about the same time as those for A16N. I 
          estimate completion to be approximately January 2006. We had two 
          successive years when funding did not appear as expected (this year a  
          4 month gap) and all NOAA related work had to stop. 

10/28/05  Anderson   BTL             Updating files from Bullister
          I am working on merging, updating the a16n_2003a line using the files 
          the Bullister sent yesterday.

12/12/05  Smith      MET             Submitted
          Hello John, I just wanted to let you know that we received the 
          meteorological data from your A16N cruise from the Ronald Brown's 

          The data underwent quality control at FSU and are available as part 
          of a larger set of Ron Brown meteorology data at: 
          http://www.coaps.fsu.edu/RVSMDC/cgi-bin/nonwoce-ship.cgi?id=WTEC

01/19/06  Kappa      Cruise Report   Updated
          Added Chief Scientist Report
          Deleted redundant Oxygen Report
          Updated these Data Processing Notes


DATE      CONTACT            PARAMETER  EVENT            SUMMARY
--------  -----------------  ---------  ---------------  ---------------------------------
01/30/06  Jim Bishop         XMISS      Submitted        raw data only
          A16N_2003 & A16S_2005 wil be completed together

          All I can do is work forward on this. A16N and A16S data will be 
          completed together, after Ocean Sciences. The raw data are on line at 
          SIO. 

05/10/06  John L. Bullister  CrsRpt     To go online     OK'd by Bullister
          Thanks for sending the file. I read through it and it looks OK. 

05/22/06  Alexander Kozyr    DOC        Submitted        None 
          I submitted the DOC data from P02_2004 and A16N_2005 using CCHDO 
          submission page. I received the A20 and A22 DOC data files from you, 
          so I guess you have these files, but I did not see the DOC numbers for 
          these cruises were merged at CCHDO yet.

          Here are attached 3 files for DOC data from P02_2004, A16N_2003, and 
          A16S_2005 cruises. Please, let me know if you received these files OK 
          and when are you planning to merge these data. 

09/06/06  Sarilee Anderson   DOC/TDN    Website Updated  Data OnLine; no exchange 
          Sept. 6, 2006

          Merged the final DOC and TDN data submitted by Alex Kozyr (see B.Key 
          8/26/05 email) into the online file. No apparent problems. 

          Was not able to make the exchange file. Program needs to be modified 
          to accept DOC and TDN. 

11/15/06  Alexander Kozyr    CO2        status summary   None 
          Here are the latest update on the Carbon Data status at CCHDO and 
          CDIAC.

          A16N_2003:
          TCO2 - OK;
          TALK - OK;
          pCO2 - OK;
          pH - OK;
          DOC, DTN - data were not merged in CCHDO exchange file.

03/02/07  Wilford Gardner    POC/PON    Submitted        None 
          File: a16n1POC_submission-redo2.xls Type: Excel Status: Public
          Name: Gardner, Wilford D 
          Institute: Texas A&M University 
          Country: USA
          Expo:33RO2003_01 Line: A16N
          Date: 06/2003
          Action:Merge Data,Place Data Online
          Notes:
          These are POC and PON bottle data
          Upload directory: 
          /incoming_data/20070307.070610_A16N_Gardner,_Wilford_D 


DATE      CONTACT            PARAMETER  EVENT            SUMMARY
--------  -----------------  ---------  ---------------  ---------------------------------
03/28/07  Alexander Kozyr    PH         Update Needed    Do Not Use 
          pH data for A16N_2003 have major problems and will be revised. I am 
          going to put a note on a web that nobody should use pH numbers at this 
          time. Could you do the same, please? I will send you new numbers as 
          soon as I get the new file from Frank Millero. 

10/04/07  Alexander Kozyr    CO2/PH     Submitted        New params: 
          FCO2, FCO2_TMP, PH_SWS, PH_TMP 
          Type: Status: public
          Name: Kozyr, Alex
          Institute: CDIAC/ORNL
          Country: USA
          Expo:33RO200306_01 Line: A16N_2003a
          Date: 2003-06-04
          Action:Merge Data, Place Online, Updated Parameters
          Notes:Please, replace all carbon-related parameters with these ones in 
            the attached file. Note that PCO2 was replaced with FCO2 and extra 
            column for FCO2_TMP, also PH was replaced with PH_SWS (pH on the sea 
            water scale) with extra column for PH_TMP. Please, let me know when 
            the data in this file will be merged with the master file at CCHDO.

01/02/08  Alexander Kozyr    CO2        Submitted         Replaces all previous CO2 data 
          Please, replace all carbon-related parameters with these. Note that 
          PCO2 was replaced with FCO2 and extra column for FCO2_TMP, also PH was 
          replaced with PH_SWS (pH on the sea water scale) with extra column for 
          PH_TMP. 

08/06/08  Wilf Gardner       POC/PON    Submitted        Revision of 7/7/08 data file 
          Attached are two files - a revision of the file you sent and the file 
          we sent in with the data for the bottles. In your revised file we have 
          indicated what to do with each file. As you suspected, many of them 
          should have been posted as cast 2. Most of the others are in-line 
          samples (inflow) or bucket samples for which you don't have any other 
          data. They were taken on station as indicated by the same lat-lon as 
          the stations with which they were associated. You can add these or 
          ignore them as you wish. The stations in question are highlighted in 
          yellow or by a different font color in the other attached file.

07/07/08  Danie Bartolocci   POC/PON    Website Updated  Sumbitted by Wilf Gardner 
          Notes on Completed WOCE Bottle file:

          Created exchange file with no apparent errors. File named 
          a16n_2003a_hy1.csv

          Following parameters were not recognized nor included in the exchange file:
          FCO_TMP
          PH_SWS
          PH_SWS_FLAG_W
          PH_TMP
          POC
          POC_FLAG_W
          PON
          PON_FLAG_W
          TDN
          TDN_FLAG_W

          The exchange conversion code changed FCO2 to PCO2 during conversion. 
          This was edited back in file.

          Checked file with JOA, which also calls FCO2 by another parameter 
          name, however this appears to be a JOA bug and FCO2 values appear 
          accurate.

          Created netcdf files with no apparent errors. Zipped file is named 
          a16n_2003a_nc_hyd.zip


DATE      CONTACT            PARAMETER  EVENT            SUMMARY
--------  -----------------  ---------  ---------------  ---------------------------------
07/08/08  Danie Bartolocci   CO2        Website Updated  Submitted by Alex Kozyr 
          2008.07.08 DBK

          Merge notes for merging Alex Kozyr's final carbon data into the 
          a16_2003a bottle file.

          Data submitted by Alex on 10.05.2007. File named 
          a16n_2003a_final_Carbon.csv contained the following parameters: 
          FCO2,FCO2_TMP,PH_SWS_25C,PH_TMP,TALK,TALK_FLAG_W,TCO2,DOC,TDN and 
          their associated quality flags.

          Instructions as per Alex's web submission entry were:
          Notes: Please, replace all carbon-related parameters with these ones 
            in the attached file. Note that PCO2 was replaced with FCO2 and 
            extra column for FCO2_TMP, also PH was replaced with PH_SWS (pH on 
            the sea water scale) with extra column for PH_TMP. Please, let me 
            know when the data in this file will be merged with the master file 
            at CCHDO.

          MERGE NOTES:
          Original file was .csv and had to be converted to fixed width in order 
          to use merge software mrgsea.

          mrgsea did not accept FCO2_TMP as an integer for merging. This 
          parameter was edited to a floating point number with precision of 1 (f8.1).

          PH_SWS missing values of -999.0000 are larger than the woce format 
          allows and were edited to -9.0000.

          All parameters merged without problems or errors. Ran wocecvt with no 
          errors, however some parameters were unrecognized. 

07/09/08  Danie Bartolocci   DELC14/13  Website Updated  Sumbitted by Bob Key 
          2008.07.09 DBK

          Merging notes for C14/13 into a16n_2003a bottle file.

          file submitted by Bob Key on 2008.06.26 called A16N.2003.CIsotopes.csv 
          contains:
            DELC14,C14ERR,DELC13 and associated errors

          All parameters merged with no apparent errors. Checked the format of 
          the file using woccvt. No errors were reported.

          Bottle file still needs PON/POC data merged.


DATE      CONTACT            PARAMETER  EVENT            SUMMARY
--------  -----------------  ---------  ---------------  ---------------------------------
07/14/08  Shari Yvon Lewis   HCFC       Submitted        HCFC-22,HCFC142b,HCFC141b 

07/14/08  Shari Yvon Lewis   CH3        Submitted        CH3Cl,CH3Br,CH3I 

12/12/08  Chris Measures     BTL        Submitted        Updated Fe/Al params 
          Status: public
          Action: Updated Parameters
          Notes: These are the shorebased corrected values of the shipboard 
            generated trace elements Fe and Al. They are in tab delimited text 
            the output from an ODV file containing location, station, bottle 
            cast information etc. Quality flags are assigned using the ODV 
            mapping 0= good, 1=unknown, 4= questionable, 8= bad

08/07/09  Chris Measures     Tracers    Submitted        AL/FE/MAN 
          the data are public

           parameter names and units
           Station number
           Cast number + bottle number
           Aluminum (unit: nM)
           Flag
           Iron (unit: nM)
           Flag
           Manganese (unit: nM)
           Flag 

07/31/10  Carolina Berys     CH3        Website Update   Available under 
                                                               'Preliminary/Unprocessed' 
          A16N_MeX_HY1.csv submitted by Shari Yvon Lewis on 2008-07-14 available 
          under 'Preliminary/Unprocessed', unprocessed by CCHDO. 

08/02/10  Carolina Berys     POC/PON    Website Update   Available under 'Preliminary/Unprocessed' 
          a16n1POC_submission-_149944.xls submitted by Danie Kincadeon behalf of 
          Wilf Gardner on 2008/08/06 available under 'Preliminary/Unprocessed', 
          unprocessed by CCHDO. POC/PON data not merged in Exchange file, these 
          data are merged in WOCE format file. 

09/21/10  Carolina Berys     CDOM       Website Update   Available under 'as received' 
          File a16ncdom_final.txt containing CDOM data submitted by Norm Nelson 
          on 2005-04-20, resubmitted by email from Susan Piercy on behalf of 
          Norm Nelson on 2010-09-21, available under 'as received', unprocessed 
          by CCHDO. 

09/21/10  Carolina Berys     CDOM       Submitted        resubmission of text file 
          Action: Merge Data
          Notes: CDOM data submitted by Norm Nelson on 2005-04-20, resubmitted 
            by email from Susan Piercy on behalf of Norm Nelson on 2010-09-21. 

08/23/11  Alex Kozyr         Carbon     Submitted        Final data to go online 
          I've just discovered that the CCHDO Exchange file for the a16n_2003a 
          cruise 33RO200306, does not have PH, PH_TMP, PH_FLAG, FCO2_TMP, and 
          TDN data. I'vesend the final carbon data file with all these data to 
          CCHDO on 10.05.2007, according to my notes. Attached is the final 
          a16n_2003a_final_Carbon.csv data file for your use. Please merge the 
          data into CCHDO Exchange file.



DATE      CONTACT            PARAMETER  EVENT            SUMMARY
--------  -----------------  ---------  ---------------  ---------------------------------
08/24/11  Carolina Berys     CO2        Website Updated  Exchange, NetCDF files online 
          2011-08-24
          A16N 2003 ExpoCode 33RO200306_01
          WOCE to Exchange conversion notes C Berys

          Converted WOCE bottle file to Exchange using hyd_to_exchange.rb (J Fields)

          The following changes were made to the WOCE bottle file:

          FCO_TMP changed to FCO2TMP
          FCO2TMP units changed from 'ITS-90' to 'DEG C'
          PH_TMP units changed from 'ITS-90' to 'DEG C'
          NOTE: Units for PON and POC are 'UMOL/L' which does not match the 
            value in the parameter descriptions table 'UG/KG'.

          All comment lines from original file copied back into new file 
          following merge

          NetCDF bottle file created using exbot_to_netcdf.pl (S Diggs), files 
          zipped

          NetCDF and Exchange files opened in JOA with no apparent problems

          Working directory:
         /data/co2clivar/atlantic/a16/a16n_2003a/original/20110823_carbon_cberys 

11/22/11  Carolina Berys     CDOM       Website Updated  Updated NetCDF, Exchange, WOCE 
                                                         files online 
          2011-11-22
          A16N 2003 ExpoCode 33RO200306_01 merge notes - CDOM
          C BerysSUBMISSION
          a16ncdom_final.txt submitted by Norm Nelson on 2005-04-20, resubmitted 
          by email from Susan Piercy on behalf of Norm Nelson on 2010-09-21, 
          containing CDOM data merged into online file using 
          merge_exchange_bot.rb (J Fields)

          The following parameters were added:
          CDOM325
          CDOM325_FLAG_W
          CDOM340
          CDOM340_FLAG_W
          CDOM380
          CDOM380_FLAG_W
          CDOM412
          CDOM412_FLAG_W
          CDOMSL
          CDOMSL_FLAG_W
          CDOMSN
          CDOMSN_FLAG_W

          The following changes were made to the submission file: added 
          parameter mnemonics and units added cast 1 to all stations in 
          accordance with sum file changed bottle numbers to 3 digits with 
          leading zeros



DATE      CONTACT            PARAMETER  EVENT            SUMMARY
--------  -----------------  ---------  ---------------  ---------------------------------
11/22/11  Carolina Berys     CDOM       Website Updated  Updated NetCDF, Exchange, WOCE 
                                                         files online 
          ORIGINAL
          The following changes were made to the original Exchange Bottle file:
          DEPTH units changed from "" to "METERS"
          CTDRAW units changed from "" to "DBAR"
          NOTE: PON and PON have units "UMOL/L" which do not match the expected 
            "UG/KG"

          MERGED FILE
          All comment lines from original file copied back in following merge
          NetCDF bottle file created using exbot_to_netcdf.pl (S Diggs)
          WOCE bottle file created using exchange_to_wocebot.rb (J Fields)
          Exchange and NetCDF files opened in JOA with no apparent problems

          Working directory:
          /data/co2clivar/atlantic/a16/a16n_2003a/original/2011.11.21_cdom_cberys/ 

05/04/12  Jerry Kappa        CrsRpt     Website Updated  new PDF & TXT versions online
          Additions/changes include:
          • New CFC report
          • New Summary/Introduction
          • New sections on Dissolved Organic Carbon, 14C & Helium/Tritium
          • Expanded Nutrients report
          • expanded data processing notes

