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A.  Cruise Narrative: A05
    (Updated June, 2007)

A.1.  Highlights

                          WHP CRUISE SUMMARY INFORMATION

          WOCE section designation  A05
 Expedition designation (EXPOCODE)  29HE06-1-3
       Chief Scientist/affiliation  Gregorio Parrilla/IEO*
                              Ship  B.I.O. Hespérides
                             Dates  Leg 1: July 14  to  July 17, 1992
                                    Leg 2: July 17  to  July 18, 1992
                                    Leg 3: July 19  to  August 15, 1992
                     Ports of call  Leg 1: Cádiz to Sta. Cruz de Tenerife.
                                    Leg 2: Sta. Cruz de Tfe. to Las Palmas de  G.C.
                                    Leg 3: Las Palmas de G.C. to Miami
                Number of stations  118
                                               26°04.19'N
     Station geographic boundaries  80°03.95'W            15°58.08'W
                                               24°28.40'N
      Floats and drifters deployed  none
    Moorings deployed or recovered  none

                              Contributing Authors
      E. Alvárez       A. Cruzado   J. Escánez      M. Garcia   M.J. Garcia
      J. García-Braun  M.D. Gelado  J.J. Hernández  R. Millard  F. Millero
      R. Molina        A.F. Ríos    G. Rosón        W. Smethie  Z.R. Velásquez

           *Dr. Gregorio Parrilla • Instituto Espanol de Oceanografia
      Ministerio de Agricultura • Pesca y Alimentacion • Corazon de Maria 8
       Madrid, 28002 • SPAIN • TEL: +34-1-347-3608 • FAX: +34-1-413-5597
                       EMAIL: gregorio.parrilla@md.ieo.es



1.1.2.  Cruise summary

Sampling: 
Water sampling included measurements of salinity both by CTD and bottle 
samples, CTD and bottle sample Oxygen determination, CTD temperature, 
nutrients (silicate, nitrate, nitrite and phosphate), CFC, pH, alkalinity, 
C02, particulate matter, chlorophyll pigments, C14. Al.ACDP.

Type and Number of stations:
During the cruise 118 CTD/rosette stations were ocuppied using a 24
bottle rosette equipped with 10 or 12 liter in GO water sampling
bottles; 6 test stations were made between Cadiz and Las Palmas de
G.C., 101 on the A-5 section and 11 on the Strait of Florida Section.
For navigation and placement of stations, GPS and dynamic positioning
were used.


1.1.3.  LIST OF PRINCIPAL INVESTIGATORS

             NAME             RESPONSIBILITY  AFFILIATION
             ---------------  --------------  -----------
             G. Parilla       CTD             IEO
             H. Bryden        CTD             JRC
             R. Molina        S               IEO
             J. Escánez       O2              IEO
             A. Cruzado       Nutrients       CEAB
             W. Smethie       CFC             LDGO
             A. Ríos          ph, Alk, CO2    IIM
             F. Millero       ph, Alk, CO2    RSMAS
             G. Rosón         Calcium         IIM
             J. Garcia Braun  Chlorophyll     IEO
             Z. Velásquez     Chlorophyll     CEAB
             J. Hernández     Al              FCMLP
             W. Broecker      C14             LDEO
             M. García        ADCP            UPC


1.1.4.  Preliminary results

The ship departed from Cadiz on July 14, 1992 and 4 stations were made
to test CTD and Rossete before arriving to Sta. Cruz de Tenerife on the
17th.

After the ship left Tenerife on the 18th and before arriving to L.
Palmas the same day two more test stations were performed and the ACDP
was checked.

During these stations several tests of a Falmouth Scientific Inst. CTD
were also carried out.

The ship departed from L. Palmas in the early hours of the 20th to
arrive to the first station of the section A-5 the same day. This
section was finished, after 101 stations were made, at the Bahamas on
August 14 th. During the next day the Strait of Florida Section was
completed and the cruise accomplished.

We carried 3 CTDs, 2 belonging to IEO and 1 to WHOI. They are EG&G NBIS
MARK III instruments equipped with Sensor Medics dissolved oxygen
sensors and titanium pressure sensor(Millard et al 1991). All were
calihrated at the WHOI facilities before the cruise. Because the delays
inflicted by the hurricane Andrew on the equipment shipment from Miami
to Woods Hole the post-cruise calibration were not performed on the
CTDs until December. The conductivity and oxygen sensors were also
calibrated at sea using the analysis of the water samples collected at
each station. The depths of the sampling were based on the classical
standard ones although they were varied on a station by station basis
according to participants need to sample a particular layer provided
there was no impairment of the in situ calibration activities.

Table I

         STN  LATITUDE   LONGITUDE  DPTH  DATE      TIME
         ---  ---------  ---------  ----  --------  -----
           1  24 29.97N  15 58.08W    51  07 20 92  17 23
           2  24 29.96N  16 24.27W   120  07 20 92  20 07
           3  24 29.95N  16 29.95W   570  07 20 92  21 31
           4  24 30.18N  16 55.87W  1505  07 21 92  00 32
           5  24 29.98N  17 04.93W  1895  07 21 92  05 47
           6  24 29.72N  17 30.81W  2402  07 21 92  11 52
           7  24 30.02N  18 00.04W  2555  07 21 92  16 02
           8  24 29.43N  18 20.29W  2734  07 21 92  21 41
           9  24 30.04N  18 45.04W  2944  07 22 92  02 22
          10  24 30.08N  19 09.82W  3034  07 22 92  07 08
          11  24 30.26N  19 35.04W  3378  07 22 92  22 25
          12  24 30.20N  20 00.02W  3739  07 23 92  04 41
          13  24 30.09N  20 40.01W  4162  07 23 92  11 12
          14  24 30.00N  21 20.13W  4350  07 03 92  17 46
          15  24 30.09N  21 59.07W  4673  07 04 92  01 00
          16  24 29.85N  22 40.00W  4700  07 24 92  08 17
          17  24 30.14N  23 20.32W  4991  07 04 92  15 22
          18  24 30.04N  23 59.95W  5101  07 24 92  21 55
          19  24 29.91N  24 40.21W  5197  07 05 92  04 23
          20  24 29.90N  25 20.13W  5285  07 25 92  11 11
          21  24 30.17N  25 59.92W  5347  07 25 92  17 40
          22  24 30.17N  26 40.06W  4854  07 26 92  00 20
          23  24 30.28N  27 19.65W  5536  07 26 92  06 51
          24  24 30.00N  27 59.83W  5601  07 26 92  13 40
          25  24 30.20N  28 39.39W  5655  07 26 92  20 15
          26  24 30.16N  29 20.01W  5648  07 27 92  03 20
          27  24 30.01N  29 59.90W  5408  07 27 92  09 57
          28  24 30.01N  30 38.90W  5678  07 27 92  16 03
          29  24 30.06N  31 20.27W  6080  07 27 92  22 45
          30  24 30.17N  31 59.72W  5830  07 28 92  05 10
          31  24 30.19N  32 39.57W  6320  07 28 92  12 05
          32  24 29.95N  33 20.06W  6195  07 28 92  18 25

Table I, continued

         STN  LATITUDE   LONGITUDE  DPTH  DATE      TIME
         ---  ---------  ---------  ----  --------  -----
          33  24 30.22N  33 59.85W  5650  07 29 92  01 24
          34  24 30.27N  34 40.03W  5950  07 29 92  07 44
          35  24 30.02N  35 19.85W  5035  07 29 92  14 22
          36  24 30.10N  36 00.13W  5600  07 29 92  20 20
          37  24 30.07N  36 39.91W  5020  07 30 92  02 55
          38  24 30.06N  37 19.98W  5835  07 30 92  08 44
          39  24 30.13N  38 00.05W  5567  07 30 92  15 38
          40  24 30.14N  38 39.67W  4501  07 30 92  22 02
          41  24 30.03N  39 19.93W  4370  07 31 92  03 39
          42  24 30.15N  40 00.04W  5100  07 31 92  09 22
          43  24 30.15N  40 34.85W  4572  07 31 92  14 45
          44  24 29.95N  41 10.08W  5200  07 31 92  19 57
          45  24 30.17N  41 44.97W  4789  08 01 92  01 37
          46  24 30.00N  42 19.82W  4000  08 01 92  06 53
          47  24 30.08N  42 54.88W  3574  08 01 92  12 15
          48  24 30.02N  43 29.73W  3797  08 01 92  16 35
          49  24 30.02N  44 04.85W  4177  08 01 92  21 39
          50  24 30.21N  44 40.07W  3000  08 02 92  02 37
          51  24 30.01N  45 15.08W  3640  08 02 92  07 00
          52  24 29.93N  45 49.79W  2778  08 02 92  11 34
          53  24 29.95N  46 24.91W  3511  08 02 92  14 58
          54  24 29.95N  47 00.00W  3707  08 02 92  20 40
          55  24 30.08N  47 34.98W  3980  08 03 92  01 25
          56  24 29.84N  48 09.84W  3894  08 03 92  06 24
          57  24 29.99N  48 44.97W  4379  08 03 92  11 27
          58  24 30.03N  49 19.94W  5135  08 03 92  16 53
          59  24 30.07N  49 54.77W  4796  08 03 92  22 29
          60  24 29.90N  50 29.74W  4994  08 04 92  03 51
          61  24 30.00N  51 04.95W  5076  08 04 92  09 25
          62  24 30.08N  51 39.87W  4810  08 04 92  15 32
          63  24 30.02N  52 14.99W  4728  08 04 92  22 03
          64  24 29.99N  52 50.00W  5100  08 05 92  03 27
          65  24 30.06N  53 24.93W  5637  08 05 92  09 04

Table I, continued

         STN  LATITUDE   LONGITUDE  DPTH  DATE      TIME
         ---  ---------  ---------  ----  --------  -----
          66  24 29.92N  53 59.61W  6140  08 05 92  15 18
          67  24 29.96N  54 40.00W  6209  08 05 92  21 34
          68  24 29.94N  55 19.80W  5540  08 06 92  03 46
          69  24 29.95N  56 00.01W  6444  08 06 92  09 57
          70  24 30.03N  56 40.03W  6180  08 06 92  16 42
          71  24 29.88N  57 19.79W  6116  08 06 92  23 51
          72  24 29.91N  58 00.05W  6123  08 07 92  06 30
          73  24 29.94N  58 39.96W  6071  08 07 92  13 09
          74  24 30.08N  59 19.49W  5827  08 07 92  19 48
          75  24 30.06N  60 00.12W  5937  08 08 92  02 04
          76  24 30.00N  60 39.92W  5794  08 08 92  08 29
          77  24 30.17N  61 19.40W        08 08 92  14 56
          78  24 29.93N  61 59.88W  5891  08 08 92  21 37
          79  24 30.07N  62 39.90W  5909  08 09 92  03 51
          80  24 29.95N  63 20.12W  5850  08 09 92  10 33
          81  24 29.95N  63 59.90W  5771  08 09 92  16 43
          82  24 29.93N  64 39.94W  5762  08 09 92  23 12
          83  24 30.37N  65 20.39W  5642  08 10 92  10 25
          84  24 29.96N  65 59.98W  5764  08 10 92  17 05
          85  24 30.04N  66 39.93W  5647  08 10 92  22 58
          86  24 29.98N  67 19.99W  5658  08 11 92  05 14
          87  24 30.01N  68 00.04W  5739  08 11 92  11 34
          88  24 29.95N  68 39.93W  5712  08 11 92  17 32
          89  24 29.92N  69 19.93W  5620  08 11 92  23 27
          90  24 29.97N  70 00.00W  5561  08 12 92  05 20
          91  24 29.87N  70 40.00W  5541  08 12 92  11 10
          92  24 29.88N  71 19.92W  5519  08 12 92  16 50
          93  24 30.00N  71 59.97W  5510  08 12 92  22 35
          94  24 45.05N  72 35.94W  5497  08 13 92  04 10
          95  24 59.80N  73 10.00W  5344  08 13 92  09 56
          96  24 59.97N  73 49.95W  5242  08 13 92  15 38
          97  25 00.00N  74 20.04W  4948  08 13 92  20 23
          98  25 06.11N  74 49.77W  4702  08 14 92  01 47
          99  24 32.77N  75 27.70W  3347  08 14 92  08 22
         100  24 37.41N  75 19.12W  4800  08 14 92  11 45
         101  24 30.00N  75 31.00W   930  08 14 92  16 03


Water samples were collected from 10 or 12 liters PVC Niskin GO bottles
mounted on a GO Rosette Sampler.All the water sample conductivity and
oxygen measurements were made in a constant temperature laboratory soon
after each cast was completed. Descriptions of analytical techniques,
precision and accuracy are given later in this report. Additional
samples were also collected for the analysis of the other parameters
listed above, description of which are presented in other sections of
this report.

According to the WOCE Implementation Plan this line was located at
24N. As two oceanographic sections had been made previously in 1957
and 1981)  around 24.5N (Roemmich and Wunsch,1985) we asked the
WOCEIPO to move the WOCE section A5 to this latitude, which was agreed
to. With respect to the station separations and because we were
constrained by ship time, we decided to use the following judgment: the
first 6 stations were located at the 50,100,150,1500,2000 and 2500
isobaths (about 18 nm separation), from there to the 4000 m depth
(stl2) the separation was about 23 nm. From station 12 to the eastern
limits of the Mid Atlantic Ridge we separated the stations by 36 nm.
Across the Ridge the separation was 32 nm. From its western limits to
the 5000 isobath near the Bahamas,stations were separated again 36nm.
Stations close to the Bahamas were separated by less than 30 nm.The
stations across the Straits of Florida were ocuppied every 5 nm.

Near to Bahamas we deviated the heading of the section slightly from
the original plan in order to cross the continental slope perpendicular
to the direction of the isobaths and to obtain a clear crossing of the
Deep Western Boundary Current.

The ADCP and a thermosalinograph recorded continuous during the whole
cruise. Wind information was recorded every hour.

At the end of the cruise the ship was checked for Tritium and C14
contamination by the Tritium laboratory of the U.of Miami.

Vertical profiles for T, S and O2 together with a listing of this data
for standard depths for each station are given in the Annex.


1.1.5.  Incidents.

During the test stations, there were problems with the rosette: several
of the bottles were not triggered. The trouble had to do, probably,
with too much friction on the bolts since this rosette had never been
used before. After some lubrication the problem disappeared. There were
also some problems, during the test stations and some of the first
stations of the A-5 section,with the portside winch. The oil of the
hydralic circuit became too hot causing the winch to lose power. After
station 11 we switched to the other winch that worked from the stern.

On station 62, CTD # 1 stop sending conductivity data and it was
replaced by CTD # 2 until station 74 when CTD# 1 was brought back, only
for 7 stations since we started getting pressure spiking. From station
81 to 88 we used CTD #2 and from there on we used CTD# 1 after it was
repaired on board.

On station 83 the wire was reterminated after cutting off 10 m of wire
because of a faulty electrical contact. It was also reterminated after
station 110 (in the Florida Strait) because of two-blocking the CTD on
recovery at this station.

On station 61 the CTD hit the bottom because of a failure of the depth
recorder.

The portable hydrophone-recording system for use with the pinger failed
from the begining and we were not able to repair it. We tried to use
the EA500 SIMRAD echosounder of the ship,but there was not the
necessary documentation on board so we could not effectively use the
pinger at all.We decided to keep the CTD package between 50 or 100 m
above the bottom when the floor was too rough and less that 50 m when
it was flat.

The proposed Tritium and Helium survey by Dr.Z.Top could not be made
since the equipment was lost during shipment from Miami and it never
arrived to the ship.


1.1.6.  LIST OF PARTICIPANTS

      ----------------------------------------------------------
       NAME             RESPONSIBILITY              AFFILIATION
       ---------------  --------------------------  -----------
       G. Parrilla      Chief Scientist             IEO
       H. Bryden        Co-Chief Scientist          WHOI
       J. Alonso        CTD Watch                   IEO
       E. Alvarez       CTD Watch/Thermosalingraph  PCM
       B. Amengual      S, O2                       IEO
       G. Bond          CTD Watch/CTD Electronics   WHOI
       J. Garcia-Braun  O2, Chlorophyll             IEO
       J. Hernández     Al                          FCMLP
       A. Cantos        CTD Watch/ADCP              Ainco I
       A. Cruzado       Nutrients                   CEAB
       J. Escánez       O2                          IEO
       S. Fiol          CO2                         U. La Coruña
       M.J. García      CTD Watch/Data Processing   IEO
       D. Gelado        Al                          FCMLP
       E. Gorman        CFC                         LDGO
       A. Lavín         CTD Watch/Data Processing   IEO
       R. Millard       CTD Watch/CTD Programming   WHOI
       R. Molina        CTD Watch/S                 IEO
       J. Molinero      Electronics                 IEO
       A. Osiroff       CTD Watch/ Data Processing  SHMA
       A.F. Ríos        CO2/M.O.P.                  IIM
       G. Rosón         Calcium                     IIM
       P. Sánchez       CTD Watch/Data Processing   IEO
       W. Smethie       CFC                         LDGO
       Z. Velasquez     Chlorophyll                 CEAB
       A. Fougere       Falmouth SI CTD             WHOI
       C. Heuer         Tritium/Helium              RSMAS
       G. Mathieu       CFC                         LDGO
      ----------------------------------------------------------

1.1.7.  Acronyms

        IEO    Instituto Espanol de Oceanografia
        IIM    Instituto de Investigaciones Marinas
        CEAB   Centro de Estudios Avanzados Blanes
        FCMLP  Facultad de C. del Mar
        PCM    Programa Clima Maritimo
        RSMAS  Rosenstiel School of Marine and Atmospheric Sciences
        WHOI   Woods Hole Oceanographic Institution
        LDGO   Lamont Doherty Geological Observatory
        UPC    Unversidad Politecnica de Cataluna
        JRC    James Rennell Centre



2.  CTD measurements
    (R. Millard and M J Garcia)

2.1.  Instrumentation, Calibrations ad Standards

Two EG&G/NBIS Mark IIIb CTD underwater units each equipped with
pressure, temperature, conductivity and polographic oxygen sensors were
used throughout the cruise. The CTD instrument numbers are 1100 and
2326 and they belong to the Instituto Espanol de Oceanografia (IEO).
Each CTD is configured identically with the same data scan length,
variables, and scanning rate of 31.25 Hz. (A detailed description of
the Mark IIIb CTD can be found in Brown and Morrison, 1978.) Both
instruments were modified at Woods Hole Oceanographic Institution
(WHOI) to add a titanium pressure sensor with a separately digitized
resistive temperature device (RTD). A third EG&G/NBIS Mark IIIb CTD was
provided by WHOI (WHOI instrument No. 8) but was not used during this
expedition. A General Oceanics (GO) rosette fitted with 24 10 liters
Niskin bottles was used with the CTD for collecting water samples. The
GO rosette bottles are mounted approximately 0.5 m above the CTD
sensors.

Titanium pressure sensors were manufactured by Paine Instrument and
were installed with a separate pressure-temperature sensor in both CTD
s prior to the cruise. The pressure data has a resolution of 0.1
decibars and and an overall accuracy of + 2.0 decibars for CTD# 1100
and + 5.0 decibars for CTD # 2326. The pre-cruise pressure calibration
was used for CTD # 1100 while a combination of pre and post cruise
pressure calibration was used to process CTD # 2326. The Titanillm
pressure transducer processing methods follow Millard, et. al (1993).
Pressure is calibrated across the pressure sensor's range in the
laboratory before and after the cruise. These calibrations are carried
out at both room temperature and at the ice point.

The temperature sensor is a Rosemount platinum # 171. The fast response
temperature thermistor normally employed in the Mark IIIb has been
removed. The temperature resolution is 0.0005 C and the accuracy is
better than +/- 0.0015 C (Millard & Yang  (1993)) over the range O to
30.0 C.   Temperature was calibrated in the laboratory before and after
the cruise with the CTD instrument fully immersed as described by
Millard & Yang  (1993).  A large (0.01 to 0.015 C) shift of
temperature in the same direction was observed to occur with both CTD's
1100  and 2326.  This shift was traced to a faulty pre-cruise
laboratory temperature standardization. The conductivity sensor is a 3
centimeter alumina cell manufactured by EG&G/NBIS. The resolution of
conductivity is 0.001 Ms/cm and the accuracy is directly tied to the
water sample salinity accuracy which is discussed elsewhere in this
report. The overall accuracy of the CTD conductivity calibrated to the
rosette water bottle salinities is believed to be better than +/-
0.0025 psu.

The CTD oxygen is measured with a polographic sensor manufactured by
Sensormedics. The CTD oxygens are calibrated to shipboard Winkler
oxygens.


2.2.  CTD DATA COLLECTION AND PROCESSING

The CTD data logging and processing was accomplished on two MSDOS PCs.
The data logging was handled on an IBM compatible 80386 system with an
80387 math co-processor. The EG&G data logging program CTDACQ was used
to record down and up profiles, separately on disk together with a
rosette bottle file. The CTD data was edited to flag spurious data
using the EG&G program CTDPOST. The remainer of the CTD post-processing
was performed using the WHOI PC-based CTD processing system as
described by Millard and Yang (1993). The post-processing was performed
on an IBM compatible 80486 system with a 600 Mbyte optical disk (Sony
SMO-C501) used for data archiving.


2.3.  CTD CALIBRATION CONSTANTS

The standard Alumina conductivity cell materials expansion factors: Alpha = -6.5
E-6, Beta = 1.5 E-8 were applied to CTD #1100 and CTD #2326.  When the pre-
cruise pressure calibration was applied to CTD 2326 data, a Beta = -1.5 E-8 was
required to produce a salinity without a depth dependence; but a combination of
pre/post-cruise pressure calibration allowed the use of the standard Beta value.
The combined pressure calibration was used to process all CTD #2326 data because
it produced CTD salinities free of depth dependence and yielded the pressure
bias observed at sea.


2.4.  PRE AND POST-CRUISE LABORATORY CALIBRATIONS POLYNOMIAL COEFFICIENTS

                                 Eng = E+Dr+Cr2

(where r is the measured raw CTD data value and Eng is the standard engineering
unit of the variable).

The coefficients for each sensor are:


A) Pressure: (Loading/unloading)

   CTD #1100
     E= -1.075;  D= .108604;   C=  0.593893 E-9 pre-cruise

   CTD #2326
     E =   0.15;    D = 0.104831;      C= -0.799383 E-9 (pre-cruise)
     E = -12.5;     D = 0.105437;      C= -0.752607 E-9 (post-cruise)
     E =  -6.3;     D = 0.105127;      C= -0.752607 E-9 (pre/post cruise combined)


B) Temperature: (post-cruise)

   CTD #1100 (2nd order fit, stand. dev. = 0.00035)
     E =  -0.4055;  D = 0.499576 E-3;  C = 0.13946  E-11: Lag = 0.225 s

   CTD #2326 (1st order fit, stand. dev. = 0.0006)
     E =   0.0026;  D = 0.499889 E-3;                     Lag = 0.250 s


C)  Conductivity:

For CTD #2326 and CTD #1100 conductivity calibrations the post-cruise
temperatures were used.  For CTD #2326 the data was pressure averaged again
after the cruise using the combined pre/post-cruise pressure calibrations while
CTD 1100 used the pre-cruise pressure calibration.  The conductivity (salinity)
calibration was examined closely at the change of instruments during the cruise
(i.e. instrument swap outs at stations 62 - 63, 73 - 74, 80 - 81, 88 - 89) and
no shifts were found that were not arguably due to oceanic variability.

CTD #1100
This CTD required some fine-tuning of conductivity slope calibrations.
Bias, E= -0.0116 for all the stations

             STATIONS                        SLOPE D=
             ------------------------------  --------------
             1 - 62                          0.1000 453 E-2
             74 (fit to itself)              0.1000 565 E-2
             75                              0.1000 512 E-2
             76                              0.1000 510 E-2
             77                              0.1000 508 E-2
             78                              0.1000 506 E-2
             79                              0.1000 505 E-2
             80                              0.1000 503 E-2
             89 - 91                         0.1000 500 E-2
             92 - 101 (fit to sta. 93 - 95)  0.1000 483 E-2


Stations 96, 97 and 98 salinities are low compared to the water samples, but we
believe that water sample salinities are suspect for these stations.

CTD #2326

For this CTD, there is significant down-up hysteresis in one of the salinity
sensors (P, T, or C: mostly likely Conductivity).  The up-profile salinity is
.005 - .007 fresher than the corresponding down-profile at a given potential
temperature.  Of course, at the bottom of the profile the salinity agrees but by
2.5°C (3500 dbars) on the 6000 dbar profiles a .005 psu discrepancy exists.  A
program was written to extract and create down-profile conductivity calibration
data and we have to refit CTD #2326 conductivities below 2500 dbars.

Stations 63 - 73, bias; E= 0.0083

             STATION                               SLOPE, D=
             ------------------------------------  --------------
             63(Fit to down profile conductivity)  0.1000 2693 E-2
             64(Fit to down profile conductivity)  0.1000 1727 E-2
             65                                    0.1000 1699 E-2
             66                                    0.1000 1671 E-2
             67                                    0.1000 1642 E-2
             68                                    0.1000 1614 E-2
             69                                    0.1000 1585 E-2
             70                                    0.1000 1557 E-2
             71                                    0.1000 1529 E-2
             72                                    0.1000 1500 E-2
             73                                    0.1000 1472 E-2
             81 - 88 Bias, E= 0.0121               0.999936 E-3
             (01-27-93 calibration)


Final CTD data edit:

Two mean profiles were created.  One for the West African Basin and a second for
the North American Basin, by averaging all deep BIO Hésperides stations on
pressure surfaces.  These mean profiles have been used to screen the individual
casts of each basin for question able temperature, salinity and oxygen data,
comparing individual profiles to respective mean profile.

Two edit criteria were used to flag questionable data:
   • Temperature, Salinity and Oxygen variations whose difference from the mean
     profile exceeding 5.5 standard deviations;
   • Stability parameter exceeding -1.0E-5 per meter.

A list of stations with bad or questionable data at the surface is given below:

                       |        1        |         2
          -------------|-----------------|-------------------
          W African B. | 17, 26, 32, 35, |  2,  5, 10, 18, 19,
                       | 39, 41, 44, 47  | 20, 22, 23, 27, 28,
                       |                 | 29, 31, 33, 34, 36,
                       |                 | 37, 38, 42, 43, 45,
                       |                 | 46, 48, 50, 51, 52,
                       |                 | 53
          -------------|-----------------|-------------------
          N American B.| 57, 74, 76, 81  | 55, 56, 58, 59, 60,
                       |                 | 61, 62, 68, 69, 70,
                       |                 | 72, 77, 78, 79, 80,
                       |                 | 82, 85, 86, 87

          1. Stations with bad or too low surface salinities.
          2. Stations with questionable surface salinities.

D)  Oxygen

The oxygen parameters were adjusted as shown on tables II and III.  The header
abbreviations denote the following:

   • STA= First and last station numbers of the group used for calibration.
   • BIAS, SLOPE, PCOR, TCOR, WT, LAG and Edit factor are parameters of the fit
     as described by Millard and Yang (1993).
   • STD DEV= Standard deviation of the fit after some outlying water sample
     observations are discarded.
   • OBS= Number of water sample observations used for the calibration.


Table II:  COEFFICIENTS FOR OXYGEN CALIBRATIONS

 ---------------------------------------------------------------------------
   STN   | BIAS |   SLOPE   |   PCOR    |   TCOR    |     WT    |    LAG
  ------ | ---- | --------- | --------- | --------- | --------- | ---------
  1-11   | .029 | .1104e-02 | .1664e-03 | -.2783e-1 | .7510e+00 | .7560e+01
  12-14  | .049 | .1139e-02 | .1461e-03 | -.2990e-1 | .7500e+00 | .7500e+01
  15-19  | .031 |           | .1504e-03 | -.2939e-1 | .8219e+00 | .4167e+01
  15     |   "  | .1129e-02 |     "     |     "     |     "     |     "
  16     |   "  | .1156e-02 |     "     |     "     |     "     |     "
  17     |   "  | .1158e-02 |     "     |     "     |     "     |     "
  18     |   "  | .1170e-02 |     "     |     "     |     "     |     "
  19     |   "  | .1182e-02 |     "     |     "     |     "     |     "
  20-22  | .024 | .1197e-02 | .1517e-03 | -.3090e-1 | .7408e+00 | .7299e+01
  23-31  | .032 | .1205e-02 | .1491e-03 | -.3033e-1 | .7934e+00 | .3211e+01
  32-40  | .024 | .1228e-02 | .1501e-03 | -.2926e-1 | .9210e+00 | .7833e+01
  41-43  | .015 | .1233e-02 | .1553e-03 | -.2998e-1 | .7740e+00 | .7000e+01
  44-46  | .006 | .1229e-02 | .1616e-03 | -.3065e-1 | .6702e+00 | .1623e+02
  47-50  | .000 | .1235e-02 | .1673e-03 | -.3092e-1 | .5287e+00 | .2187e+02
  51-55  | .012 | .1226e-02 | .1590e-03 | -.2953e-1 | .8080e+00 | .7340e+01
  56-62  | .032 | .1216e-02 | .1499e-03 | -.2906e-1 | .8221e+00 | .1549e+02
  63-71  |-.036 | .1256e-02 | .1683e-03 | -.3041e-1 | .7448e+00 | .4612e+01
  70     |   "  | .1269e-02 |     "     |      "    |     "     |     "
  72-73  |-.047 | .1338e-02 | .1686e-03 | -.3241e-1 | .6362e+00 | .2927e+01
  74-80  | .027 | .1201e-02 | .1515e-03 | -.2865e-1 | .8869e+00 | .1027e+02
  81-83  |-.053 | .1276e-02 | .1788e-03 | -.3177e-1 | .6312e+00 | .3351e+01
  84-87  |-.030 | .1284e-02 | .1645e-03 | -.3047e-1 | .8147e+00 | .1998e+00
  88     |   "  | .1320e-02 |     "     |      "    |     "     |     "
  89-101 | .039 | .1200e-02 | .1459e-03 | -.2779e-1 | .9109e+00 | .1390e+02
 ---------------------------------------------------------------------------


Table III:  STATISTICS OF ADJUSTMENTS FOR OXYGEN CALIBRATIONS

     -------------------------------------------------------------------
      STN   | STD DEV    |    OBS     |  STN   |  STD DEV  |    OBS
      ------|------------|------------|--------|-----------|-----------
      1-11  | .7188e-01  |  59 of 59  | 47-50  | .5274e-01 |  84 of 91
      12-14 | .4233e-01  |  46 of 60  | 51-55  | .5526e-01 |  83 of 100
      15-19 |            |            | 56-62  | .3870e-01 | 116 of 131
      15    | .6791e-01  |  19 of 21  |        |           |
      16    | .1566e+00  |  18 of 20  | 63-71  | .5401e-01 | 176 of 189
      17    | .5021e-01  |  19 of 21  | 70     | .7953e-01 |  22 of 23
      18    | .3341e+00  |  21 of 21  |        |           |
      19    | .5171e-01  |  21 of 22  | 72-73  | .8711e-01 |  45 of 45
      20-22 | .56355e-01 |  62 of 67  | 74-80  | .6576e-01 | 159 of 161
      23-31 | .6148e-01  | 189 of 203 | 81-83  | .6388e-01 |  64 of 66
      32-40 | .5958e-01  | 150 of 170 | 84-87  | .7946e-01 |  72 of 72
            |            |            | 88     | .8969e-01 |  24 of 24
      41-43 | .7023e-01  |  68 of 69  |        |           |
            |            |            | 89-101 | .5241e-01 | 213 of 229
      44-46 | .4442e-01  |  68 of 69  |        |           |
     -------------------------------------------------------------------
     Notes to these tables
       • Parameters obtained from stations 7 to 9 apply to stations 1 - 11.
       • Stations 15 to 19 were fit fixing parameters of 15 - 21 except slope.
       • Stations 32 to 39 calibrations applied to stations 32 to 40.
       • Station 70 calibrated as group 63 - 71 except slope
       • Station 88 calibrated as 84 - 87 except slope
       • Station 89 to 101.  Sta. 96 and 98 are excluded in setting calibration
         parameters.  When they were included WT was negative.


Figure 2 shows the histograms for salinity and oxygen differences between CTD
and bottle samples deeper than 2500 db.  The mean and standard error for the
first one are 1.9 E-4 and 1.3 E-4 respectively.  For oxygen, they are 1.1 E-4
and 2 E-3.


3.  BOTTLE DATA

3.1.  Carbon System Parameters

                                                   ORNL/CDIAC-125
                                                          NDP-074

     CARBON DIOXIDE, HYDROGRAPHIC, AND CHEMICAL DATA OBTAINED
      DURING THE R/V HESPERIDES CRUISE IN THE ATLANTIC OCEAN
           (WOCE SECTION A5, JULY 14 - AUGUST 15, 1992)

                          Contributed by
       Frank J. Millero,* Sara Fiol,* Douglas M. Campbell,*
                      and Gregorio Parrilla**

       *Rosenstiel School of Marine and Atmospheric Science
                        University of Miami
                          Miami, Florida

                **Instituto Espanol de Oceanografa
                      Madrid, 28002, Spain


        Prepared by Linda J. Allison and Alexander Kozyr***
            Carbon Dioxide Information Analysis Center
                   Oak Ridge National Laboratory
                       Oak Ridge, Tennessee

           ***Energy, Environment, and Resources Center
                    The University of Tennessee
                       Knoxville, Tennessee


                  Environmental Sciences Division
                        Publication No. 4988


                     Date Published:  May 2000


                         Prepared for the
                  Environmental Sciences Division
          Office of Biological and Environmental Research
                     U.S. Department of Energy
      Budget Activity Numbers KP 12 04 01 0 and KP 12 02 03 0

                          Prepared by the
            Carbon Dioxide Information Analysis Center
                   OAK RIDGE NATIONAL LABORATORY
                  Oak Ridge, Tennessee 37831-6335
                            managed by
                         UT-BATTELLE, LLC
                              for the
                     U.S. DEPARTMENT OF ENERGY
                 under contract DE-AC05-00OR22725


    This report was  prepared as an account  of work sponsored
    by anagency of the  United States Government.  Neither the
    United States Government  nor any agency thereof,  nor any
    of their employees, makes any warranty, express or implied,
    or assumes any  legal  liability or responsibility for the
    accuracy, completeness, or usefulness of,  any information,
    apparatus,  product,  or process disclosed,  or represents
    that  its use  would not  infringe  privately owned rights.
    Reference herein to any specific commercial product,  pro-
    cess, or service by trade name, trademark, manufacture, or
    otherwise, does not necessarily constitute or imply its en-
    dorsement, recommendation, or favoring by the United States
    Government or any agency thereof. The views and opinions of
    authors expressed herein do not necessarily state or reflect
    those of the United States Government or any agency thereof.



ACKNOWLEDGMENTS

The authors wish to acknowledge the National Oceanographic and Atmospheric
Administration, the Oceanographic Section of the National Science Foundation,
the Department of Energy, and the Office of Naval Research for supporting this
study.


ACRONYMS

        14C    radiocarbon
        ADCP   acoustic Doppler current profiler
        ASCII  American Standard Code for Information Interchange
        CDIAC  Carbon Dioxide Information Analysis Center
        CEAB   El Centro de Estudios Avanzados de Blanes
        CFC    chlorofluorocarbon
        CO2    carbon dioxide
        CRM    certified reference material
        CTD    conductivity, temperature, and depth sensor
        DOE    U.S. Department of Energy
        emf    electromotive force
        FCMLP  Facultad de Ciencias del Mar
        fCO2   fugacity of CO2
        FTP    file transfer protocol
        GC     gas chromatography
        GMT    Greenwich Mean Time
        GO     General Oceanics
        GPS    global positioning system
        IEO    Instituto Espanol de Oceanografia
        IIM    Instituto de Investigaciones Marinas
        IPO    WOCE International Program Office
        IR     infrared
        JGOFS  Joint Global Ocean Flux Study
        LDEO   Lamont-Doherty Earth Observatory
        NBIS   Neil Brown Instruments Systems
        NDP    numeric data package
        nm     nautical mile
        NOAA   National Oceanic and Atmospheric Administration
        PSS    practical salinity scale
        QA     quality assurance
        RSMAS  Rosenstiel School of Marine and Atmospheric Science
        RTD    resistive temperature device
        R/V    research vessel
        SIO    Scripps Institution of Oceanography
        TALK   total alkalinity
        TCO2   total carbon dioxide
        UPC    Universidad Politecnica de Cataluna
        URL    universal resource locator
        WCRP   World Climate Research Program
        WHOI   Woods Hole Oceanographic Institution
        WHPO   WOCE Hydrographic Program Office
        WOCE   World Ocean Circulation Experiment



ABSTRACT

Millero, F.J., S. Fiol, D.M. Campbell, G. Parrilla, and L.J. Allison and
    A. Kozyr (eds.). 2000.  Carbon Dioxide, Hydrographic, and Chemical Data
    Obtained During the R/V Hesperides Cruise in the Atlantic Ocean (WOCE
    Section A5, July 14 - August 15, 1992).  ORNL/CDIAC-125, NDP-074.  Carbon
    Dioxide Information Analysis Center, Oak Ridge National Laboratory, U.S.
    Department of Energy, Oak Ridge, Tennessee, U.S.A.  51 pp.

This data documentation discusses the procedures and methods used to measure
total carbon dioxide (TCO2), total alkalinity (TALK), and pH at hydrographic
stations during the R/V Hesperides oceanographic cruise in the Atlantic Ocean
(Section A5).  Conducted as part of the World Ocean Circulation Experiment
(WOCE), the cruise began in Cadiz, Spain, on July 14, 1992, and ended in
Miami, Florida, on August 15, 1992.  Measurements made along WOCE Section A5
included CTD pressure, temperature, salinity, and oxygen; and bottle salinity,
oxygen, phosphate, nitrate, nitrite, silicate, TCO2, TALK, and pH.

The TALK, TCO2, and pH were determined from titrations of seawater collected
at 33 stations.  The titration systems for measuring TALK and TCO2 were
calibrated in the laboratory with certified reference materials (CRMs) before
the cruise to ensure that they gave reliable results for these parameters.
Standard reference seawater provided by Andrew Dickson of Scripps Institution
of Oceanography (SIO) was used at sea to monitor the performance of the
titration systems.  The results agree with the laboratory results to
±2 µmol/kg for TALK and ±1 µmol/kg for TCO2.  The titration systems used to
measure pH were calibrated with TRIS seawater buffers prepared in the
laboratory and measured with an H2, Pt/AgCl, Ag electrode.  The initial
electromotive force (emf) of the titrations was used to determine the pH.  The
values of pH are thought to be reliable to ±0.01 and are internally consistent
with the measured values of TALK and TCO2 to ±7 µmol/kg.  The measured carbon
dioxide system parameters have been used to calculate the in situ values of
the fugacity of CO2 (fCO2) for the surface water.  The surface results are
briefly discussed.

The WOCE Section A5 data set is available free of charge as a numeric data
package (NDP) from the Carbon Dioxide Information Analysis Center.  The NDP
consists of two oceanographic data files, two FORTRAN 77 data-retrieval
routine files, a documentation file, and this printed report, which describes
the contents and format of all files as well as the procedures and methods
used to obtain the data.  Instructions on how to access the data are provided.

Keywords: Carbon dioxide; World Ocean Circulation Experiment; North Atlantic
          Ocean; hydrographic measurements; alkalinity; carbon cycle



                                     PART 1:
                                    OVERVIEW

3.1.1.  BACKGROUND INFORMATION

There is currently much interest in understanding the inorganic carbon
dioxide (CO2) system in the oceans because of the so-called greenhouse effect
of the increasing atmospheric concentration of CO2 on the climate.
Approximately 40% of the CO2 added to the atmosphere as a result of the
burning of fossil fuels is thought to be going into the oceans.  The flux of
carbon dioxide across the air-sea interface is controlled by the difference in
the partial pressure of CO2 in the atmosphere and in the surface waters.  Once
the CO2 is in solution it can equilibrate with the bicarbonate and carbonate
ions.  The carbonate ion concentration in the oceans controls the rate of
precipitation and dissolution of calcium carbonate (CaCO3) in the oceans.  The
carbon dioxide system can be characterized by measuring two of the four
measurable parameters [pH, the fugacity of CO2 (fCO2), the total carbon
dioxide (TCO2), and the total alkalinity (TALK)].  The other parameters can be
calculated using thermodynamic relations.

To learn more about the role of the world ocean in climate and climatic
changes, several large experiments have been conducted.  The World Ocean
Circulation Experiment (WOCE) is the largest experiment ever attempted.  A
major component of the World Climate Research Program (WCRP), WOCE brings
together scientists from more than 30 nations.  Although TCO2 is not an
official WOCE measurement, carbonate chemists are participating in the WOCE
cruises as part of the Joint Global Ocean Flux Study (JGOFS) to measure the
components of the carbon dioxide system in the oceans.  These studies are
being sponsored in the United States by the U.S. Department of Energy (DOE)
and the National Oceanographic and Atmospheric Administration (NOAA).  The
carbon dioxide system parameters measured, in order of preference, are the
TCO2, TALK, and pH.  The preferred analytical methods are infrared (IR) or gas
chromatography (GC) for fCO2, coulometery for TCO2, titration for TALK, and
spectroscopy for pH.  Because systems to measure fCO2 and TCO2 were not
available on the R/V Hesperides cruise, and only one berth was available, the
TALK, TCO2,  and pH were determined by titration.  Although this is not ideal,
it was believed that some reasonably precise data were better than no data.

The present report gives the results of carbonate measurements made during
the 32 days of the expedition of the R/V Hesperides along WOCE section A5
(along 25°N).


3.1.2.  DESCRIPTION OF THE EXPEDITION
        Hesperides Cruise Information

          Ship name        R/V Hesperides
          Expedition code  29HE06/1
          WOCE Section     A5
          Location         Cadiz, Spain to Santa Cruz de Tenerife; 
                           to Las Palmas, Gran Canaria; 
                           to Miami, Florida, U.S.A.
          Dates            July 14 - August 15, 1992
          Chief scientist  Gregorio Parrilla

         ------------------------------------------------------
          Parameter                   Insti-   Principal
          measured                    tution   Investigator
          --------------------------  ------   ---------------
          CTD*                         IEO     G. Parrilla
                                       WHOI    H. Bryden
          Salinity                     IEO     R. Molina
          Oxygen                       IEO     J. Escanez
          Nutrients                    CEAB    A. Cruzado
          Chlorofluorocarbons (CFCs)   LDEO    W. Smethie
          pH, TALK, TCO2               IIM     A. Rios
                                       RSMAS   F. Millero
          Calcium                      IIM     G. Roson
          Chlorophyll pigments         IEO     J. Garcia Braun
                                       CEAB    Z. Velazquez
          Primary productivity         IEO     J. Garcia Braun
          Aluminum                     FCMLP   J. Hernandez
          Radiocarbon (14C)            LDEO    W. Broecker
          ADCP**                       UPC     M. Garcia
         ------------------------------------------------------
          *Conductivity, temperature, and depth sensor.
         **Acoustic Doppler current profiler.


Participating Institutions

          CEAB   El Centro de Estudios Avanzados de Blanes
          FCMLP  Facultad de Ciencias del Mar
          IEO    Instituto Espanol de Oceanografia
          IIM    Instituto de Investigaciones Marinas
          LDEO   Lamont-Doherty Earth Observatory
          RSMAS  Rosenstiel School of Marine and Atmospheric Science
          UPC    Universidad Politecnica de Cataluna
          WHOI   Woods Hole Oceanographic Institution




3.1.3.  Brief Cruise Summary

According to the WOCE Implementation Plan, the cruise line for WOCE Section
A5 was to be located at 24°N.  As two oceanographic sections had previously
been made (1957 and 1981) around 24.5°N (Roemmich and Wunsch 1985), the WOCE
International Program Office (IPO) agreed to a request to move WOCE Section A5
to this latitude.

The R/V Hesperides departed from Cadiz, Spain, on July 14, 1992.  The
cruise track and station locations are shown in Fig. 1 in the hard copy report.
During the cruise, 118 CTD/rosette stations were occupied.  Six stations were
made to test the CTD and rosette.  Four test stations (three casts in the
first station and one in the second) were occupied before the ship arrived at
Santa Cruz de Tenerife on July 17.  The ship left Tenerife on July 18 and
occupied two more test stations and also checked the ADCP before arriving at
Las Palmas de Gran Canaria the same day.  During these stations, several tests
of a Falmouth Scientific Instrument CTD were also carried out.  The ship
departed from Las Palmas in the early hours of July 20 and arrived at the
first station of WOCE Section A5 the same day.  After 101 stations were made,
the ship arrived at the Bahamas on August 14 and WOCE Section A5 was
completed.  During the next day, 11 additional stations were collected in the
Straits of Florida and the cruise was concluded.  For navigation and placement
of stations, a global positioning system (GPS) and dynamic positioning were
used.

Because of ship time constraints, station spacing was determined as follows:
The first six stations of WOCE Section A5 were located at the 50-, 100-, 150-,
1500-, 2000-, and 2500-m isobaths and were about 18 nautical miles (nm) apart;
from there to the 4000-m depth (Station 12), the distance between stations was
about 23 nm.  From station 12 to the eastern limits of the Mid-Atlantic Ridge,
the stations were separated by 36 nm.  Across the Ridge, the separation was 32
nm.  From the western limits of the Mid-Atlantic Ridge to the 5000-m isobath
near the Bahamas, stations were again separated by 36 nm.  Stations close to
the Bahamas were separated by less than 30 nm.  The stations across the
Straits of Florida were occupied every 5 nm.

Near the Bahamas, the expedition deviated slightly from the planned
direction heading in order to cross the continental slope perpendicularly to
the direction of the isobaths and to obtain a clear crossing of the Deep
Western Boundary Current.

The ADCP and a thermosalinograph recorded continuously during the whole
cruise.  Wind information was recorded every hour.  Basic sampling equipment
included three CTDs and a 24-bottle General Oceanics (GO) rosette system
equipped with 10- or 12-L water sampling bottles.

The TCO2 concentration was determined in 660 samples from 33 of the 112 CTD
stations occupied during the cruise.

At the end of the cruise the ship was checked for tritium and 14C
contamination by the Tritium Laboratory of the University of Miami.


3.1.4.  DESCRIPTION OF VARIABLES AND METHODS

3.1.4.1.  Hydrographic Measurements

The R/V Hesperides carried three CTDs, two belonging to the Instituto
Espanol de Oceanografia (IEO) and one to Woods Hole Oceanographic Institution
(WHOI).  The two EG&G/NBIS Mark IIIb CTD underwater units belonging to IEO
were each equipped with pressure, temperature, conductivity, and polygraphic
oxygen sensors and were used throughout the cruise.  Each CTD was configured
identically with the same data scan length, variables, and scanning rate of
31.25 Hz.  (A detailed description of the Mark IIIb CTD can be found in Brown
and Morrison 1978.)  Both instruments were modified at WHOI to add a titanium
pressure sensor with a separately digitized resistive temperature device (RTD)
(Millard et al. 1993).  The third EG&G/NBIS Mark IIIb CTD was provided by WHOI
but was not used during this expedition.  A General Oceanics (GO) rosette
fitted with 24 10- or 12-L Niskin bottles was used with the CTD for collecting
water samples.  The GO rosette bottles were mounted approximately 0.5 m above
the CTD sensors.  The conductivity and oxygen sensors were also calibrated at
sea using the analysis of the water samples collected at each station.  The
depths of the sampling stations were based on classical standard depths,
although they varied on a station by station basis according to participants'
needs to sample a particular layer, provided there was no impairment of the in
situ calibration activities.  Because of delays inflicted by Hurricane Andrew
on the equipment shipment from Miami to Woods Hole, the post-cruise
calibrations were not performed on the CTD sensors until December.

All the water sample measurements for bottle salinity and bottle oxygen
were made in a constant temperature laboratory soon after each cast was
completed.  Water samples for salinity were collected from the Niskin bottles
in Ocean Scientific International glass bottles, and the measurements were
made within 24 hours after the station was finished.  In total, 2,294 samples
were measured.  The bottle salinities were measured with a Guildline Autosal
Model 8400A salinometer.  The manufacturer claims a precision of 0.0002 and an
accuracy of 0.003 when the instrument is operated at a temperature between +4
and -2 C of ambient temperature.  All the salinity measurements were made in a
temperature-controlled laboratory about 1-3°C below that of the salinometer
water bath.

Bottle oxygen determinations were carried out following the Winkler method
and using the reagents prepared according to Carpenter (1965).  On this
cruise, the modified Carpenter's equation as given by Culberson et al. (1991)
was used.  The endpoint of tritration was determined visually using starch as
the indicator.  Reagents were dispensed with 0- to 2-ml capacity Dispensette
glass and teflon dispensers from BRAND GMBH & CO.  The dispensers had a
certified accuracy of < or =0.6% and a coefficient of variation of < or =0.1%.
The tips of the dispensers were lengthened up to 6 cm with thin plastic tubing
to avoid the precipitation of manganese hydroxide in the neck of sample flasks.
Titration was done with a Metrohm Dosimat E.412 automatic burette.

Samples for nutrient analyses (silicate, nitrate, nitrite, and phosphate)
were collected in 150-mL acid-rinsed polythene flasks directly from the Niskin
bottles, following the protocol established by the WOCE Hydrographic Program.
Analyses were performed onboard with a four-channel Skalar, Inc. segmented
flow autoanalyzer.  Analyses were carried out immediately without any
treatment of the samples.  When necessary, samples were kept in the cold room
(unfrozen and never for more than 10 hours) without additives.  The analytical
techniques followed were those described by Whitledge et al. (1981) with minor
modifications to adapt them to the particular conditions of the instrument
used and concentration ranges observed.  Primary standards were prepared at
the beginning and in the middle of the cruise following Whitledge et al.
(1981).  Secondary standards were prepared every two days and preserved with
several drops of chloroform in the refrigerator.  Running standards of various
concentrations were prepared daily, and calibration curves were run at the
beginning of each session.  Standards were interleaved with unknown samples
in order to provide a measure of analytical stability.  Whenever changes in
sensitivity were noticed (particularly in the case of nitrate), the standards
allowed for a correction to be applied.  All concentrations were referred to
double distilled water prepared by reverse osmosis.  No seawater sample has
ever given a concentration negative with respect to this double distilled
water.  Phosphate analyses were corrected for the change in absorbance as a
result of the salinity effect.  Surface seawater was used as a carrier and,
except for silicate, it always showed the minimum concentrations in the water
column.  Silicate concentrations below the surface were often found to be
lower than those at the surface and very close to the values given by double
distilled water.  Replicate samples were analyzed at various depths.

More detailed information on hydrographic measurements can be found at:

       http://whpo.ucsd.edu/data/onetime/atlantic/a05/index.htm.


3.2.  Carbon Measurements

The total alkalinity (TALK), total carbon dioxide (TCO2), and pH were
determined from titrations of seawater collected at 33 stations.  The
titration systems were calibrated with Dickson standard seawater before and
during the cruise.  The pH was determined from the initial emf reading
relative to TRIS buffers.  The results for Dickson samples agree with
laboratory spectroscopic measurements to ±0.005.


Methods for Measurement and Computation

Three titration systems (Thurmond and Millero 1982) were used to
determined the TALK.  Each system consisted of a Metrohm 655 Dosimat titrator
and an Orion 720A pH meter that was operated by a personal computer (PC)
(Millero et al. 1993a).  The titration was made by adding HCl to the seawater
past the carbonic acid end point (pH ~ or = 3.5). The solutions were contained 
in water-jacketed cells (230 cm3) controlled to a constant temperature of 25°C 
with a Forma temperature controller. The computer program used to perform the 
titration was developed in the Rosenstiel School of Marine and Atmospheric 
Science (RSMAS) laboratory using RS232 interfaces. A BASIC program was used to 
run the titration and record the volume of the added acid and the emf of the 
electrode system. A typical titration recorded the emf after the readings became 
stable (0.09 mV) and added enough acid to change the voltage to a preassigned 
value (13 mV). A full titration (25 points) took about 20 minutes.  Using two 
systems, a 24-station cast could be analyzed in 4-5 hours.

The electrode systems used to measure the emf of the sample during a
titration consisted of a ROSS glass pH electrode and an Orion double-junction
reference electrode.  A number of electrodes were screened to select those to
be used in the titration systems.  Electrodes with non-Nerstian behavior
(slopes 1.0 mV different from theoretical) in acidic solutions were discarded.
The reliability of a glass-reference electrode pair was determined by
titrating 0.7-M NaCl solutions with HCl, by using seawater buffers (Ramette et
al. 1977), and by determining the TALK of TCO2 CRMs provided by Dr. Andrew
Dickson of SIO.  The titrations of 0.7-M NaCl solutions were used to evaluate
the electrode slope in acidic solutions (pH > or = 2 and < or = 4).  Seawater
buffers (Millero et al. 1993b) were used to evaluate the electrode slope near
a pH of 8.  The resulting experimental electrode slopes found for the cells
used in the present study are given in Table 1.  The slopes near a pH of 8 were
lower than the theoretical value (59.16 mV), whereas the slopes near a pH of 3
were near the theoretical value.  The electrodes were also evaluated by
determining the TALK, TCO2, and pH of TCO2 CRMs.  The results are given in
Table 2.  The results indicate that precise values of TALK (±1.8 µmol/kg),
TCO2 (±5 µmol/kg), and pH (±0.005) can be obtained on weighed samples of
seawater. The precision of the pH measurements for a given electrode (0.003)
is better than the average deviation from the mean (0.005).


Table 1:  Summary of the calibration results for the cells at 25°C

--------------------------------------------------------------------------
       Volume   Electrode slope    Standard   Electrode slope   Standard
 Cell  (cm3)   buffer calibration  deviation  acid calibration  deviation
 ----  ------  ------------------  ---------  ----------------  ---------
 1.00  212.59        58.40          -0.80         59.00           -0.20
 6.00  218.50        57.50          -1.70         59.60            0.40
 7.00  234.29        58.00          -1.20         59.50            0.30
--------------------------------------------------------------------------


Table 2:  Titrations of certified reference materials (S = 33.82) in the
          laboratory
       ----------------------------------------------------------------
        Seawater       TALK            TCO2            pH           N
        ---------    ------------    ----------    --------------   --
        Batch #12    2227.0 ± 1.8    2002.0 ± 5    7.93  ± 0.01     13
                                                   7.942 ± 0.0005*
        Standard     2226.6            1984        7.940 ± 0.0002**
       ----------------------------------------------------------------
        *Calculated from the initial emf using TRIS buffer calibration.
       **From spectroscopic measurements.


The HCl acid solutions used throughout the cruise were standardized in
the laboratory.  The approximately 0.25-M HCl solutions used contained 0.45-M
NaCl to yield an ionic strength equivalent to average seawater (0.7 M).
Approximately 20 liters of acid were made up in the laboratory.  The
calibrated acid was stored in 500 cm3 bottles for use at sea.  The acid was
standardized by titrating weighed amounts of Na2CO3 and TRIS dissolved in
0.7-M NaCl solution.  The blanks in the 0.7-M NaCl solutions were determined
by using coulometery and by titrations of the NaCl solutions with and without
added Na2CO3 and TRIS.  The TCO2 in the blanks and carbonate solutions was
measured daily by a UIC coulometer.  The coulometer was calibrated using CO2
gas loops and CRMs.  The blanks of the titrations of TRIS were obtained by
extrapolation to zero-added salt.  The alkalinity blanks in the NaCl were
generally about 14 ± 1 µM.  The concentrations of the standard acids obtained
from Na2CO3 and TRIS were in good agreement (Millero et al. 1993a).

The volumes of the cells used at sea were determined in the laboratory
by weighing the cells filled with water.  The density of water at the
temperature of the measurements (25°C) was calculated from the international
equation of state of seawater (Millero and Poisson 1981).  The nominal volumes
of all the cells was about 230 cm3 and the values were determined to ±0.03 cm3.
The reliability of the volumes was assessed by comparing the values of TALK
obtained for standard solutions with open and closed cells.

A FORTRAN computer program has been developed to calculate the CO2
parameters (pHsws, emf, TALK, TCO2, and pK1*) in Na2CO3 and seawater
solutions.  These programs are patterned after those developed by Dickson
(1984).  This program requires an input of the concentration of the acid, the
volume of the cell, the salinity, the temperature of analysis, volume of added
HCl (VHCl), and the corresponding measured values of the emf.  To obtain a
reliable TALK from a full titration, at least 25 points have to be collected.
The precision of the fit is less than 0.4 µmol/kg when pK1* is allowed to vary,
and 1.5 µmol/kg when pK1* is fixed.  This titration program has been compared
with the titration programs used by others (Dickson 1981; C. Goyet, WHOI,
personal communication, 1992; Bradshaw and Brewer 1988), and the values of
TALK agree to within ±1 µmol/kg.  Copies of the titration and calculation
programs used are available upon request.


Calibrations

Before the cruise a number of titrations were made on CRMs (#12) in the
laboratory.  The laboratory titration results for TALK, TCO2, and pH are given
in Table 2 along with the assigned TCO2 and the pH measured relative to TRIS
buffers (Dickson 1993) and spectrophotometrically (Byrne and Breland 1989;
Robert-Baldo et al. 1985; Millero et al. 1993b; Clayton and Byrne 1993).  It
should be pointed out that the values of pH are on the seawater scale defined
by Dickson (1984):

            pHsws = -log[H+]sws = -log{[H+] + [HSO4-] + [HF]}          (1)

The precision in the values of TALK (±2 µmol/kg), TCO2 (±5 µmol/kg), and pH
(±0.005) was quite good. The titration values of TCO2 were 18 ± 4 µmol/kg higher
than the values assigned and measured by coulometery. The titration values of pH
(7.93 ± 0.01) were 0.01 lower than the values measured by spectrophotometric
methods (7.940 ± 0.002) and using seawater buffers (Millero et al. 1993b). The
differences in pH and TCO2 are caused by the non-ideal behavior of the
electrodes near a pH of 8 (Millero et al. 1993a). Calibration of the electrodes
using TRIS seawater buffers yielded a pH of 7.942 ± 0.005 from the initial emf
readings of the titration. These results are in excellent agreement with the
spectrophotometrically determined pH and show a lower standard error than the
values determined from the titrations.

The program used to calculate the TCO2 parameters assumed that the
electrodes would respond to a change in pH with an ideal slope of 59.2 mV at
25°C as determined from the Nernst equation.  The slopes of the electrodes
using buffers and titrating with HCl frequently gave non-ideal behavior.  The
parameters produced by varying this slope indicated (Millero et al. 1993a)
that the deviations resulting from these changes were much greater for TCO2
than for TALK.  Errors of 1.0 mV in the slope yielded differences in TALK and
TCO2, respectively, of 2.1 and 22.8 µmol/kg when the pK1* was also allowed to
vary (Millero et al. 1993a).  The values of TALK were not strongly affected by
the behavior of the electrodes.  The values of TCO2 and pH determined for the
CRMs with the buffer-derived slope (58.4) were in good agreement with the
correct values (pH = 7.935 and TCO2 = 1984 µmol/kg).  These calculations
indicated that the deviations in the TCO2 derived from titration were a result
of errors in the slope of the electrode, and not a result of unknown
protolytes (Bradshaw and Brewer 1988).  If the slope determined from the
buffers was used, the titrations yielded reliable values of pH, TALK and TCO2.
This fact was used to make sure that the field titration measurements yielded
the most reliable values of pH and TCO2.

During the cruise the electrodes in each titration system were calibrated with 
TRIS seawater buffers (Millero 1986) of known pHsws (8.057) determined with a 
H2, Pt/AgCl, Ag electrode (Millero et al. 1993b). Titrations of CRMs (#12) were 
also made during the cruise. The results are given in Table 3. The average 
values, TALK = 2229 ± 7 µmol/kg, TCO2 = 1984 ± 6 µmol/kg, and pH = 7.944 ± 0.01, 
are in good agreement with the laboratory results. The deviations are larger at 
sea than obtained in the laboratory (Table 2) but indicate that the titration 
systems performed well throughout the cruise. The large errors are related to 
problems in reproducing the volume in the glass cells. Presently, a plastic cell 
with a more reproducible volume is used, making it possible to reproduce the 
CRMs to ±2 µmol/kg for TALK, to ±3 µmol/kg for TCO2, and to ±0.005 for pH 
(Millero et al. 1993a).


Table 3:  Titrations of certified reference materials at sea (Batch #12)

      ----------------------------------------------------------------
       Cell             TALK         TCO2           pH             N
       ----           --------     --------    -------------       --
       1              2229 ± 6     1983 ± 5    7.937 ± 0.009*      14
       6              2230 ± 8     1981 ± 8    7.944 ± 0.021*       5
       7              2229 ± 6     1984 ± 8    7.948 ± 0.013*      12
       --------------------------------------------------------------
       Average        2229 ± 7     1984 ± 6    7.942 ± 0.014       31
       --------------------------------------------------------------
       Standard       2226.6**     1984***     7.940****
      ----------------------------------------------------------------
       *Calculated from the initial emf using TRIS buffer calibration.
       **Certified value from weighted titrations.
       ***Certified value from manometric extraction technique.
       ****Results obtained in the laboratory using spectrophotometric methods


Results

The cruise track of the R/V Hesperides is shown in Fig. 1 in the hard copy
report.  A summary of the 33 TCO2  stations that were sampled during the cruise
is given in Table 4.  Based upon the CRM calibrations at sea, the accuracy of
the measured parameters is estimated to be ±7 µmol/kg for TALK and TCO2 and
±0.02 for pH.  The thermodynamic consistency of the measurements can be shown
by comparing the calculated values of pH (7.944), TALK (2334 µmol/kg), and TCO2
(1984 µmol/kg) using the constants of Roy et al. (1993) with the measured values
(Table 3).  The agreement is quite good.  The values of TALK, TCO, and pH as a
function of depth for all of the samples are shown in Figs. 3-5 in the hard copy
report.  Plots of the surface properties of the waters sampled are shown in
Figs. 6-8 in the hard copy report.

The temperature increases from 22°C near the Spanish coast to 27°C off the coast 
of Florida. The salinities go through a maximum (37.5) between stations 20 to 50 
(30°to 45°W). The surface values of TALK (Fig. 7 in hard copy) follow this 
trend. The TCO2 is fairly constant from stations 1 to 60 (2108 ± 10 µmol/kg) and 
decreases off the coast of Florida to 2020 µmol/kg. The pH at 25°C increases 
from 8.05 off the coast of Spain to about 8.12 off the coast of Florida (average 
pH = 8.05 ± 0.03). The values of TALK and TCO2 normalized to S = 35 are shown in 
Fig. 8 (in hard copy). The average normalized TALK is 2293 ± 4 µmol/kg for the 
surface waters, whereas the average normalized TCO2 is 1970 ± 20 µmol/kg. The in 
situ fugacities of CO2 (fCO2) calculated from the measured values of TALK and 
TCO2 are shown in Fig. 8 (in hard copy). From the secalculations, the surface 
waters (fCO2 = 402 ± 15 µatm) are supersaturated with CO2(delta fCO2 = 42 ± 15 
µatm) for all the surface waters.


Table 4:  Summary of carbonate system stations occupied during the cruise

       ---------------------------------------------------------------
        Station      Latitude      Longitude      Depth       Date
          no.          (°N)           (°W)          (m)
        -------      --------      ---------      -----     ---------
           1          24°29'         15°58'          53      7/20/1992
           3          24°29'         16°29'         575      7/20/1992
           8          24°29'         18°20'        2736      7/20/1992
          11          24°30'         19°35'        3393      7/22/1992
          13          24°30'         20°40'        4186      7/23/1992
          15          24°30'         21°59'        4705      7/24/1992
          18          24°30'         23°59'        5149      7/24/1992
          21          24°30'         25°59'        5403      7/25/1992
          25          24°30'         28°39'        5723      7/26/1992
          28          24°30'         30°38'        5745      7/27/1992
          31          24°30'         32°40'        6426      7/28/1992
          34          24°30'         34°40'        5354      7/29/1992
          37          24°30'         36°40'        5008      7/30/1992
          40          24°30'         38°40'        4580      7/30/1992
          43          24°30'         40°35'        4551      7/31/1992
          46          24°30'         42°20'        4430      8/01/1992
          49          24°30'         44°04'        4182      8/01/1992
          53          24°30'         46°24'        3518      8/02/1992
          57          24°30'         48°44'        4541      8/03/1992
          60          24°30'         50°29'        4975      8/04/1992
          62          24°30'         51°39'        4888      8/04/1992
          64          24°30'         52°50'        5231      8/05/1992
          67          24°30'         54°40'        6275      8/05/1992
          70          24°30'         56°40'        6024      8/06/1992
          73          24°30'         58°39'        6145      8/07/1992
          77          24°30'         61°19'        5965      8/08/1992
          81          24°30'         63°59'        5858      8/09/1992
          84          24°30'         65°59'        5832      8/10/1992
          82          24°30'         68°00'        5805      8/11/1992
          90          24°30'         70°00'        5626      8/12/1992
          93          24°30'         71°59'        5571      8/12/1992
          97          25°00'         74°20'        4994      8/13/1992
         101          24°30'         75°31'        1040      8/14/1992
       ---------------------------------------------------------------



3.1.5.  DATA CHECKS AND PROCESSING PERFORMED BY CDIAC

An important part of the NDP process at the Carbon Dioxide Information
Analysis Center (CDIAC) involves the quality assurance (QA) of data before
distribution.  Data received at CDIAC are rarely in a condition that would
permit immediate distribution, regardless of the source.  To guarantee data of
the highest possible quality, CDIAC conducts extensive QA reviews that involve
examining the data for completeness, reasonableness, and accuracy.  The QA
process is a critical component in the value-added concept of supplying
accurate, usable data for researchers.

The following information summarizes the data processing and QA checks
performed by CDIAC on the data obtained during the R/V Hesperides cruise along
WOCE Section A5 in the Atlantic Ocean.

1.  Carbon-related data and hydrographic measurements were provided to CDIAC
    by Frank Millero of the Rosenstiel School of Marine and Atmospheric 
    Science (RSMAS) at the University of Miami, Miami, Florida.  The final 
    hydrographic and chemical measurements and the station information files 
    were provided by the WOCE Hydrographic Program Office (WHPO) after quality  
    evaluation. A FORTRAN 77 retrieval code was written and used to merge and 
    reformat all data files.

2.  To check for obvious outliers, all data were plotted by use of a
    PLOTNEST.C program written by Stewart C. Sutherland (Lamont-Doherty Earth
    Observatory).  The program plots a series of nested profiles, using the
    station number as an offset; the first station is defined at the beginning,
    and subsequent stations are offset by a fixed interval (Figs. 9-11 in hard
    copy).  Several outliers were identified and marked with the quality flags
    of 3 (questionable measurement) or 4 (bad measurement) (see File
    Descriptions in Section 7 of this documentation).

3.  To identify noisy data and possible systematic, methodological errors,
    property-property plots for all parameters were generated (Fig. 12 in hard
    copy), carefully examined, and compared with plots from previous expeditions
    in the Atlantic Ocean.

4.  All variables were checked for values exceeding physical limits, such as
    sampling depth values that are greater than the given bottom depths.

5.  Dates, times, and coordinates were checked for bogus values (e.g.,
    values of MONTH < 1 or > 12; DAY < 1 or > 31; YEAR < or > 1992; TIME < 0000
    or > 2400; LAT < 20.000 or > 30.000; and LONG < -90.000 or > 0.000).

6.  Station locations (latitudes and longitudes) and sampling times were
    examined for consistency with maps and cruise information supplied by F. J.
    Millero of RSMAS.

7.  The designation for missing values, given as -9.0 in the original files,
    was changed to -999.9.



3.1.6.  HOW TO OBTAIN THE DATA AND DOCUMENTATION

This database (NDP-074) is available free of charge from CDIAC.  The
data are available from CDIAC's anonymous file transfer protocol (FTP) area
via the Internet.  Please note:  Your computer needs to have FTP software
loaded on it (this is built in to most newer operating systems).  Use the
following commands to obtain the database.

      ftp cdiac.esd.ornl.gov or  >ftp 128.219.24.36
      Login: anonymous or ftp
      Password: your e-mail address
      ftp> cd pub/ndp074/
      ftp> dir
      ftp> mget (files)
      ftp> quit

The complete documentation and data can also be obtained from the CDIAC
oceanographic Web site (http://cdiac.esd.ornl.gov/oceans/doc.html), through
CDIAC's online ordering system (http://cdiac.esd.ornl.gov/pns/how-order.html),
or by contacting CDIAC.

Contact information:

                    Carbon Dioxide Information Analysis Center
                    Oak Ridge National Laboratory
                    P.O. Box 2008
                    Oak Ridge, Tennessee 37831-6335
                    U.S.A.

                    Telephone: 865-574-3645
                    Telefax:   865-574-2232 (Fax)
                    E-mail:    cdiac@ornl.gov
                    Internet:  http://cdiac.esd.ornl.gov/



REFERENCES

Bradshaw, A. L., and P. G. Brewer. 1988. High precision measurements of
     alkalinity and total carbon dioxide in seawater by potentiometric 
     titration-1. Presence of unknown protolyte(s). Marine Chemistry 23:69-86.

Brown, N., and G. Morrison. 1978. WHOI/Brown Conductivity, Temperature, and
     Depth Microprofiler.  WHOI Technical Report #78-23. Woods Hole Oceanographic
     Institution, Woods Hole, Mass., U.S.A.

Byrne, R. H., and J. A. Breland. 1989. High precision multiwavelength pH
     determinations in seawater using cresol red. Deep-Sea Research 36:803-10.

Carpenter, J. H. 1965. The Chesapeake Bay Institute technique for the Winkler
     dissolved oxygen titration. Limnology and Oceanography 10:141-3.

Clayton T., and R. H. Byrne. 1993. Spectrophotometric seawater pH measurements:
     total hydrogen ion concentration scale calibration of m-cresol purple and
     at-sea results. Deep-Sea Research 40:2115-29.

Culberson, C. H., G. Knapp, M. C. Stalcup, R. T. Williams, and F. Zemlyak. 1991.
     A comparison of methods for the determination of dissolved oxygen in
     seawater. Report No. WHPO 91-2. WOCE Hydrographic Program Office. Woods 
     Hole Oceanographic Institution, Woods Hole, Mass., U.S.A.

Dickson, A. G. 1981. An exact definition of total alkalinity and a procedure for
     the estimation of alkalinity and total CO2 from titration data. Deep-Sea
     Research 28:609-23.

Dickson, A. G. 1984. pH scales and proton-transfer reactions in saline media
     such as seawater. Geochemica et Cosmochemica Acta 48:2299-2308.

Dickson A. G. 1993. pH buffers for sea water media based on the total hydrogen
     ion concentration scale. Deep-Sea Research 40:107-18.

Millard, R., G. Bond, and J. Toole. 1993. Implementation of a titanium strain-
     gauge pressure transducer for CTD applications. Deep-Sea Research
     40(5):1009-21.

Millero, F. J. 1986. The pH of estuarine waters. Limnology and Oceanography
     31:839-847.

Millero, F. J., and A. Poisson. 1981. International one-atmosphere equation of
     state of seawater. Deep-Sea Research 28:625-629.

Millero F. J., J.-Z. Zhang, K. Lee, and D. M. Campbell. 1993a. Titration
     alkalinity of seawater.  Marine Chemistry 44:153-66.

Millero F. J., J.-Z. Zhang, S. Fiol, S. Sotolongo, R. N. Roy, K. Lee, and S.
     Mane. 1993b. The use of buffers to measure the pH of seawater. Marine
     Chemistry 44:143-52.

Ramette, R. W., C. H. Culberson, and R. G. Bates. 1977. Acid base properties of
     tris (hydrolymethyl) aminomethane (tris) buffers in seawater from 5 to 
     40°C.  Analytical Chemistry 49:867-70.

Robert-Baldo, G., M. J. Morris, and R. H. Byrne. 1985. Spectrophotometric
     determination of seawater pH using phenol red. Analytical Chemistry 
     57:2564-67.

Roemmich, D., and C. Wunsch. 1985. Two transatlantic sections: Meridional
     circulation and heat flux in the subtropical North Atlantic Ocean. Deep-Sea
     Research 32(6):619-64.

Roy R. N., L. N. Roy, K. M. Vogel, C. P. Moore, T. Pearson, C. E. Good, F. J.
     Millero, and D. M. Campbell. 1993Determination of the ionization constants
     of carbonic acid in seawater. Marine Chemistry 44:249-68.

Thurmond, V. L., and F. J. Millero. 1982. Ionization of carbonic acid in sodium
     chloride solutions at 25°C. Journal of Solution Chemistry 11(7):447-56.

Whitledge, T. E., S. C. Malloy, C. J. Patton, and C. D. Wirick. 1981. Automated
     analysis of sea water. BNL-51398. Brookhaven National Laboratory, U. S.
     Department of Energy, Upton, New York, U.S.A.



3.2.  SALINITY
      (R. Molina)

For the salinity measurements the recommendations given in the training Course
Notes (Ocean Scientific Int., Funchal, July 1991) were followed.  The water
sample salinities were measured with a Guildline Autosal Model 8400A
salinometer.  The manufacturer claims a precision of 0.0002 and an accuracy of
0.003 when the instrument is operated at a temperature between +4˚ and -2˚C of
ambient temperature.  All the salinity measurements were made in a temperature
controlled laboratory about 1˚ to 3˚C below that of the salinometer water bath.

Two different batches of standard water were used: batch P120 (April 6, 1992)
with 50 ampoules and 20 ampoules from batch P117 (July 10, 1991).  After the
salinometer was standardized with water from the first batch, 8 samples from an
ampoule of the second batch were measured, and the labelled value of 34.994 was
obtained within 2x10-5.  On the average, the salinometer was standardized every
31 samples.

Water samples were collected from the Niskin bottles in Ocean Scientific
International glass bottles and the measurements were made within the 24 hours
after the station was finished.  In total 2294 samples were measured.

In determining the conductivity ratio, three measurements were made from every
sample providing the differences were smaller than 2x10-5.  If not, more
measurements were made until three consecutive values exhibited differences
smaller than 2x10-5.

In 3 stations, samples were replicated with the following results:

         ----------------------------------------------------------
          STA.  DEPTH   BOTTLE NO.   NO. OF SAMPLES  STANDARD DEV.
          ----  -----  ------------  --------------  -------------
           50   2500   02,3,4,5,6,7        6          ± 3.6x10-4
           64   2532        6              8          ± 1.3x10-4
           72    249        16             8          ± 2.1x10-4
         ----------------------------------------------------------

During one day when the air conditioning of the laboratory broke down, salinity
measurements for stations 2 to 3 were made with the laboratory temperature 0.3˚C
above the salinometer bath temperature.


3.3.  OXYGEN
      (J. Escánez)

Oxygen determinations were carried out following the Winkler method and using
the reagents prepared according to Carpenter (1965).  We used the modified
Carpenter's equation as given by Culberson et al (1991).  The endpoint of
titration was determined visually using starch as indicator.

Reagents were dispensed with all glass and teflon dispensers "Dispensette" from
Brand GMBH and Co. (0-2 ml capacity) with certified accuracy of ± 0.6% and a
coefficient of cariation of ± 0.1%.  The tips of the dispensers were lengthened
up to 6 cm with thin plastic tubing to avoid the precipitation of manganese
hydroxide in the neck of sample flasks.

Titration was done with a Metrohm Dosimat E.412 automatic burette using
Potassium Iodate "pro.anlaysi" Merck (Lot Nº 150 BZ 252853.  Assay 99.95 -
100.05%) at a concentration of 0.0100 N.

Standards and blanks were dispensed with class "A" calibrated hand pipets with 
certified accuracy of ± 0.02 ml for 10 ml pipets and ± 0,006 ml for 1 ml pipets.

In total, 2338 samples were taken (Table IV). In order to assess good quality 
results, calibration sets were run through 7 stations. Inter-sample calibrations 
were run on 3 stations by taking 1 sample from 6 Niskin bottles triggered at the 
same depth, while on 4 stations intra-samples calibrations were performed taking 
6 samples of 2 Niskin bottles triggered at the maximum and minimum O2 layers 
respectively. Values are shown in Tables V and VI.


Table IV:  DISTRIBUTION OF CASTS/ANALYSTS

     -----------------------------------------------------------------------
      ANALYSTS    STATION CASTS  STATIONS ANALYZED  NO. OF SAMPLES ANALYZED
      ----------- -------------  -----------------  -----------------------
      J.G. Braun       36               11                   234
      B. Amengual      38               20                   446
      J. Escánez       38               81                  1658
     -----------------------------------------------------------------------


Table V:  CALIBRATIONS BETWEEN CASTS

       -------------------------------------------------------------------
        STN   DEPTH   BOTTLE NO.      O2 (ML/L) MEAN  O2 (ML/L) STD. DEV.
        ---  -------  --------------  --------------  -------------------
          1     40 m  12,13,14,15,17     X= 5.711        sd= ± 0.009
          1     40 m  1,2,3,4,5,6        X= 4.661        sd= ± 0.031
         50   2500 m  2,3,4,5,6,7        X= 5.655        sd= ± 0.005
        107    378 m  3,4,5,6,7,8        X= 2.998        sd= ± 0.005
       -------------------------------------------------------------------


Table VI:  CALIBRATIONS WITHIN CASTS (MAXIMUM AND MINIMUM)

                 ----------------------------------------------
                  STN  BOTTLE  MAX/MIN  O2 (ml/l)   O2 (ml/l)
                        NO.      O2       MEAN      STD. DEV.
                  ---  ------  -------  ---------  -----------
                  14     1       Max    X= 5.601   sd= ± 0.015
                  14    10       Min    X= 2.575   sd= ± 0.003
                  32     8       Max    X= 5.622   sd= ± 0.002
                  32    12       Min    X= 3.294   sd= ± 0.014
                  67     6       Max    X= 5.907   sd= ± 0.009
                  67    12       Min    X= 3.513   sd= ± 0.002
                  89     5       Max    X= 6.193   sd= ± 0.003
                  89    11       Min    X= 3.469   sd= ± 0.005
                 ----------------------------------------------


3.4.  NUTRIENTS
      (A. Cruzado)

Analyses were performed on board with a four channel SKALAR segmented flow
autoanalyzer. Samples were collected in 150 ml acid-rinsed polythene flasks
directly from the Niskin bottles, following the protocol established by the WOCE
Hydrographic Programme. Analyses were carried out immediately without any
treatment of the samples. When necessary, samples were kept in the cold room
(unfrozen and never for more than 10 hours) without additives.

The analytical techniques followed were those described by Whitledge et al.
(1981) with minor modifications to adapt them to the particular conditions of
the instrument used and concentration ranges observed. Primary standards were
prepared at the beginning and in the middle of the cruise prepared every two
days and preserved with some drops of chloroform in the fridge. Running
standards were interleaved with unknown samples in order to provide a measure of
analytical stability. Whenever changes in sensitivity (particularly in the case
of nitrate) were noticed, these standards allowed for a correction to be applied.

All concentrations were referred to double distilled water prepared by reverse
osmosis through milliRo, dionization through Milli-Q and distillation. No sea
water sample has ever given a concentration negative with respect to this double
distilled water. Phosphate analysis corrected for the change in absorbance due
to the salinity effect. Surface seawater was used as carrier and, except for
silicate, it always showed the minimum concentrations in the water column.

Silicate concentrations below the surface were often found to be lower than the
surface values and very close to the values given by double distilled water.
Replicate samples were analysed at various depths both from the same and from
different Niskin bottles. A comparison of all the primary and secondary
standards used during the cruise is underway and may introduce some small
corrections to the results. A statistical assessment of such analyses is being
prepared. Some nutrient diagrams are shown in figure 3.


Addendum to the Nutrients Report on A05
(A. Cruzado)

During the HE06 cruise (July/August 1992) along the WOCE line A-5, dissolved
inorganic nutrients (orthophosphate, nitrate+nitrite, nitrite, and
orthosilicate) were collected and analyzed on board the R/V Hesperides using a
continuous flow analyzer by Antonio Cruzado (Centro de Estudios Avanzados de
Blanes, Spain) following methods adapted from Withledge et al. (1981). These
methods were used in the fifth 1989/1990 ICES international inter-comparison
exercise for nutrients in seawater (Aminot and Kirkwood, 1995). Three different
quality control procedures were applied to the A5 nutrient data. First, spurious
chemical data were flagged according to WOCE quality control codes. These are
data values shown to be analytically incorrect ("Bad"). Second, the A5 chemical
data were compared to the August 1992, Trident cruise on the RV Baldrige between
Abaco Island, the Bermuda Rise and the Mid-Atlantic Ridge (Garcia, 1996). This
provided a mean to compare the two cruises in the western basin only. Third, the
A5 data were compared to historical oceanographic data collected since the
GEOSECS program (Table 1). The long-term precision of the A5 chemical data was
estimated following the method of Saunders (1986). Potential temperature
(Fofonoff and Millard, 1983) was fitted to the nutrient data from the HE06 and
AT109 cruises by linear least-squares for water with temperatures less than or
equal to 1.8ºC and 2.1ºC in the western (45-75 W) and eastern (20-44 W) Atlantic
basins, respectively (Garcia, 1996). The standard deviation of the measured
values for each chemical variable from the expected values calculated from the
coefficients of the regression lines for stations in the western and eastern
basins are shown in Table 2. Chemical data points which deviated significantly
(more than 5 SD from the mean) were flagged as questionable. No quality control
was applied to the nitrite data.


Table 1:  HISTORICAL DATA (1972-92) USED IN THIS WORK

          --------------------------------------------------------------
           CRUISE/LEG  SHIP         CRUISE DATES            INSTITUTION
           ----------  -----------  ---------------------   -----------
           AT109-II    Atlantis II  August-September,1981   WHOI
           AT109-I     Atlantis II  June-July,1981          WHOI
           Trident     Baldridge    August,1992             LDEO
           EN129       Endeavor     April,1985              WHOI
           GEOSECS     Knorr        July,1972-April,1973    SIO
           TTO-NAS     Knorr        April-October,1981      SIO
           TTO-TAS     Knorr        December-February,1983  SIO
           KN104       Knorr        July-August,1983        WHOI
           OC133-II    Oceanus      January,1983            WHOI
           OC202       Oceanus      July-September,1988     SIO
          --------------------------------------------------------------


Table 2:  ESTIMATES OF PRECISION (1 SD) OF THE AT109-II AND HE06 CHEMICAL 
          DATA.  NUMBERS IN PARENTHESIS INDICATES THE NUMBER OF DATA POINTS 
          IN THE CALCULATION DESCRIBED IN THE TEXT ABOVE (GARCIA, 1996).

          -------------------------------------------------------
           CRUISE   | PHOSPHATE |   N+N   |  SILICATE | OXYGEN
           -----------------------------------------------------
                        WESTERN ATLANTIC (75-45 W)
           AT109-II | 0.04 (81) | 0.5 (83)|  1.8 (83) | 2.2 (86)
           HE06     | 0.08 (58) | 0.3 (79)|  1.9 (82) | 1.4 (83)
           -----------------------------------------------------
                        EASTERN ATLANTIC (20-44 W)
           AT109-II | 0.03 (65) | 0.2 (64)|  0.6 (64) | 1.9 (74)
           HE06     | 0.08 (62) | 0.2 (88)|  0.9 (94) | 1.6 (99)
          -------------------------------------------------------



3.5.  CFC-11 AND CFC-12
      (W. Smethie)

The objective of the CFC measurement program on this cruise was to measure the
distribution of CFC-11 and CFC-12 in the thermocline along 24˚N in the Atlantic
and in recently ventilated components of North Atlantic Deep Water, including
the Deep Western Boundary Current, spreading southward in the western North
Atlantic.

The CFC measurements were made on board with a CFC analysis system interfaced to
a gas chromatograph with an electron capture detector.  This method is described
in Smethie et al. (1988) and is similar to the Bullister and Weiss (1988)
technique.

One difference for this cruise was the use of a Porasil B precolumn and a
SP21000 main column instead of Porasil B for both columns.  This combination
allowed CFC-113 and carbon tetrachloride to be detected as well as CFC-11 and
CFC-12.  However carbon tetrachloride and CFC-113 were not measured on every
station because of the longer analysis time required.  The purpose of these
measurements was to obtain preliminary information on the distribution of these
substances in the ocean and they are not of the same quality as the CFC-11 and
CFC-12 measurements.

Some problems were encountered.  A set of new syringes had a low level CFC-11
contamination (0.02 - 0.04 pmol/kg).  Blanks for these syringes were determined
and monitored by analyzing zero CFC water from the deep eastern basin or by
comparison to duplicate samples collected in old syringes which were not
contaminated.  These blanks decreased during the cruise.  There was a high (20-
30% of surface water concentration) and variable CFC-113 system blank and the
Niskin bottles became severely contaminated with CFC-113 at station 75, probably
due to a fire control exercise by ship's personnel, and remained contaminated
for the remainder of the cruise.

The general sampling strategy was to sample every other station which resulted
in approximately 60 nm spacing.  Every station was sampled near the western
boundary.  Generally 10 or 11 samples were taken between the surface and 1000 m
along the entire section.  In the eastern basin the deep water contained no
CFCs, but samples were collected to determine Niskin bottle/sampling blanks and
syringe blanks.  In the western basin, CFCs were detected throughout the water
column.  Vertical spacing varied between 150 and 400 m with more closely spaced
samples at about 1500 m and 3500-4000m to resolve CFC maxima at these levels.  A
section was also taken across Florida Strait with approximately 5 nm horizontal
resolution and 50-100 m vertical resolution.  A total of about 1100 water
samples, not including duplicates, were analyzed.

In the figure 4, shown are vertical profiles of preliminary shipboard values of
F-11.


3.6.  PARTICULATE ORGANIC MATTER
      (A.F. Ríos)

Two liters of seawater at levels (10, 15, 50, 100, 200 and 400 m) on 25 stations
were filtered through a glass fiber filter (Whatman GF/F of 25 mm diameter) in
order to determine the particulate carbon and nitrogen using a 2400 Perkin Elmer
Elemental Analyzer.

To determine particulate phosphorous, samples of one liter of seawater retained
I filters (Millipore AAWPO2500) were taken at the same stations and levels as
before.  These samples will be oxydized with percloric-sulphuric acid (Ríos and
Fraga, 1987) and later determination of phosphate will be carried out by the
method described by Grasshoff et al. (1983). Carbohydrates will be determined by
the technique of Antron reagent (Rios, 1992) from samples of one liter of
seawater retained in filters (Millipore AAWP02500) taken at these same stations
and levels.


3.7.  CALCIUM
      (G. Rosón)

The 450 samples analyzed for this parameter were taken on 20 stations at all
levels.

The method used for determining calcium is a volumetric titration of about 130 g
of seawater with potentiometric detection of end point by calcium selective
electrode, using EGTA (ethyleneglycol-bis) (B-aminoethyleter), N, N, N1, N1,
tetraacetic acid) as titrant (0.18 M) and 25 ml of borax (0.1 M) as buffer 
(Rosónand Pérez, 1990; Rosón, 1992).  The reproducibility of the method, made on 
a 25 l storage bottle, was 0.07% for 70 samples.


3.8.  CARBON-14
      (W. Smethie for W. Broecker)

Carbon-14 samples were collected in the thermocline at a few select stations.
These samples will be analyzed by accelerator mass spectrometry.  This is part
of a larger program to collect samples over the entire North Atlantic from ships
of opportunity during the next few years.  The objective is to determine the
distribution of bomb carbon-14 in the thermocline and compare this distribution
to the distributions measured in 1981 on the TTO program and 1972 on the GEOSECS
program.  The evolving bomb carbon-14 distribution will be used to investigate
circulation and mixing in the thermocline and uptake of carbon dioxide by the
ocean.

Samples were collected at stations 13, 24, 35, 53, 66, 81, and 92.  In general 8
samples were collected at each station, one in the surface mixed layer and seven
at the following sigma-theta surfaces: 26.2, 26.4, 26.6, 26.8, 27.0, 27.2, and
27.4.  Samples were also collected at stations 103 (one in the oxygen maximum)
and 107 (six throughout the water column) in the Straits of Florida and at test
station (ten samples) just west of the Strait of Gibraltar.  A total of 71
samples were collected.


3.9.  ADCP
      (M. Garcia)

The ADCP model used was a RD-VMO 150.  The selected sampling intervals were 180
s, 40 depth bins of 8 m length.  The profiler was recording continuously during
the whole cruise and the data was recorded on diskettes.


3.10.  THERMOSALINOGRAPH
       (E. Alvárez)

During W.O.C.E. A-5 section, temperature and salinity were measured across the 
Atlantic Ocean surface using a Seabird thermosalinometer (serial number 626a). 
Data acquisition began on station number one and finished close to Miami harbor. 
The time step between each acquisition was three minutes. The obtained data were 
stored in groups of files, each group corresponding to one navigation day. Water 
conductivity was recorded from the third navigation day on. Two electricity 
failures (during the second and fourth days) and at least one water flux 
stoppage (during the fourth day) interrupted the continuous time series.


2.12.  CHLOROPHYLL PIGMENTS AND PRIMARY PRODUCTION

Two kinds of analysis have been undertaken for pigment studies. One was based on
spectrophotometric equations with readings of absorbances at 664, 645, 630 and
750 nm.  In the other smaller volumes of seawater were used for analysis of
chlorophyll and phaeopigments based on fluorescence readings before and after
acidification of the sample.


3.11.1.  CHLOROPHYLL PIGMENTS
         (Z.R. Velásquez)

Water samples were taken at several depths (0-250m) on all stations of the WOCE
A-5 section from NW Africa to the Bahamas.

The phytoplanktonic pigments were determined on board immediately after sampling
by the spectrophotometric technique described by Jeffrey and Humphrey (1975).
About 3.3 liters of seawater were filtered under vacuum through 4.7 cm Whatman
GF/F filters.  After extraction during a minimum of 24 hours with 5 ml (90%)
acetone in the dark at 0˚C, the resulting suspension was centrifuged at 3000 rpm
for 30 minutes.

The absorbances at 664, 645 and 630 nm, required for the computation of the
concentrations of Chlorophyll A, B and C, were determined in the supernatant (5
ml), allowance being made for the eventual presence of turbidity by measuring
also the absorbance at 750 nm.  All absorbance measurements were done with a LBK
spectrophotometer linked to a computer.

The following formula was used for the computation of the pigment concentration
in the supernatant in µg/l.

Chlorophyll (µg/l) =OD* Vac/Vsw

          OD (a) = 11.85*(D664-D750)-1.54*  (D645-D750)-0.08*(D630-D750)
          OD (b) = 21.03*(D645-D750)-5.43*  (D664-D750)-2.26*(D630-D750)
          OD (c) = 24.52*(D645-D750)-1.67*  (D664-D750)-7.66*(D645-D750)

where
    Vac = volume of acetone (in ml);
    Vsw = volume of seawater (in l);
   Dxxx = optical density at wavelength xxx and 1 cm optical path

Pheopigments were determined by acidifying the extracts with two drops of 10%
HCl and reading at the same wavelengths.

Samples of water at the same level were preserved with Lugol (Potassium
Iodate/Iodine solution buffered with sodium acetate) for further phytoplankton
analysis with an Olympus inverted microscope to which a computer/video
digitizing system has been adapted.

In the figure 7 vertical profiles of total chlorophyll for stations 1 through 60
are shown.


3.11.2.  CHLOROPHYLL PIGMENTS AND PRIMARY PRODUCTION
         (J. García-Braun)

Water samples were taken for pigment analysis at several depths (mainly, 0 - 200
m) on 90 stations for a total of 1152 analyses for chlorophyll and phaeophytin.

With respect to the pigment distribution in the water column, ours main
objectives were: to obtain the vertical distribution of chlorophyll a, based on
fluorescence readings, calibrated against spectrophotometer following SCOR-
UNESCO (1966) and the vertical distribution of chlorophyll and phaeophytin,
based on fluorescence readings, before and after acidification, according to
equations by Lorenzen (1966); and to estimate the pigments biomass including
size classes, evaluating picoplankton less than 2 microns and populations bigger
than 2 microns.

Two samples of 1 liter sea water for each depth were filtered through Whatman
GF/F filters.  Pigments were extracted in 10 ml of 90% acetone during about 12
hours in the dark at 0˚C.  The fluorescence measurements (before and after
acidification with two drops of 10% ClH) were used to calculate the pigments
according with the following equations:

               Chlorophyll a = 11.64 e663 - 2. 16 e645 + 10 e630

where e663, e645 and e630 are the absorbances at 663, 645 and 630 nm after
substration of the absorbance at 750 nm, using 1 cm spectrophotometer cell.  If
the obtained value is multiplied by the extract volume in ml and divided by the
volume of seawater filtered in liters, the amount of chlorophyll a in mg/m3 is
obtained.

The equation proposed by SCOR-UNESCO (1966) was used to calibrate the
Fluorometer Turner Design in which all the readings of Fluorescence were made
during the cruise.  Concentrations of chlorophyll a and phaeophytin a were also
calculated following the equations given by Lorenzen (1966).

Vertical profiles of chlorophyll and phaeophytin for several stations are shown
in figure 8.


3.11.3.  PRIMARY PRODUCTION
         (J. García-Braun)

Water samples for primary production experiments were taken at several depths in
the photic zone, representing approximately 100%, 25%, 10% and 1% of surface
light.  The standard C14 method proposed by Steeman Nielsen (1952) was used with
some modifications.  The incubations were done in incubators under artificial
light during 2-3 hours.  The selected stations (11 stations and 99 samples) were
chosen in order to make the incubations in early hours during the morning.

For each depth, samples of 100 cc of seawater were inoculated with 4 µ Ci of C14
bicarbonate.  After incubation one sample was passed through Nucleopore filter
(2 micron pore size) and the other sample through Whatman GF/F filters.  A
separate sample was incubated in the dark in order to substract the incorporated
radioactivity with respect to the light bottles.  The filters were preserved in
the deep freeze for future readings of counts per minute in a Liquid
Scintillation Counter.


3.12.  ALUMINUM
       (M.D. Gelado and J.J. Hernández)

A voltametric method was used for aluminum determination during WOCE-AS Cruise.

The procedure is based on complexation of aluminum with 1,2-
dihydroxyanthraquinone-3-suplhonic acid (DASA) and measurement of reduction
current of this complex using high speed cathodic stripping voltametry (HSCSV).
Reduced Al-DASA complex produces an intensity of faradaic current proportional
to dissolved Al concentration.  The free DASA ligand has a cathodic peak at -
0.63 V while Al-DASA peak is more negative at -1.1 V (Ag/ClAg).

Optimal experimental parameters include an accumulation potential of -0.95 V
during 45 s, DASA concentration 2x10-6 M and staircase scan mode to 30 V/s
speed.  Samples are buffered at 7.1 pH using N, N1bis(2-hydroxyethyl)-2-
aminoethane suphonic acid(BES).  The method (Gelado-Caballero, 1992) is
specially adapted for on board determinations. The electrochemical system has
been designed to measure the instantaneous currents at short times with a low
noise level (Hernandez-Brito et al., 1990).  Thus, the analytical time required
for each sample is substantially reduced, allowing an increase of the number of
measurements in situ. A PAR303A electrochemical cell with hanging mercury drop
electrode (HMDE) was connected to a specially made computer-controlled
potentiostat.

The detection limit was 1.75 nM for 30 s adsorption time.  The deviation was
less than 3% for a 19 nM Al concentration based on repetitions for 7 seawater
samples.

In total 1000 samples were taken in 52 stations.  In most of the stations,
except in those close to the African coast, maximum was detected at the surface
layers.  Below a minimum at intermediate depths the dissolved Al concentrations
increased with depth.



ACKNOWLEDGEMENTS

This project was supported by IEO (Proy.1308), CICYT (Acc. Esp. AMB92-1114-E).
Participation on this cruise by H. Bryden, R. Millard and G. Bond and subsequent
processing and analysis of the measurements by H. Bryden and R. Millard were
supported by NSF and NOAA.  We are grateful to Junta de Gestión del B.I.O.
Hespérides for its support and collaboration, as well as to those colleagues of
the IEO who encouraged us and lent us their help.  We also wish to acknowledge
the seamanship, ability and friendship displayed by the captain and crew of the
B.I.O. Hespérides who contributed specially to the completion of the cruise.



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Jeffrey, S.W., G.F. Humphrey. 1975.  New spectrophotometric equations for
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________________________________________________________________________________________
________________________________________________________________________________________


DQE OF CTD DATA FOR THE 6TH CRUISE OF THE R/V "HESPERIDES",
WOCE SECTION A5 ACROSS THE NORTH MID-LATITUDE ATLANTIC.
(Eugene Morozov, 1995 MAY 02)


Data quality of 2-db CTD temperature, salinity and oxygen profiles and reference
rosette samples were examined.  Vertical distributions and theta-salinity curves
were compared for individual stations using the data of up and down CTD casts
and rosette probes.  Data of several neighboring stations were compared.

Questionable data in *.hy2 file were marked in QUALT2 word.

The calibration of upcast CTDSAL and CTDOXY data seem to be worse than downcast
data.

There were two data sets for WCT files.  One for the eastern part of the section
the (station numbers 49 and less) and the western part (stations 50-112).  The
data sets came different sources so I analyzed them separately.

Listing of results from the comparison of salinity and oxygen data. Only those
stations are listed which have data remarks.

Eastern part

STATION  PRESSURE  REMARKS
9         585 db   OXYGEN is low (2.61) compared with upcast CTDOXY (3.94) and
                    downcast CTDOXY (3.06).  Downcast CTDOXY seems reasonable.
                    I flag both OXYGEN and upcast CTDOXY 4 -Bad.  Upcast CTDTEMP
                    is wrong (3.943)
11       3045 db   OXYGEN (5.59) is high compared with upcast CTDOXY (5.45) and
                    downcast CTDOXY (5.44), flag 4.
         3372 db   SALNTY is 0.02 PSU higher that CTD upcast and downcast, the
                    flag is 4 - SALNTY - Bad
12                 A strange sequence of samples is given in .hy2 file. It is
                    not in accordance with pressure. It causes difficulties to
                    work with such a file. Some of samples correspond to negative
                    pressure, they should be removed from the file. Enormous
                    differences (over 2.3 PSU) are found between SALNTY and
                    CTDSAL at several levels. Some of them are flagged 4 - Bad,
                    some not.
                      I flag bad SALNTY at:                        343 db
                                                                   367 db
                                                                   401 db.
          454 db   SALNTY (35.750) and upcast CTDSAL (35.846) both are
                    Bad.  They do not match with downcast CTDSAL (35.720).
                    Similar problems with oxygen at the same levels:
                      I flag OXYGEN 4 - Bad at levels:             343 db
                                                                   367 db
                                                                   401 db
                                                                   454 db
                      I flag upcast CTDOXY 4 - Bad at levels:       78 db
                                                                   343 db
                                                                   367 db
                                                                   401 db
13       2025 db   SALNTY (35.050) is high compared with 35.039 upcast and
                    35.041 downcast CTDSAL, flag 4.
         2533 db   SALNTY (34.989) is high compared with 34.982 upcast and
                    34.979 downcast CTDSAL, flag 4.
         3053 db   SALNTY (34.946) is high compared with 34.940 upcast and
                    34.941 downcast CTDSAL, flag 3.
         4078 db    SALNTY (34.894) is low compared with 34.896 upcast and 34.896
                    downcast CTDSAL, flag 3, these are very deep waters.
14                 SALNTYes are lower than upcast CTDSAL by at least 0.01 for
                    the whole station, better for downcast CTDSAL.The flag is 3
                    for the whole station SALNTYes
          403 db   SALNTY (35.789)is high compared with 35.742 upcast and
                    35.734 downcast CTDSAL, flag 4.
         4070 db   SALNTY (34.884) is low compared with 34.898 upcast and
                    34.899 downcast CTDSAL, flag 4.
         4377 db   SALNTY (34.881) is low compared with 34.894 upcast and
                    34.894 downcast CTDSAL, flag 4.
15         65 db   There is a strange 20 m thick layer of low salinity water.
                    It is temperature compensated and even the oxygen is
                    slightly less.  It seems true because it is supported by
                    bottle measurements although there are differences between
                    CTDSAL and SALNTY.  They can be explained by high salinity
                    gradient.  There is no such a layer on neighboring stations.
                    I cannot make out where this freshened water could appear
                    from in the middle of the Canary Basin.
         1515 db   There are differences between SALNTY (35.170) and downcast
                    CTDSAL (35.157).  Upcast CTDSAL matches well with SALNTY
                    (35.172).  I don't flag anything questionable and attribute
                    these differences to tidal internal waves which are extremely
                    large here.
         4646 db   SALNTY (34.901) is high compared with upcast 34.892 and
                    downcast CTDSAL 34.892 flag 4.
16        762 db   SALNTY (35.223) is high compared with upcast CTDSAL 35.212
                    and downcast CTDSAL 35.198, flag 4.
         4734 db   SALNTY (34.905) is high compared with upcast CTDSAL 34.890
                    and downcast CTDSAL 34.890, flag 4.
              CTDOXY downcast calibration is wrong below 1500 db.  The values
              are higher that OXYGEN and measurements on neighboring stations.
         4734 db    OXYGEN (5.59) is low compared with upcast CTDOXY
                    5.79 and downcast CTDOXY 5.78, flag 4.
18       1316 db   SALNTY (35.158) is very low compared with upcast
                    CTDSAL 35.220 and downcast CTDSAL 35.216, flag 4.
19       3553 db   OXYGEN (5.68) is high compared with upcast CTDOXY
                    5.61 and downcast CTDOXY 5.60, flag 3.
         4066 db   SALNTY (34.896) is low compared with upcast CTDSAL
                    34.899 and downcast CTDSAL 34.900, flag 4.
21        204 db   SALNTY (36.663) does not match with upcast CTDSAL(36.645)
                    I flag them both 3 - Qble. There is a large salinity gradient
                    at this pressure, but nevertheless the discrepancy is very
                    large and they both differ from downcast CTDSAL (36.507).
22       4069 db   SALNTY (34.891) is low compared with upcast CTDSAL
                    34.901 and downcast CTDSAL 34.902, flag 4.
24                  You have a wonderful Meddy around 1200 db and CTDSAL is
                    questioned by originators.  It is absolutely true.
         1517 db   SALNTY (35.120) is high compared with upcast CTDSAL
                    35.118 and downcast CTDSAL 35.117, I don't flag
                    these differences as questionable they must be
                    accounted for internal waves.
         5663 db   OXYGEN (5.61) is low compared with upcast CTDOXY
                    (5.68) and downcast CTDOXY (5.68), flag 4.
25       3107 db   OXYGEN (5.70) is high compared with upcast CTDOXY
                    (5.65) and downcast CTDOXY (5.65), flag 3.
27       5472 db   SALNTY (34.890) is high compared with upcast CTDSAL
                    (34.887) and downcast CTDSAL (34.888), I flag SALNTY 3.
28       2526 db   SALNTY (35.056) is high compared with upcast CTDSAL
                    (34.985) and downcast CTDSAL (34.991).  Originators
                    flag upcast CTDSAL Qble, I flag SALNTY 4.
         4067 db   SALNTY (34.908) is high compared with upcast CTDSAL
                    (34.900) and downcast CTDSAL (34.902), I flag SALNTY 4.
         4581 db   SALNTY (34.894) is high compared with upcast CTDSAL
                    (34.891) and downcast CTDSAL (34.892), I flag SALNTY 3.
         5092 db   SALNTY (34.890) is high compared with upcast CTDSAL
                    (34.886) and downcast CTDSAL (34.888), I flag SALNTY 3.
28       5718 db   SALNTY (34.888) is high compared with upcast CTDSAL
                    (34.886) and downcast CTDSAL (34.886), I flag SALNTY 3.
29       1213 db   OXYGEN (4.36) is high compared with upcast CTDOXY
                    (4.15) and downcast CTDOXY (4.12), flag 4.
         2430 db   OXYGEN (5.48) is low compared with upcast CTDOXY
                    (5.58) and downcast CTDOXY (5.58), flag 4.
30       5613 db   SALNTY (34.887) is high compared with upcast CTDSAL
                    (34.884) and downcast CTDSAL (34.885), I flag SALNTY 3.
         5924 db   SALNTY (34.886) is high compared with upcast CTDSAL
                    (34.884) and downcast CTDSAL (34.884), I flag SALNTY 3.
31       1517 db   SALNTY (35.165) is high compared with upcast CTDSAL.
                    (35.163) and downcast CTDSAL (35.154), I do not flag
                    these data questionable as I think that the differences
                    are caused by internal waves
Stations 30, 31, 32.  Calibration of downcast CTDOXY is wrong in the
                    interval 2000-5500.  CTDOXY is lower than bottle measurements
33        809 db   OXYGEN (3.65) is high compared with upcast
                    CTDOXY(3.42) and downcast CTDOXY (3.35), flag - 4.
34       3556 db   OXYGEN (5.73) is high compared with upcast CTDOXY
                    (5.62) and downcast CTDOXY (5.61), flag 4.
         4066 db   OXYGEN (5.72) is high compared with upcast CTDOXY
                    (5.66) and downcast CTDOXY (5.65), flag 4.
         4572 db   SALNTY (34.898) is high compared with upcast CTDSAL
                    (34.891) and downcast CTDSAL (34.892), I flag SALNTY 4.
         5091 db   SALNTY (34.879) is low compared with upcast CTDSAL
                    (34.884) and downcast CTDSAL (34.885), I flag SALNTY 4.
35       3555 db   SALNTY (34.912) is low compared with upcast CTDSAL
                    (34.914) and downcast CTDSAL (34.916), I flag SALNTY 3.
         4068 db   SALNTY (34.895) is low compared with upcast CTDSAL
                    (34.899) and downcast CTDSAL (34.899), I flag SALNTY 4.
         4581 db   SALNTY (34.888) is low compared with upcast CTDSAL
                    (34.892) and downcast CTDSAL (34.893), I flag SALNTY 4.
Stations 35, 36.   Calibration of downcast CTDOXY is wrong in the
                    interval 2500-4500.  CTDOXY is lower than bottle measurements
                    and measurements on neighboring stations.
37       4068 db   SALNTY (34.902) is low compared with upcast CTDSAL
                    (34.903) and downcast CTDSAL (34.905), I flag SALNTY 3.
38       3001 db   SALNTY (34.973) is high compared with upcast CTDSAL
                    (34.945) and downcast CTDSAL (34.945), I flag SALNTY 4.
Stations 37, 38.   Calibration of downcast CTDOXY is wrong in the
                    interval below 1500 db.  CTDOXY is higher than bottle
                    measurements and measurements on neighboring stations.
Station 40.        Calibration of downcast CTDOXY is wrong in the interval
                    1800-2800.  CTDOXY is higher than bottle measurements and
                    measurements on neighboring stations.
44       4998 db   SALNTY (34.887) is low compared with upcast CTDSAL
                    (34.889) and downcast CTDSAL (34.890), I flag SALNTY 3.
46       4434 db   SALNTY (34.903) is high compared with upcast CTDSAL
                    (34.900) and downcast CTDSAL (34.900), I flag SALNTY 3.

WESTERN PART
Salinity and oxygen are examined separately because there were many problems
with CTDOXY calibration.

SALINITY

STATION  PRESSURE  REMARKS
58       2535 db   SALNTY (34.980) is high compared with upcast CTDSAL
                    (34.960) and downcast CTDSAL (34.962), I flag SALNTY 4.
64                  Some bad CTDSAL measurements are flagged 3 -Qble. 
                    They arereally bad.
67       5012 db   SALNTY (34.846) is low compared with upcast CTDSAL
                    (34.855) and downcast CTDSAL (34.855), I flag SALNTY 4.
75       4579 db   SALNTY (34.886) is low compared with upcast CTDSAL
                    (34.889) and downcast CTDSAL (34.890), I flag SALNTY 3.
         5609 db   SALNTY (34.842) is low compared with upcast CTDSAL
                    (34.844) and downcast CTDSAL (34.845), I flag SALNTY 3.
83       1703 db   SALNTY (35.000) is low compared with upcast CTDSAL
                    (35.030) and downcast CTDSAL (35.030), I flag SALNTY 4.
89                  There is great difference between SALNTY and upcast and
                    downcast CTDSAL in the upper 80 db layer.  Bottle samples
                    taken at 11; 28; 53; 77 dbars

OXYGEN
There are problems with calibration of CTD oxygen sensor for many of the
stations.  Some CTD casts contain data that are definitely bad and they are not
flagged bad at all.

STATION  PRESSURE  REMARKS
52       2002 db   OXYGEN (5.65) is high compared with upcast CTDOXY
                    (5.60) and downcast CTDOXY (5.57), flag - 4.
53       1518 db   OXYGEN (5.27) is high compared with upcast CTDOXY
                    (5.14)and downcast CTDOXY (5.14), flag - 4.
55       3973 db   OXYGEN (5.84) is low compared with upcast CTDOXY
                    (5.87) and downcast CTDOXY (5.88), flag - 4.
58       5157 db   OXYGEN (5.75) is low compared with upcast CTDOXY
                    (5.80) and downcast CTDOXY (5.82), flag - 4.
63       4306 db   OXYGEN (5.85) is high compared with upcast CTDOXY
                    (5.79) and downcast CTDOXY (5.80), flag - 4.
68       3564 db   OXYGEN (5.96) is high compared with upcast CTDOXY
                    (5.87) and downcast CTDOXY (5.87), flag - 4.
         CTDOXY calibration is wrong below 2500 db.  CTD measurements
                    are less than bottle.
69       CTDOXY calibration is wrong below 5000 db.  CTD measurements
                    are less than bottle OXYGEN approximately by 0.02ml/l.
70       2505 db   OXYGEN (5.72) is low compared with upcast CTDOXY
                    (5.80) and downcast CTDOXY (5.80), flag - 4.
     Almost all CTDOXY measurements to the west of station 70 are noisy.
     Many of them have wrong CTDOXY calibration mostly in deep waters.
73       CTDOXY calibration is wrong below 1500 db.  CTD measurements
           are less than bottle OXYGEN approximately by 0.02ml/l.
74        CTDOXY calibration is wrong below 5000 db.  CTD measurements
           are greater than bottle OXYGEN approximately by 0.02ml/l.
84       CTDOXY calibration is wrong below 1500 db.  CTD measurements
           are less than bottle OXYGEN approximately by 0.02ml/l.
85       CTDOXY calibration is wrong in the interval 2500-4000 db.  CTD
           measurements are lower than bottle OXYGEN approximately by 0.02ml/l.
86       CTDOXY calibration is wrong below 1500 db.  CTD measurements
           are lower than bottle OXYGEN approximately by 0.02ml/l.
87       CTDOXY calibration is wrong below 1500 db.  CTD measurements
           are lower than bottle OXYGEN approximately by 0.02ml/l.
88       CTDOXY calibration is wrong below 1500 db.  CTD measurements
           are lower than bottle OXYGEN approximately by 0.02ml/l.
89       4003 db   OXYGEN (6.06) is high compared with upcast CTDOXY
                    (6.17) and downcast CTDOXY (6.15), flag - 4.
         The calibration is better but problems below 5000 db. CTDOXY is
           higher than norm.
95       5408 db   OXYGEN (6.03) is high compared with upcast CTDOXY
                    (5.97) and downcast CTDOXY (5.94), flag - 4.
97       1904 db   OXYGEN (5.80) is low compared with upcast CTDOXY
                    (6.01) and downcast CTDOXY (5.99), flag - 4.
99       CTDOXY calibration is wrong below 2500 db. CTD measurements are
           lower than bottle OXYGEN approximately by 0.02ml/l.
107       618 db sample 15 OXYGEN is bad, flag - 4.
          622 db sample 14 OXYGEN is bad, flag - 4.
109-111        The stations are not deep.  CTDOXY calibration is bad in the
                entire depth.


FIGURES

Fig. 1   Positions of the stations.
Fig. 2   The histograms for a) salinity and b) oxygen differences between CTD
         and bottle samples deeper than 2500 db
Fig. 3   Nutrients diagrams.
Fig. 4   Vertical profiles of preliminary shipboard values of F-11 for minor
         and major depths of a)1000m and b) respectively.
Fig. 5a  Total carbonate according to the depth for all the stations in which
         it was measured.
Fig. 5b  Calculated pressure of CO2 throughout the passage of the cruise.
Fig. 6a  Vertical distribution of pH and O2 dissolved for station 47.
Fig. 6b  Vertical distribution of the alkalinity and total carbon for station 47.
Fig. 7   Vertical distribution of the chlorophyll for stations 1 to the 60.
Fig. 8   Vertical profiles of chlorophyll and phaeophytin for stations 1, 11,
         50 and 95.


________________________________________________________________________________________
________________________________________________________________________________________


WHPO-SIO DATA PROCESSING NOTES

Date        Contact      Data Type         Summary
----------  -----------  ----------------  ------------------------------------
1994-01-14  Smethie      CFCs              Submitted for DQE

1995-02-02  Parrilla     BTL               original data submission

1995-05-02  Parrilla     CTD/S/O           DQE Report sent to PI

1995-05-02  Morozov      CTD/S/O           DQE Report Submitted

1997-05-08  Parrilla     BTL/DOC           Submitted for DQE
            includes NUTs, supplement to DOC file

1997-06-08  Peng         DELC14            Submitted via email: txt/unformatted

1997-11-21  Parrilla     SUM/SEA/CTD       Data are Public

1997-12-09  Rios         ALKALI            Submitted

1998-02-04  Kozyr        CO2               Final Data Submitted
            I have put 2 files with final CO2-related data to your ftp 
            area: File a15co2fin.dat is the data obtained during the R/V Knorr 
            cruise along WOCE Section A15. The data were submitted to CDIAC by 
            Dr. Catherine Goyet of WHOI. File a5co2fin.dat is the data 
            obtained during Spanish R/V Hesperides cruise along WOCE Section 
            A5. These data were submitted to CDIAC by Dr. Frank Millero of 
            RSMAS.

1999-04-14  Kappa        Cruise Report     PDF version made

1999-04-30  Kappa        Cruise Report     PDF Version Made
            a05_cruzpln.pdf added

1999-11-15  Buck         Cruise Report     Website Updated:
            pdf version created & online

2000-02-14  Kozyr        ALKALI/TCARBN/PH  DQE'd Data Submitted
            I've just put a total of 13 files [carbon data measured in 
            Indian (6 files)\rand Atlantic (7 files) oceans] to the WHPO ftp 
            area. 

2000-05-22  Huynh        Cruise Report     Website Updated: files added 
            to website

2000-05-24  Kozyr        CO2               Final Data Submitted
            Frank Millero has adjusted his 1992 A5 TCO2 and pH 
            measurements right before our NDP went to press. I have changed 
            these numbers in the data file for this cruise and put it in your 
            INCOMING area. Please use this file when you merge the CO2 data 
            into your hydro file.

2000-05-30  Kozyr        CO2               Final Data Submitted
            please replace the A5 data file I have put to your ftp site 
            on May 24 with the a5.dat file I've put today. I found some 
            problems in pH data. Now all data are correct and final and 
            public.


Date        Contact      Data Type         Summary
----------  -----------  ----------------  ------------------------------------
2000-09-07  Chapman      DELC14            Submitted
            re-submission of Peng's 6/8/97 email w/ data

2000-10-31  Bartolacci    BTL/SUM          Website Updated:
            Reformatted BTL/SUM files online. OXY values converted.
            replaced the current online sumfile and bottle file with 
            reformatted files produced by S. Anderson. Please note in addition 
            to usual reformatting procedures, the oxygen values were converted 
            from ML/L to UMOL/KG, however it is unclear and as yet unknown 
            whether the nutrient units are correct or mislabled.

2000-12-11  Uribe        Cruise Report     Submitted; titled "sum file" 
                2000.12.11 KJU
            File contained here is a CRUISE SUMMARY and NOT sumfile. 
            Documentation is online.
                2000.10.11 KJU
            Files were found in incoming directory under whp_reports. This 
            directory was zipped, files were separated and placed under proper 
            cruise. All of them are sum files.
            Received 1997 August 15th.

2001-03-21  Uribe        CTD               Website Updated: (Expocodes)
            Expocodes in all ctd files have been editted to match the 
            underscored expocode in the sum and bottle files. New files were 
            zipped and replaced existing ctd files online. Old files were 
            moved to original directory. 

2001-06-21  Uribe        CTD/BTL           Online CSV file modified
            The exchange bottle file name in directory and index file 
            was modified to lower case.
            CTD exchange files were put online.

2001-11-29  Peng         DELC14            Data are Public
            Jim Swift called Peng to verify public status

2001-12-02  Diggs        CTD               Website Updated: Exchange file online
            CTD-Exchange files updated and placed online. It was a 
            simple matter of using my new code to generate the CTD files.

2001-12-02  Diggs        C14               Re-submitted
            T.S. Peng's A05 C14 data from 6/7/1997 is ready and waiting 
            to be decyphered and merged. We suffered a disk crash when these 
            data were sent, but luckily, T.S. Peng sent a copy to Piers 
            Chapman of TAMU and he forwarded these data on to the WHPO on 
            9/7/2001. T.S. Peng originally sent this file via email.

2001-12-20  Hajrasuliha  CTD               Internal DQE completed
            Created *check.txt file for this cruise. sal and oxy .Ps 
            files have Not been created for this cruise.

2002-08-16  Diggs        BTL               Data merge requested
            Danie, Could you please merge these 14C values into the 
            online bottle file for WOCE line A05?  If you have questions, 
            please let me know. 


Date        Contact      Data Type         Summary
----------  -----------  ----------------  ------------------------------------
2002-08-20  Uribe        CTD               Flags edited, exchange files remade
            Original CTD files had a problem on a couple of files. Some 
            lines were given 0 as a flag. This was changed to 9 and -9 for 
            NUMB of OBS. Exchange/NetCDF files were remade.

2002-08-21  Key          BTL               Update Needed
            The data disposition is:
                 Public  
            The bottle file has the following parameters:
                 STATION, CAST, BTLNBR, CTDPRS, DELC14, C14ERR, C14F
            The file format is:
                 Comma Separated Values 
            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)
            KEY, BOB would like the following action(s) taken on the data:
                 Merge Data
                 Place Data Online
            Any additional notes are:
            Data Rcd by me from J. Severinghaus on 8/21/02. I think that W. 
            Broecker should be listed as PI for these data.  I assigned QC 
            flags, but since the A20/A22 data are not yet available all 
            existing values are flagged 2

2002-08-21  Anderson     C14/CO2           C14/pH/ALK/TC02 Online
            Merged the DELC14 and C14ERR submitted by Bob Key. Made new 
              exchange file. 
            More a05 notes:
              Merged the DELC14 and C14ERR data submitted by Bob Key.
            Moved the submitted file from the website submittal area to 
              ...a05/original/20020821.065747_KEY_A05_A05.C14.
            Station 108, cast 1, sample 3 had 5 identical values.  The mrgsea 
              program only merges the first one.
                  Sarilee Anderso

2003-03-21  Kozyr        CFCs              CFCs flags are wrong
            Could you check a05hy.txt file (EXPOCODE 29HE06_1 WHP-ID A05  
            DATES 072092-081792 20020821WHPOSIOSA), it has wrong CFCs flags.

2003-04-11  Anderson     CFCs              Flags corrected
            Corrected wrong cfc flags by remerging cfcs from a05_sea.txt 
              found in original directory into online file. Made new exchange 
              file, sent notes to Jerry.
            Alex Kozyr noted (see 2003-03-21 e-mail) that the flags for CFC11 
              and CFC12 were not correct. The flags were all 1s.
              I found a file in the a05/original directory (a05_sea.txt) that 
              had cfc's with correct flags.  I did a comparison of the cfc11 and 
              cfc12 values between this file and the online file.  The values 
              are the same.  I copied the QUALT1 flags to the QUALT2 flags for 
              both files and then merged the cfc's from the a05_sea.txt file 
              into the online file 2020821WHPOSIOSA.


Date        Contact      Data Type         Summary
----------  -----------  ----------------  ------------------------------------
2003-08-14  Coartney     Cruise Report     New PDF and text docs online

2005-01-28  Kozyr        CO2               Data Report available @ CDIAC website
            You can find the information for Indian Ocean in 2002 on 
            Charles Darwin cruise at: 
              http://cdiac.ornl.gov/oceans/RepeatSections/clivar_i05.html
            and 26°N in the Atlantic
              http://cdiac.ornl.gov/oceans/RepeatSections/clivar_a05.html
            However we do not have any data submitted by PIs from these 
              cruises. Please, let me know, if you get more information or even 
              better the data from these cruises. And if I have anything, I will 
              let you know.
            I am planning to make the Repeat Section Cruise summary Table that 
            I've sent you last week in .doc format available on line as an 
              HTML document through our web site. I am off to the European 
              CarboOcean Program kick off meeting next week, so I will make this 
              table available after I come back.

2005-06-16  Kozyr        CO2               Submitted Final Data
            I have put 2 files with final CO2-related data to your ftp 
              area:
            File a15co2fin.dat is the data obtained during the R/V Knorr 
              cruise along WOCE Section A15. The data were submitted to CDIAC by 
              Dr. Catherine Goyet of WHOI.
            File a5co2fin.dat is the data obtained during Spanish R/V 
              Hesperides cruise along WOCE Section A5. These data were submitted 
              to CDIAC by Dr. Frank Millero of RSMAS.

2007-06-20  Kappa        Cruise Report     Updated; CO2 Report added
            Incorporated Kozyr's carbon report into cruise report; 
            updated these Data Processing Notes, re-numbered figs