CRUISE REPORT: A24 (Updated: 27 NOV 2006) A. HIGHLIGHTS A.1. WHP Cruise Summary Information WOCE section designation A24 Expedition designation (EXPOCODE) 316N151_2 Chief Scientist Lynne Talley/SIO Dates 1997.MAY.30 - 1997.JUL.05 Ship R/V KNORR Ports of call Ponta Delgada, Azores to Halifax, Nova Scotia Number of stations 153 Stations' geographic boundaries 97° 64.8' N 98° 42.9' W 49° 9.3' W 01° 38.8' N Floats and drifters deployed 12 PALACE floats and 17 RAFOS floats Moorings deployed or recovered 1 URI RAFOS Mooring 2 RAFOS sources on initial transit Contributing Authors (in order of appearance) F. Delahoyde, K. Sanborn, E. Firing, M. Vollmer, L. Arlen, S. Khatiwala Chief Scientist Contact Information LYNNE TALLEY Scripps Institution of Oceanography • UCSD 9500 Gilman Dr. • MS 0230 • La Jolla, CA • 92093-0230 Phone: 858-534-6610 • Fax: 858-534-9820 • email: ltalley@ucsd.edu WWW homepage: http://sam.ucsd.edu World Ocean Circulation Experiment A24 R/V Knorr Voyage 151/2 WHPO Expocode: 316N151/2 Final ODF Cruise Report October 18, 2006 WOCE A24 Cruise Track Shipboard Technical Support (Oceanographic Data Facility/Shipboard Electronics Group) Scripps Institution of Oceanography La Jolla, Ca. 92093-0214 Summary A hydrographic survey consisting of CTD/rosette sections between the Azores and Greenland was carried out May to July, 1997. The R/V Knorr departed Ponta Delgada, Azores on 30 May 1997. 153 CTD/Rosette stations were occupied from 30 May through 28 June. Water samples (up to 31) and CTD data were collected in most cases to within 10 meters of the bottom, for a total of 3450 bottles. Salinity, dissolved oxygen and nutrient samples were analyzed from every level sampled by the rosette. The cruise ended in Halifax, Nova Scotia on 5 July 1997. 1 URI RAFOS Mooring, 12 ALACE floats, 17 Rafos floats, and 45 XBT's were deployed during the cruise. Two RAFOS moorings were also deployed on the transit from Woods Hole to Ponta Delgada. Table 0.0: Scientific Personnel WOCE A24 ____________________________________________________________________________ Scientific Personnel ---------------------------------------------------------------------------- Name Affiliation Duties ------------------- ------------ ----------------------------------------- Talley, Lynne SIO/PORD Chief Scientist Arlen, Linda LDEO TCO2 Becker, Susan SIO/STS/ODF Nutrients Boaz, John SIO/STS/ODF Watch Leader/O2/Rosette/Bottle data Chen, Shuiming UH ADCP/LADCP Costello, Lawrence WHOI Mooring, RAFOS Floats, Rosette Delahoyde, Frank SIO/STS/ODF CTD data Processing Firing, Eric UH ADCP/LADCP Galanter, Meredith UM/RSMAS Alkalinity Goen, Jamie UM/RSMAS Alkalinity Ha Min, Dong SIO/GRD CFC Johnson, Kenneth BNL TCO2 Khatiwala, Samar LDEO Helium, Tritium, O-18 Lavender, Kara SIO/PORD CTD Console/Sample Cop/Salinities/Rosette Mask, Andrea FSU CTD Console/Sample Cop/Salinities Masten, Douglas SIO/STS/ODF Nutrients Mattson, Carl SIO/STS/ODF TIC/Watch Leader/ET/Rosette Newton, David SIO/MLRG CTD Console/Rosette/Sample Cop Packard, Greg WHOI SSSG Technician Rusk, Steven SIO/STS/ODF O2/Rosette Sanborn, Kristin SIO/STS/ODF Bottle data/Salinities/Rosette/O2 Smith, Daniel LDEO Helium, Tritium, O-18 Van Woy, Frederick SIO/GRD CFC Vollmer, Martin SIO/GRD CFC Wilson, Angela LDEO pCO2 ____________________________________________________________________________ NARRATIVE The R/V Knorr left Ponta Delgada, Azores at 11:00 on May 30, 1997 to begin the one-time WHP survey sections A24 in the subpolar North Atlantic. These sections are part of the WOCE Atlantic Climate Change Experiment, and their purpose is to assist in measuring the upper water transports in the eastern subpolar gyre, including those which feed the Norwegian Sea and the Labrador Sea, and to observe the overflows from the Greenland-Iceland- Norwegian Seas in the Denmark Strait, Iceland Basin and Rockall Trough. Primary measurement programs included hydrography (CTDO, salinity, oxygen, nutrients, CFC's, carbon dioxide, helium, tritium), and velocity (shipmounted ADCP, lowered ADCP, neutrally buoyant floats - ALACE and RAFOS). A RAFOS sound source mooring was placed during the Greenland- Azores leg of the cruise. A transit leg to the Azores left from Woods Hole, MA on May 15, 1997, with chief scientist Tom Rossby. Underway to Ponta Delgada, two RAFOS sound source moorings were deployed, at 47N, 39W and 47N, 31W. Four sections were completed as part of the main cruise. After departing Ponta Delgada, we sailed to Terceira, Azores and began the first section there, proceeding northeastward towards the Goban Spur. Upon completion of the first section, we diverted into the harbor in Cork, Ireland, for an emergency exchange of crewmembers. The time associated with this was approximately 22 hours beyond that which was expected for a direct transit to the next section. The first section crossed the Mediterranean Water/Labrador Sea Water mixing zone obliquely, with large variations between groups of station dominated by Mediterranean Water and those dominated by Labrador Sea Water. The second (short) section crossed the southern Rockall Trough, from Porcupine Bank to the southern end of Rockall Bank. Due to time limitations imposed by the emergency trip to Cork, the full set of short sections occupied near Porcupine Bank in November 1996 were not repeated. The northernmost section was angled more northwest-southeast than in fall, 1996, in order to reach a portion of Rockall Bank which would still allow a boundary for the Wyville Thomson overflow, which was found below 1200 meters in the northern part of Rockall Trough. This strategy was successful, and overflow water was found on our short section, hugging Rockall Bank. The third section crossed the northern part of the subpolar gyre, from the Hebrides to Rockall Bank, to Hatton Bank, to the Reykjanes Ridge and to Greenland near Angmassalik. The eastern end of this section was moved north from that in November 1996 because the Meteor (chief scientist Walter Zenk) completed a section identical to the November section in May, 1997, just weeks before our arrival in the area. Therefore we chose to cross Rockall Trough farther north, just north of Anton Dohrn Seamount. The relocated section joined the original section in the middle of the Iceland Basin and then exactly duplicated the November, 1996 section to Greenland. Ice conditions at Greenland were favorable, and stations were completed well up onto the deep shelf (average depth 500 meters), although not as far west as in November, 1996. This section as a whole clearly delineated the overflow waters in each of the three troughs - Irminger Basin, Iceland Basin and Rockally Trough. After a transit southward to Cape Farewell, Greenland, the fourth section was completed from Cape Farewell southeastward to the Charlie Gibbs Fracture Zone (CGFZ), and thence to Terceira. Time permitted an additional station in the CGFZ, allowing the cross-channel velocity (LADCP) and temperature/salinity structure to be delineated and a geostrophic velocity profile to be computed. Full water column bottle sampling was not included on the northern station. Time permitted additional stations on the southern end of the section. The last station was a double cast, with the first cast being a test of LADCP bottom tracking, and the second cast being the complete cast with bottle sampling. PROGRAMS The principal programs of A24 are shown in Table 0.1. The SIO ODF hydrographic measurements program is described in detail in this report. Table 0.1: Principal Programs of WOCE A24 ____________________________________________________________________________________ Analysis Institution Principal Investigator -------------------------- ----------- ------------------------------------------- Basic Hydrography (SALNTY, SIO Lynne Talley O2, Nutrients, CTD) CFC SIO Ray Weiss He/Tr/O-18 LDEO Peter Schlosser TCO2 BNL Doug Wallace TCO2 (reference samples) SIO Charles Keeling Alkalinity UH/RSMAS Frank Millero Transmissometer TAMU Wilf Gardner ADCP and LADCP UH Eric Firing, Peter Hacker PALACE/SOLO Floats SIO Russ Davis RAFOS Floats WHOI Amy Bower, Phil Richardson RAFOS Floats/Moorings URI Tom Rossby, Mary Elena Carr and Mike Prater pCO2 LDEO Taro Takahashi, Dave Chipman UW pH, TCO2 (Transit only) WHOI Catherine Goyet UW pH, TCO2 BNL Doug Wallace UW Meteorology/XBTs WHOI Barry Walden UW Thermosalinograph SIO Lynne Talley UW Sea surface & air gas SIO Ray Weiss analysis, pCO2, pN2O, pCH4, CH4, CO2, N20 ____________________________________________________________________________________ DESCRIPTION OF MEASUREMENT TECHNIQUES AND CALIBRATIONS 1. BASIC HYDROGRAPHY PROGRAM The basic hydrography program consisted of salinity, dissolved oxygen and nutrient (nitrite, nitrate, phosphate and silicate) measurements made from bottles taken on CTD/rosette casts plus pressure temperature, salinity and dissolved oxygen from CTD profiles. Rosette casts were made to within 10 meters of the bottom. No major problems were encountered during the operation. The resulting data set met and in many cases exceeded WHP specifications. The distribution of samples is illustrated in figures 1.0-1.3. Figure 1.0: Sample distribution, stations 1-34. Figure 1.1: Sample distribution, stations 35-48. Figure 1.2: Sample distribution, stations 49-97. Figure 1.3: Sample distribution, stations 98-153. 2. WATER SAMPLING PACKAGE Hydrographic (rosette) casts were performed with a 36-place 10-liter rosette system consisting of a 36-bottle rosette frame (ODF), a 36-place pylon (General Oceanics 1016, SBE 32) and 31 10-liter PVC bottles (ODF). Underwater electronic components consisted of an ODF-modified NBIS Mark III CTD with dual conductivity and temperature sensors, SeaTech transmissometer, RDI LADCP, Simrad altimeter and Benthos pinger. The CTD was mounted horizontally along the bottom of the rosette frame, with the transmissometer, dissolved oxygen and SBE 35 PRT sensors deployed alongside. The LADCP was mounted vertically, inside the rosette frame bottle rings. The Simrad altimeter provided distance-above-bottom in the CTD data stream. The Benthos pinger was monitored during a cast with a precision depth recorder (PDR) in the ship's laboratory. The rosette system was suspended from a new three-conductor 0.322" electro-mechanical (EM) cable which was installed prior to the ship's departure from Woods Hole. Power to the CTD and pylon was provided through the cable from the ship. Separate conductors were used for the CTD and pylon signals with the General Oceanics 1016 pylon (casts 001/01-010/01). A single conductor was used with the SBE 32 pylon and SBE 33 deck unit (casts 011/01-153/02). The rosette system was deployed from the starboard side hangar, using an air-powered cart to move the rosette into the sampling area. The portside Markey CTD winch was used throughout the leg. The deck watch prepared the rosette 45 minutes prior to a cast. All valves, vents and lanyards were checked for proper orientation. The bottles were cocked and all hardware and connections rechecked. Upon arrival on station, time, position and bottom depth were logged and the deployment begun. The rosette was moved into position under a projecting boom from the rosette room using an air-powered cart on tracks. Two stabilizing tag lines were threaded through rings on the frame. CTD sensor covers were removed and the pinger turned on. Once the CTD acquisition and control system in the ship's laboratory had been initiated by the console operator and the CTD and pylon had passed their diagnostics, the watch leader would verify with the bridge that deployment could begin. The winch operator would raise the package and extend the boom over the side of the ship. The package was then quickly lowered into the water, the tag lines removed and the console and winch operators notified by radio of the target depth (wire-out). During each cast, the rosette was lowered to 5-10 meters above the bottom. Bottles on the rosette were identified with unique serial numbers. These numbers corresponded initially to the pylon tripping sequence 1-31, the first trip closing bottle #1. No bottles were changed during the leg. Averages of CTD data corresponding to the time of bottle closure were associated with the bottle data during a cast. Pressure, depth, temperature, salinity and density were immediately available to facilitate examination and quality control of the bottle data as the sampling and laboratory analyses progressed. At the end of the cast, two tugger lines terminating in large snap hooks were mounted on poles and used by the deck watch to snag recovery rings on the rosette frame. The package was then lifted out of the water, the boom retracted, and the rosette lowered onto the cart. Sensor covers were replaced, the pinger turned off and the cart and rosette moved into the rosette room for sampling. A detailed examination of the bottles and rosette would occur before samples were taken, and any extraordinary situations or circumstances noted on the sample log for the cast. Rosette maintenance was performed on a regular basis. O-rings were changed as necessary and bottle maintenance performed each day to insure proper closure and sealing. Valves were inspected for leaks and repaired or replaced. 3. Underwater Electronics Packages CTD data were collected with modified NBIS Mark III CTDs (ODF CTD #3, #5). CTD #3 was used on a single cast (001/01). An unstable PRT temperature channel was traced to a small leak in the PRT turret and was repaired. CTD #3 was subsequently maintained as the backup CTD. CTD #5 was deployed on all other casts (002/01-153/02). This instrument provided pressure, temperature, conductivity and dissolved O2 channels, and additionally provided redundant PRT temperature and conductivity channels. Other data channels included elapsed-time, an altimeter, several power supply voltages, a second dissolved O2 channel and a transmissometer. The instrument supplied a standard 17-byte NBIS-format data stream at a data rate of 20 fps. Modifications to the instrument included revised pressure and dissolved O2 sensor mountings; ODF-designed sensor interfaces for O2 and the SeaTech transmissometer; implementation of 8-bit and 16-bit multiplexer channels; an elapsed-time channel; instrument id in the polarity byte and power supply voltages channels. The instrument sensor configuration is provided in Table 3.0. Table 3.0: CTD #5 sensor configuration data. ________________________________________________________________________ Sensor | Manufacturer | Serial | Notes -------------+---------------------+---------+------------------------ Pressure | Paine 211-35-440-05 | 77017 | Primary Temperature | Rosemount 171BJ | 15407 | Primary Conductivity | GO 09035-00151 | E197 | Primary Temperature | Rosemount 171BJ | 15046 | Secondary Conductivity | GO 09035-00151 | E184 | Secondary Dissolved O2 | SensorMedics | 6-02-07 | Primary Dissolved O2 | Royce | | Secondary, experimental ________________________________________________________________________ The CTD pressure sensor mounting had been modified to reduce the dynamic thermal effects on pressure. The sensor was attached to a length of coiled, oil-filled stainless-steel tubing threaded into the end-cap pressure port. The transducer was also insulated. The NBIS temperature compensation circuit on the pressure interface was disabled; all thermal response characteristics were modeled and corrected in software. The SensorMedics O2 sensor was deployed in a pressure-compensated holder assembly mounted separately on the rosette frame and connected to the CTD by an underwater cable. The O2 sensor interface was designed and built by ODF. A second, experimental O2 sensor (Royce) was also deployed to collect some comparison data. A SBE 35 Laboratory-grade reference PRT was employed as an additional temperature calibration check. This device is internally-recording and triggered by the SBE 32 pylon confirmation signal, providing a calibration point for each bottle trip. Standard CTD maintenance procedures included soaking the conductivity and O2 sensors in distilled water between casts to maintain sensor stability, and protecting the CTD from exposure to direct sunlight or wind to maintain an equilibrated internal temperature. A General Oceanics 1016 36-place pylon was employed for the first 10 casts, then was replaced by a SBE 32 36-place pylon and SBE 33 deck unit for the rest of the cruise. The SBE 32 has the advantage of requiring a single sea cable conductor for power and signals, in contrast to the 2 required for the General Oceanics 1016. It also provides for the use of the SBE 35 reference PRT. Both pylons provided generally reliable operation and positive confirmation of all bottle trip attempts. A software configuration problem that caused some erroneously reported trip failures was corrected by station 27. 4. NAVIGATION AND BATHYMETRY DATA ACQUISITION Navigation data were acquired from the ship's Trimble Pcode GPS receiver via RS-232. It was logged automatically at one-minute intervals by one of the Sun SPARCstations. Underway bathymetry was acquired from the ship's SeaBeam system (centerbeam depth) at five-minute intervals, then merged with the navigation data to provide a time-series of underway position, course, speed and bathymetry data. These data were used for all station positions, PDR depths, and for bathymetry on vertical sections [Cart80]. 5. CTD LABORATORY CALIBRATION PROCEDURES Laboratory calibrations of the CTD pressure and temperature sensors were used to generate tables of corrections applied by the CTD data acquisition and processing software at sea. Pressure and temperature calibrations were performed on CTD #5 at the ODF Calibration Facility (La Jolla) in April 1997 and July/August 1997, both before and after WOCE A24. The CTD pressure transducer (Paine 211-35-440-05 8850 psi, Serial #77017) was calibrated in a temperature-controlled water bath to a Ruska Model 2400 Piston Gage pressure reference. Calibration curves were measured to two maximum loading pressures during April/July/August: -2.06/-0.98/-1.17°C to 6080 db and 28.74/30.66/30.00°C to 1190 db. Figures 5.0-2 summarize the laboratory pressure calibrations performed in April, July and August 1997. Figure 5.0: Pressure calibration for ODF CTD #5, April 1997. Figure 5.1: Pressure calibration for ODF CTD #5, July 1997. Figure 5.2: Pressure calibration for ODF CTD #5, August 1997. CTD PRT temperatures were calibrated to a NBIS ATB-1250 resistance bridge and Rosemount standard PRT. The primary (Rosemount 171BJ, Serial #15407) and secondary (Rosemount 171BJ, Serial #15046) CTD temperatures were offset by 1.5°C to avoid the 0-point discontinuity inherent in the internal digitizing circuitry. Figures 5.3-5 summarize the laboratory temperature calibration performed on the primary PRT in April, July and August 1997. Figure 5.3: Primary Temperature calibration for ODF CTD #5, April 1997. Figure 5.4: Primary Temperature calibration for ODF CTD #5, July 1997. Figure 5.5: Primary Temperature calibration for ODF CTD #5, August 1997. The calibrations for both Pressure and Temperature were essentially unchanged between April and July/August 1997. 6. CTD DATA ACQUISITION, PROCESSING AND CONTROL SYSTEM The CTD data acquisition, processing and control system consisted of a Sun SPARCstation 5 computer workstation, ODF-built CTD deck unit, SBE 33 pylon deck unit and power supply and a VCR recorder for real-time analog backup recording of the seacable signal. The Sun system consisted of a color display with trackball and keyboard (the CTD console), 18 RS-232 ports, 4.5 GB disk and 8-mm cartridge tape. Two other Sun systems (one SPARC 5, one SPARC LX) were networked to the data acquisition system, as well as to the rest of the networked computers aboard the Knorr. These systems were available for real-time CTD data display and provided for hydrographic data management and backup. An HP 1200C color inkjet printer provided hardcopy from any of the workstations. The CTD FSK signal from the sea cable was demodulated and converted to a 9600 baud RS-232C binary data stream by the CTD deck unit. This data stream was fed to the Sun SPARCstation. The pylon confirmation signal was tied into the CTD data stream through a bi-directional 300 baud serial line, allowing rosette trips to be initiated and confirmed through the data acquisition software. A bitmapped color display provided interactive graphical display and control of the CTD rosette sampling system, including displays of real-time raw and processed data, navigation, winch and rosette trips. The CTD data acquisition, processing and control system was prepared by the console watch a few minutes before each deployment. A console operations log was maintained for each deployment, containing a record of every attempt to trip a bottle as well as any pertinent comments. Most CTD console control functions, including starting the data acquisition, were initiated by pointing and clicking a trackball cursor on the display at icons representing functions to perform. The system then presented the operator with short dialog prompts with automatically-generated choices that could either be accepted as defaults or overridden. The operator was instructed to turn on the CTD power supply, then to examine a real-time CTD data display on the screen for stable voltages from the underwater unit. Once this was accomplished, the data acquisition and processing was begun and a time and position automatically associated with the beginning of the cast. A backup analog recording of the CTD signal was made on a VCR tape, which was started at the same time as the data acquisition. A rosette trip display and pylon control window popped up, giving visual confirmation that the cast was initialized properly. Various plots and displays were initiated. When all was ready, the console operator informed the deck watch by radio. Once the deck watch had deployed the rosette and informed the console operator that the rosette was at the surface (also confirmed by the computer displays), the console operator or watch leader provided the winch operator with a target depth (wire-out) and maximum lowering rate, normally 60 meters/minute or less for this package. The package then began its descent, typically starting at 20 meters/minute and building up to 60 meters/minute, continuing at a steady rate without any stops during the down-cast. The console operator examined the processed CTD data during descent via interactive plot windows on the display, which could also be run at other workstations on the network. Additionally, the operator decided where to trip bottles on the up-cast, noting this on the console log. The PDR was monitored to insure the bottom depth was known at all times. The watch leader assisted the console operator when the package was ~400 meters above the bottom by monitoring the range to the bottom using the distance between the rosette's pinger signal and its bottom reflection displayed on the PDR. Between 100 and 60 meters above the bottom, depending on bottom conditions, the altimeter typically began signaling a bottom return on the console. The winch, altimeter and PDR displays allowed the watch leader to refine the target depth relayed to the winch operator and safely approach to within 10 meters Bottles were closed on the up cast by pointing the console trackball cursor at a graphic firing control and clicking a button. The data acquisition system responded with the CTD rosette trip data and a pylon confirmation message in a window. All tripping attempts were noted on the console log. The console operator then directed the winch operator to the next bottle stop. The console operator was also responsible for generating the sample log for the cast. After the last bottle was tripped, the console operator directed the deck watch to bring the rosette on deck. Once the rosette was on deck, the console operator terminated the data acquisition and turned off the CTD, pylon and VCR recording. The VCR tape was filed. The sample cop (usually the console operator) brought the sample log to the rosette room and logged information for samples drawn. 7. CTD DATA PROCESSING ODF CTD processing software consists of over 30 programs running under the Unix operating system. The initial CTD processing program (ctdba) is used either in real-time or with existing raw data sets to: • Convert raw CTD scans into scaled engineering units, and assign the data to logical channels • Filter various data channels according to specified filtering criteria • Apply sensor- or instrument-specific response-correction models • Provide periodic averages of the channels corresponding to the output time-series interval • Store the output time-series in a CTD-independent format Once the CTD data are reduced to a standard-format time-series, they can be manipulated in various ways. Channels can be additionally filtered. The time-series can be split up into shorter time-series or pasted together to form longer time-series. A time-series can be transformed into a pressure- series, or into a larger-interval time-series. The pressure calibration corrections are applied during reduction of the data to time-series. Temperature, conductivity and oxygen corrections to the series are maintained in separate files and are applied whenever the data are accessed. ODF data acquisition software acquired and processed the CTD data in real- time, providing calibrated, processed data for interactive plotting and reporting during a cast. The 20 Hz data from the CTD were filtered, response-corrected and averaged to a 2 Hz (0.5-second) time-series. Sensor correction and calibration models were applied to pressure, temperature, conductivity and O2. Rosette trip data were extracted from this time- series in response to trip initiation and confirmation signals. The calibrated 2 Hz time-series data, as well as the 20 Hz raw data, were stored on disk and were available in real-time for reporting and graphical display. At the end of the cast, various consistency and calibration checks were performed, and a 2.0-db pressure-series of the down-cast was generated and subsequently used for reports and plots. CTD plots generated automatically at the completion of deployment were checked daily for potential problems. The two PRT temperature sensors were inter-calibrated and checked for sensor drift. The CTD conductivity sensor was monitored by comparing CTD values to check-sample conductivities, and by deep theta-salinity comparisons between down- and up-casts as well as adjacent stations. The dissolved CTD O2 sensor was calibrated to check- sample data. A few casts exhibited conductivity offsets due to biological or particulate artifacts. On some casts, noise in the O2 channel was evident. Some casts were subject to noise in the data stream caused by sea cable or slip-ring problems, or by moisture in interconnect cables between the CTD and external sensors (i.e. O2). Intermittent noisy data were filtered out of the 2 Hz data using a spike-removal filter. A least-squares polynomial of specified order was fit to fixed-length segments of data. Points exceeding a specified multiple of the residual standard deviation were replaced by the polynomial value. Density inversions can be induced in high-gradient regions by ship- generated vertical motion of the rosette. Detailed examination of the raw data shows significant mixing occurring in these areas because of "ship roll". In order to minimize density inversions, a ship-roll filter was applied to all casts during pressure-sequencing to disallow pressure reversals. The first few seconds of in-water data were excluded from the pressure- series data, since the sensors were still adjusting to the going-in-water transition. Only station 15 exhibited a notable (-0.022 sigma theta) density drop during the top 10 db. 18 casts showed a sharply increasing density gradient (typically +0.1 to +0.25 in sigma theta) in the top few meters of the water column; however, the gradients for stations 140 and 95 were +0.33 and +0.86. A time-series data check verified these density features were probably real: the data were consistent over many frames of data at the same pressures. Sometimes the surface densities varied because of temperature instabilities as large as 0.5°C. Pressure intervals with no time-series data can optionally be filled by double-quadratic interpolation/extrapolation. The only pressure intervals missing/filled during this leg were at 0-2 db, caused by chopping off going-in-water transition data during pressure-sequencing. When the down-cast CTD data have excessive noise, gaps or offsets, the up- cast data are used instead. CTD data from down- and up-casts are not mixed together in the pressure-series data because they do not represent identical water columns (due to ship movement, wire angles, etc.). It was necessary to use two up-casts for final WOCE A24 pressure-series CTD data: stations 1 and 71. There is an inherent problem in the internal digitizing circuitry of the NBIS Mark III CTD when the sign bit for temperature flips. Raw temperature can shift 1-2 millidegrees as values cross between positive and negative, a problem avoided by offsetting the raw PRT readings by ~1.5°C. The conductivity channel also can shift by 0.001-0.002 mS/cm as raw data values change between 32768/32767, where all the bits flip at once. This is typically not a problem in shallow to intermediate depths because such a small shift becomes negligible in higher gradient areas. Raw CTD conductivity traversed 32768/32767 during most A24 casts. The software was changed before station 23 was acquired to handle this discontinuity for the rest of the cruise; stations 1-22 were also re-processed with the updated software. Appendix C contains a table of CTD casts requiring special attention. 8. CTD CALIBRATION PROCEDURES ODF CTD #3 was used for a single cast (001/01) and developed a turret leak, which was repaired. ODF CTD #5 was used for all subsequent casts. An SBE35 Laboratory-grade reference PRT was deployed on the rosette as a cross calibration for the primary and secondary PRT temperatures. CTD conductivity and dissolved O2 were calibrated to in-situ check samples collected during each rosette cast. CTD PRESSURE AND TEMPERATURE Pre-cruise calibrations were used to determine shipboard pressure and temperature corrections for CTD #5. There were no significant shifts apparent in the CTD pressure or temperature, based on the primary/secondary PRT comparisons and the conductivity calibration. The primary PRT (serial #15407) appeared to hold its calibration relative to the SBE 35 to within 0.0005 °C. The secondary PRT (serial #15046) appeared to drift by 0.003 °C over the cruise and had drifted by 0.005°C since calibration in April. Figures 8.0 and 8.1 summarize the comparisons between the SBE 35 reference PRT and the primary and secondary PRT temperatures. Figure 8.0: Comparison between SBE 35 reference and primary PRT temperatures. Figure 8.1: Comparison between SBE 35 reference and secondary PRT temperatures. Pre- and post-cruise laboratory calibrations for CTD #5 were compared during the data finalization process. CTD #5 pressure shifted 0.5 to 0.6 db between April and July for both cold and warm calibrations. The August results were one-third closer to the April calibration. Half of the cold-calibration difference, and almost all of the warm-calibration difference, can be accounted for by differences in bath temperatures, since there is a notable temperature effect on this pressure sensor. This means the pre-/post-cruise pressure shift was -0.3 db or smaller, well within WOCE specifications. No adjustments were made to pressure. Pre-cruise calibrations were within 0.0004°C and halfway between the two post-cruise calibrations in the 0-3°C range. The April/July temperature corrections cross at 5°C; July/August corrections merge from 16-32 °C. The maximum difference is 0.0005°C, with the April correction more negative than both July/August above 5°C. Pre-cruise cold data is offset -0.00055°C or less from the August post-cruise calibration. Warmer data are within 0.00015°C for all 3 temperature calibrations. Nearly all of the CTD temperatures during A24 were below 18°C, where there is at most a -0.00055°C difference in pre- to post-cruise calibration corrections. The temperatures are well within WOCE specifications without further adjustment. CONDUCTIVITY The CTD rosette trip pressure and temperature and the bottle salinity were used to calculate a bottle conductivity. Differences between the bottle and CTD conductivities were then used to derive a conductivity correction. This correction is normally linear for the 3cm conductivity cell employed in the Mark III. Conductivity differences were fit to CTD conductivity for each cast, and the mean of the conductivity correction slopes examined: Figure 8.2: Conductivity correction slopes, per station. No significant change in the conductivity correction slope occurred over the cruise. Conductivity differences were then fit to CTD conductivity for all bottles to determine a mean conductivity correction slope: Figure 8.3: Mean conductivity correction slope, all stations. Since the mean correction slope did not significantly differ from the mean of individual slopes, the mean correction slope was applied and individual correction offsets fit for each cast. The resulting correction was adjusted for minor non-linearities in conductivity and pressure. The final form of the applied conductivity correction was: Gˇcorr = Gˇraw-9.13543e-11P^2+1.80848e-07P+0.0000147071G^2ˇraw-0.00176569Gˇraw+cˇoffset (8.0) where: Gˇcorr = Corrected conductivity (mS/cm); Gˇraw = Raw sensor conductivity; P = Corrected CTD pressure (db); and cˇoffset = Coefficient derived from the fit to bottle conductivity. Deep potential temperature-salinity overlays of successive CTD casts were then examined for consistency and the corrections fine-tuned. Conductivity corrections were re-examined post-cruise. The final conductivity slope and non-linearity corrections had not been applied to stations 150-153. Since no adjustments were made to pressure or temperature post-cruise, the corrections determined shipboard were used. However, it was noted that conductivity offsets were not smoothed in groups of casts. While the statistical bottle-CTD differences would look quite good, CTD data can sometimes be shifted further apart on consecutive casts if there were any problems with drift or standardization when analyzing bottle salts. CTD data at trips were re-extracted post-cruise, to generate a more consistent 2-2.5-second average at trips, like the realtime trip data (7-second averages were used shipboard for casts reprocessed after a software improvement). Conductivity offsets were recalculated for all casts, but processing time was cut short and they still were not smoothed. A plot of the offsets vs station number was examined to check casts with anomalous offsets as compared to nearby casts. Some of these were manually adjusted, based on deep theta-S comparisons as well as bottle-CTD differences (where an occasional larger difference could distort the automatically generated offset). There was a consistent -0.001-2 mS/cm shift in the CTD conductivities at cast bottom that continued during the entire deep upcast, beginning with stations in the mid-40s. This persisted to the end of the cruise, and could affect conductivity offsets (generated by comparing upcast data at trips with bottle data) used to correct the reported downcast CTD conductivity. There was an additional intermittent problem from station 124 onward with low-level (usually -0.001-2 mS/cm, occasionally -0.004 mS/cm) back-and-forth offsetting problems during upcasts, which became persistent by the early 140s. These could affect bottle data differences, but time was not allowed to re-examine these casts more closely. However, it was observed on deep theta-S plots that the CTD signal often spiked back to the downcast values during trips. Figure 8.4 illustrates the final offsets for CTD conductivity by station, after applying the linear and non-linear corrections. Figure 8.4: Final conductivity correction offsets, all stations. Figures 8.5, 8.6 and 8.7 summarize the residual differences between bottle and CTD salinities after applying the final conductivity corrections. Figure 8.5: Salinity residual differences after correction, by pressure. Figure 8.6: Salinity residual differences after correction, by station. Figure 8.7: Deep salinity residual differences after correction, by station. Note that some pressure-related nonlinearity exists after correction. This could have been further reduced by increasing the complexity of the correction. The CTD conductivity calibration represents a best estimate of the conductivity field throughout the water column. 3σ from the mean residual in Figures 8.6 and 8.7, or +/-0.0063 PSU for all salinities and +/-0.0020 PSU for deep salinities, represents the limit of repeatability of the bottle salinities, including all sources of variation (e.g., Autosal, rosette, operators and samplers). This limit agrees with station overlays of deep theta-salinity. Within most casts (a single salinometer run), the precision of bottle salinities appears to exceed 0.001 PSU. The precision of the CTD salinities appears to exceed 0.0005 PSU. CTD DISSOLVED OXYGEN The CTD dissolved O2 sensor (serial #6-02-07) was used for the entire cruise. There was an atypically higher noise level in the raw CTD O2 data for many casts which remains in the final data set. There were also numerous problems with a very low signal at the start of many downcasts, affecting data in the top 50 db (or as much as 500 db in stations in the 70s and 80s). These low data were offset, when feasible and very shallow, to bring the CTD O2 into the realm of reality. Generally, only very shallow (less than 20 db) data were offset, and any remaining problems were quality-coded as bad. There are a number of problems with the response characteristics of the SensorMedics O2 sensor used in the NBIS Mark III CTD, the major ones being a secondary thermal response and a sensitivity to profiling velocity. Stopping the rosette for as little as half a minute, or slowing down for a bottom approach, could cause shifts in the CTD O2 profile as oxygen became depleted in water near the sensor. Because of these problems, CTD rosette trip data cannot be directly calibrated to O2 check samples. Instead, down- cast CTD O2 data are derived by matching the up-cast rosette trips along isopycnal surfaces. The differences between CTD O2 modeled from these derived values and check samples are then minimized using a non-linear least-squares fitting procedure. Down-casts were deemed to be unusable for two casts (stations 1 and 71), so up-cast CTD O2 data were processed despite the signal drop-offs typically seen at bottle stops. There were no bottle oxygens for station 153/1, so the corrections from station 152 were used to bring the profile as close as possible to 153/2 results. Figures 8.8 and 8.9 show the residual differences between the corrected CTD O2 and the bottle O2 (ml/l) for each station, after the problem surface areas were offset and/or quality-coded. Figure 8.8: O2 residual differences after correction, by station. Figure 8.9: O2 residual differences (>2000db). Note that the mean of the differences is not zero, because the O2 values are weighted by pressure before fitting. The standard deviations of 0.079 ml/l for all oxygens and 0.036 ml/l for deep oxygens are only intended as metrics of the goodness of the fits. ODF makes no claims regarding the precision or accuracy of CTD dissolved O2 data. The general form of the ODF O2 conversion equation follows Brown and Morrison [Brow78] and Millard [Mill82], [Owen85]. ODF does not use a digitized O2 sensor temperature to model the secondary thermal response but instead models membrane and sensor temperatures by low-pass filtering the PRT temperature. In-situ pressure and temperature are filtered to match the sensor response. Time-constants for the pressure response Taup, and two temperature responses TauTs and TauTf are fitting parameters. The sensor current, or Oc, gradient is approximated by low-pass filtering 1st- order Oc differences. This term attempts to correct for reduction of species other than O2 at the cathode. The time-constant for this filter, Tauog, is a fitting parameter. Oxygen partial-pressure is then calculated: ⎛ dOˇc⎞ ⎜cˇ3*Pˇl+cˇ4Tˇf+cˇ5Tˇs+cˇ6 ----⎟ Oˇpp=[cˇ1ˇOc+cˇ2]·fˇsat(S,T,P)·e⎝ dt ⎠ (8.1) where: Oˇpp = Dissolved O2 partial-pressure in atmospheres (atm); Oˇc = Sensor current (uamps); fˇsat(S,T,P) = O2 saturation partial-pressure at S,T,P (atm); S = Salinity at O2 response-time (PSUs); T = Temperature at O2 response-time (°C); P = Pressure at O2 response-time (decibars); Pl = Low-pass filtered pressure (decibars); Tf = Fast low-pass filtered temperature (°C); Ts = Slow low-pass filtered temperature (°C); dOˇc/dt = Sensor current gradient (uamps/secs). 9. BOTTLE SAMPLING At the end of each rosette deployment water samples were drawn from the bottles in the following order: • CFCs; • He-3; • O2; • pCO2; • Total CO2; • Alkalinity; • Tritium; • Nutrients; • Salinity; • O18O16. Note that some properties were subsampled by cast or by station, so the actual sequence of samples drawn was modified accordingly. The correspondence between individual sample containers and the rosette bottle from which the sample was drawn was recorded on the sample log for the cast. This log also included any comments or anomalous conditions noted about the rosette and bottles. One member of the sampling team was designated the sample cop, whose sole responsibility was to maintain this log and insure that sampling progressed in proper drawing order. Normal sampling practice included opening the drain valve before opening the air vent on the bottle, indicating an air leak if water escaped. This observation together with other diagnostic comments (e.g., "lanyard caught in lid", "valve left open") that might later prove useful in determining sample integrity were routinely noted on the sample log. Drawing oxygen samples also involved taking the sample draw temperature from the bottle. The temperature was noted on the sample log and was sometimes useful in determining leaking or mis-tripped bottles. Once individual samples had been drawn and properly prepared, they were distributed to their laboratory for analysis. Oxygen, nutrients and salinity analyses were performed on computer-assisted (PC) analytical equipment networked to Sun SPARCstations for centralized data analysis. The analyst for a specific property was responsible for insuring that their results updated the cruise database. 10. BOTTLE DATA PROCESSING The first stage of bottle data processing consisted of verifying and validating individual samples, and checking the sample log (the sample inventory) for consistency. Oxygen flask numbers were verified, as each flask is individually calibrated and significantly affects the calculated O2 concentration. At this stage, bottle tripping problems were usually resolved, sometimes resulting in changes to the pressure, temperature and other CTD data associated with the bottle. The rosette bottle number was the primary identification for all samples taken from the bottle, as well as for the CTD data associated with the bottle. All CTD trips were retained whether confirmed or not so that they could be used to help resolve bottle tripping problems. Diagnostic comments from the sample log were then translated into preliminary WOCE quality codes, together with appropriate comments. Each code indicating a potential problem would be investigated. The next stage of processing would begin after all the samples for a cast had been accounted for. All samples for bottles suspected of leaking were checked to see if the properties were consistent with the profile for the cast, with adjacent stations and where applicable, with the CTD data. All comments from the analysts were examined and turned into appropriate water sample codes. The third stage of processing would continue throughout the cruise and until the data set is judged "final". Various property-property plots and vertical sections were examined for both consistency within a cast and consistency with adjacent stations. In conjunction with this process the analysts would review (and sometimes revise) their data as additional calibration or diagnostic results became available. Assignment of a WHP water sample quality code to an anomalous sample value was typically achieved through consensus. WHP water bottle quality flags were assigned with the following additional interpretations: 3 | An air leak large enough to produce an observable | effect on a sample is identified by a code of 3 on the | bottle and a code of 4 on the oxygen (small air | leaks may have no observable effect, or may only | affect gas samples), 4 | Bottles tripped at other than the intended depth were | assigned a code of 4. There may be no problems with | the associated water sample data. 5 | No water sample data reported. This is a | representative level derived from the CTD data for | reporting purposes. The sample number should be in | the range of 80-99. WHP water sample quality flags were assigned using the following criteria: 1 | The sample for this measurement was drawn from a | bottle, but the results of the analysis were not (yet) | received. 2 | Acceptable measurement. 3 | Questionable measurement. The data did not fit the | station profile or adjacent station comparisons (or | possibly CTD data comparisons). No notes from the | analyst indicated a problem. The data could be | correct, but are open to interpretation. 4 | Bad measurement. Does not fit the station profile, | adjacent stations or CTD data. There were analytical | notes indicating a problem, but data values were | reported. Sampling and analytical errors were also | coded as 4. 5 | Not reported. There should always be a reason | associated with a code of 5, usually that the sample | was lost, contaminated or rendered unusable. 9 | The sample for this measurement was not drawn. WHP water sample quality flags were assigned to the CTDSAL (CTD salinity) parameter as follows: 2 | Acceptable measurement. 3 | Questionable measurement. The data did not fit the | bottle data, or there was a CTD conductivity | calibration shift during the cast. 4 | Bad measurement. The CTD data were determined to be | unusable for calculating a salinity. 8 | The CTD salinity was derived from the CTD down cast, | matched on an isopycnal surface. WHP water sample quality flags were assigned to the CTDOXY (CTD oxygen) parameter as follows: 2 | Acceptable measurement. 4 | Bad measurement. The CTD data were determined to be | unusable for calculating a dissolved oxygen | concentration. 5 | Not reported. The CTD data could not be reported. 9 | Not sampled. No operational dissolved oxygen sensor | was present on this cast. Note that all CTDOXY values were derived from the down cast data, matched to the upcast along isopycnal surfaces. Table 10.0 shows the number of samples drawn and the number of times each WHP sample quality flag was assigned for each basic hydrographic property: Table 10.0: Frequency of WHP quality flag assignments. _________________________________________________________ Rosette Samples Stations 001-153 ------------------------------------------------------- Reported WHP Quality Codes Levels 1 2 3 4 5 7 9 ----------++--------+---------------------------------- Bottle || 3450 | 0 3387 4 56 0 0 3 CTD Salt || 3450 | 0 3440 6 0 0 4 0 CTD Oxy || 3413 | 0 3194 133 86 35 0 2 Salinity || 3438 | 0 3406 12 20 3 0 9 Oxygen || 3434 | 0 3419 3 12 9 0 7 Silicate || 3439 | 0 3431 5 3 3 0 8 Nitrate || 3439 | 0 3436 0 3 3 0 8 Nitrite || 3439 | 0 3436 0 3 3 0 8 Phosphate || 3439 | 0 3435 0 4 3 0 8 _________________________________________________________ Additionally, all WHP quality code comments are presented in Appendix D. 11. SALINITY ANALYSIS Salinity samples were drawn into 200 ml Kimax high alumina borosilicate bottles after 3 rinses, and were sealed with custom-made plastic insert thimbles and Nalgene screw caps. This assembly provides very low container dissolution and sample evaporation. When loose inserts were found, they were replaced to ensure an airtight seal. Salinity was determined after a box of samples had equilibrated to laboratory temperature, usually within 8-12 hours of collection. The draw time and equilibration time, as well as per-sample analysis time and temperature were logged. Two Guildline Autosal Model 8400A salinometers (55-654 and 48-263) located in a temperature-controlled laboratory were used to measure salinities. The salinometers were modified by ODF and contained interfaces for computer-aided measurement. A computer (PC) prompted the analyst for control functions (changing sample, flushing) while it made continuous measurements and logged results. The salinometer cell was flushed until successive readings met software criteria for consistency, then two successive measurements were made and averaged for a final result. The salinometer was standardized for each cast with IAPSO Standard Seawater (SSW) Batch P-127, using at least one fresh vial per cast. The estimated accuracy of bottle salinities run at sea is usually better than 0.002 PSU relative to the particular Standard Seawater batch used. PSS-78 salinity [UNES81] was then calculated for each sample from the measured conductivity ratios, and the results merged with the cruise database. 3438 salinity measurements were made and 279 vials of standard water were used. Six of the vials were found to be bad. Salinometer 55-654 was used throughout this leg. Salinometer 48-263 was the backup salinometer and was not used. The temperature stability of the laboratory used to make the measurements was very good, ranging from 21.4 to 24.6°C. The salinometer bath temperature was maintained at 24°C. The salinities were used to calibrate the CTD conductivity sensor. 12. OXYGEN ANALYSIS Samples were collected for dissolved oxygen analyses soon after the rosette sampler was brought on board and after CFC and helium were drawn. Nominal 125 ml volume-calibrated iodine flasks were rinsed twice with minimal agitation, then filled via a drawing tube and allowed to overflow for at least 3 flask volumes. The sample temperature was measured with a small platinum resistance thermometer embedded in the drawing tube. Draw temperatures are useful in detecting possible bad trips even as samples were being drawn. Reagents were added to fix the oxygen before stoppering. The flasks were shaken twice; immediately after drawing, and then again after 20 minutes, to assure thorough dispersion of the MnO(OH)2 precipitate. The samples were analyzed within 4 hours of collection. Dissolved oxygen analyses were performed with an SIO-designed automated oxygen titrator using photometric end-point detection based on the absorption of 365 nm wavelength ultra-violet light. Thiosulfate was dispensed by a Dosimat 665 buret driver fitted with a 1.0 ml buret. ODF uses a whole-bottle modified-Winkler titration following the technique of Carpenter [Carp65] with modifications by Culberson et. al [Culb91], but with higher concentrations of potassium iodate standard (approximately 0.012N) and thiosulfate solution (50 gm/l). Standard solutions prepared from pre-weighed potassium iodate crystals were run at the beginning of each session of analyses, which typically included from 1 to 3 stations. Several standards were made up during the cruise and compared to assure that the results were reproducible, and to preclude the possibility of a weighing error. Reagent/distilled water blanks were determined to account for oxidizing or reducing materials in the reagents. No preservative was added to the thiosulfate. The auto-titrator generally performed very well. The samples were titrated and the data logged by the PC control software. The data were then used to update the cruise database on the Sun SPARCstations. Blanks, and thiosulfate normalities corrected to 20°C, calculated from each standardization, were plotted versus time, and were reviewed for possible problems. New thiosulfate normalities were recalculated after the blanks had been smoothed. These normalities were then smoothed, and the oxygen data were recalculated. Oxygens were converted from milliliters per liter to micromoles per kilogram using the in-situ temperature. Ideally, for whole-bottle titrations, the conversion temperature should be the temperature of the water issuing from the bottle spigot. The sample temperatures were measured at the time the samples were drawn from the bottle, but were not used in the conversion from milliliters per liter to micromoles per kilogram because the software was not available. Aberrant drawing temperatures provided an additional flag indicating that a bottle may not have tripped properly. Oxygen flasks were calibrated gravimetrically with degassed deionized water (DIW) to determine flask volumes at ODF's chemistry laboratory. This is done once before using flasks for the first time and periodically thereafter when a suspect bottle volume is detected. All volumetric glassware used in preparing standards is calibrated as well as the 10 ml Dosimat buret used to dispense standard Iodate solution. Iodate standards are pre-weighed in ODF's chemistry laboratory to a nominal weight of 0.44xx grams and the exact normality is calculated at sea. Potassium Iodate (KIO3) is obtained from Johnson Matthey Chemical Co. and is reported by the suppliers to be > 99.4% pure. All other reagents are "reagent grade" and are tested for levels of oxidizing and reducing impurities prior to use. 3434 oxygen measurements were made. There were a few times when the data acquisition computer (PC) hung up and a sample was lost. The temperature stability of the laboratory used for the analyses was fair. No major problems were encountered with the analyses. Fifty-seven pair of replicate (ie. from the same rosette bottle) oxygen samples drawn. The standard deviation of the replicates was 0.004 ml/l. The oxygen data were used to calibrate the CTD dissolved O2 sensor. 13. NUTRIENT ANALYSIS Nutrient samples were drawn into 45 ml high density polypropylene, narrow mouth, screw-capped centrifuge tubes which were rinsed three times before filling. The tubes were rinsed with 1.2N HCL before each filling. Standardizations were performed at the beginning and end of each group of analyses (one cast, usually 24 samples) with a set of an intermediate concentration standard prepared in low-nutrient seawater for each run from secondary standards. The secondary standards were prepared aboard ship by dilution from dry, pre-weighed primary standards. Sets of 6-7 different concentrations of shipboard standards were analyzed periodically to determine the deviation from linearity as a function of concentration for each nutrient. Nutrient analyses (phosphate, silicate, nitrate and nitrite) were performed on an ODF-modified 4 channel Technicon AutoAnalyzer II, generally within one hour of the cast. Occasionally some samples were refrigerated at 4°C for a maximum of 4 hours. The methods used are described by Gordon et al. [Atla71], [Hage72], [Gord92]. The colorimeter output from each of the four channels were digitized and logged automatically by computer (PC), then split into absorbence peaks. Each run was manually verified. Silicate is analyzed using the technique of Armstrong et al. [Arms67]. Ammonium molybdate is added to a seawater sample to produce silicomolybdic acid which is then reduced to silicomolybdous acid (a blue compound) following the addition of stannous chloride. Tartaric acid is added to impede PO4 color (interference). The sample is passed through a 15 mm flowcell and the absorbence measured at 660nm. ODF's methodology is known to be non-linear at high silicate concentrations (>120 uM); a correction for this non-linearity is applied in ODF's software. All silicates during this expedition were in the linear range (<100 uM). Modifications of the Armstrong et al. [Arms67] techniques for nitrate and nitrite analysis are also used. The seawater sample for nitrate analysis is passed through a cadmium column where the nitrate is reduced to nitrite. Sulfanilamide is introduced, reacting with the nitrite, then N-(1-naphthyl)ethylenediamine dihydrochloride which couples to form a red azo dye. The reaction product is then passed through a 15 mm flowcell and the absorbence measured at 540 nm. The same technique is employed for nitrite analysis, except the cadmium column is not present, and a 50 mm flowcell is used. Phosphate is analyzed using a modification of the Bernhardt and Wilhelms [Bern67] technique. An acidic solution of ammonium molybdate is added to the sample to produce phosphomolybdic acid, then reduced to phosphomolybdous acid (a blue compound) following the addition of dihydrazine sulfate. The reaction product is heated to 58°C to enhance color development, then passed through a 50 mm flowcell and the absorbence measured at 820 nm. Nutrients, reported in micromoles per kilogram, were converted from micromoles per liter by dividing by sample density calculated at zero pressure, in-situ salinity, and an assumed laboratory temperature of 25°C. Na2SiF6, the silicate primary standard, is obtained from Aesar, a division of Johnson Matthey Chemical Co., and is reported by the supplier to be >98% pure. Primary standards for nitrate (KNO3), nitrite (NaNO2), and phosphate (KH2PO4) are also obtained from Johnson Matthey Chemical Co. and the supplier reports purities of 99.999%, 97%, and 99.999%, respectively. 3439 nutrient analyses were performed. No major problems were encountered with the measurements. The pump tubing was changed 3 times, and deep seawater was run as a substandard on each run. The efficiency of the cadmium column used for nitrate was monitored throughout the cruise and ranged from 99.0-100.0%. The temperature stability of the laboratory used for the analyses ranged from 21 deg. to 28°C, but was relatively constant during any one station (+/-1.5°C). REFERENCES Arms67. Armstrong, F. A. J., Stearns, C. R., and Strickland, J. D. H., "The measurement of upwelling and subsequent biological processes by means of the Technicon Autoanalyzer and associated equipment," Deep-Sea Research, 14, pp. 381-389 (1967). Atla71. Atlas, E. L., Hager, S. W., Gordon, L. I., and Park, P. K., "A Practical Manual for Use of the Technicon AutoAnalyzer(R) in Seawater Nutrient Analyses Revised," Technical Report 215, Reference 71-22, p. 49, Oregon State University, Department of Oceanography (1971). Bern67. Bernhardt, H. and Wilhelms, A., "The continuous determination of low level iron, soluble phosphate and total phosphate with the AutoAnalyzer," Technicon Symposia, I, pp. 385-389 (1967). Brow78. Brown, N. L. and Morrison, G. K., "WHOI/Brown conductivity, temperature and depth microprofiler," Technical Report No. 78-23, Woods Hole Oceanographic Institution (1978). Carp65. Carpenter, J. H., "The Chesapeake Bay Institute technique for the Winkler dissolved oxygen method," Limnology and Oceanography, 10, pp. 141-143 (1965). Cart80. Carter, D. J. T., "Computerised Version of Echo-sounding Correction Tables (Third Edition)," Marine Information and Advisory Service, Institute of Oceanographic Sciences, Wormley, Godalming, Surrey. GU8 5UB. U.K. (1980). Culb91. Culberson, C. H. and Williams, R. T., et al., "A comparison of methods for the determination of dissolved oxygen in seawater," Report WHPO 91-2, WOCE Hydrographic Programme Office (Aug 1991). Gord92. Gordon, L. I., Jennings, J. C., Jr., Ross, A. A., and Krest, J. M., "A suggested Protocol for Continuous Flow Automated Analysis of Seawater Nutrients in the WOCE Hydrographic Program and the Joint Global Ocean Fluxes Study," Grp. Tech Rpt 92-1, OSU College of Oceanography Descr. Chem Oc. (1992). Hage72. Hager, S. W., Atlas, E. L., Gordon, L. D., Mantyla, A. W., and Park, P. K., "A comparison at sea of manual and autoanalyzer analyses of phosphate, nitrate, and silicate," Limnology and Oceanography, 17, pp. 931-937 (1972). Mill82. Millard, R. C., Jr., "CTD calibration and data processing techniques at WHOI using the practical salinity scale," Proc. Int. STD Conference and Workshop, p. 19, Mar. Tech. Soc., La Jolla, Ca. (1982). Owen85. Owens, W. B. and Millard, R. C., Jr., "A new algorithm for CTD oxygen calibration," Journ. of Am. Meteorological Soc., 15, p. 621 (1985). UNES81. UNESCO, "Background papers and supporting data on the Practical Salinity Scale, 1978," UNESCO Technical Papers in Marine Science, No. 37, p. 144 (1981). 2. SHIPBOARD ADCP AND LADCP SHIPBOARD ADCP Upper ocean current measurements were made throughout the cruise using the hull- mounted acoustic Doppler current profiler (ADCP) system that is permanently installed on the R/V Knorr. The system includes five components: 1) an incoherent (narrow bandwidth, un-coded pulse) 4-beam Doppler sonar operating at 153 kHz (model VM-150 made by RD Instruments), mounted with beams pointing 30 degrees from the vertical and 45 degrees azimuth from the keel; 2) the ship's main gyro compass, continuously providing ship's heading measurements to the ADCP via a 1:1 synchro; 3) a Global Positioning System (GPS) attitude sensor (Ashtech model 3DF), which uses a 4-antenna array to provide interferometric measurements of ship's pitch, roll, and heading; 4) a GPS navigation receiver (Trimble Tasman) providing position fixes using both GPS frequency bands (L1 and L2) and the P and Y codes (military "Precision Positioning Service", or PPS); 5) an IBM-compatible personal computer running the Data Acquisition Software (DAS) version 2.48 from RD Instruments, augmented by Firing's software interrupt handler ("user exit") program "ue4", C. Flagg's user exit "agcave", and Flagg's TSR watchdog timer program. The ADCP was configured for 16-m pulse length, 8-m processing bin, and a 4-m blanking interval (all distances being projections on the vertical and based on a nominal sound speed of 1470 m/s). The transducer depth was 5 m; 60 velocity measurements were made at 8-m intervals starting 21 m below the surface. About 240 pings were sent in each 5-minute averaging interval. For each ping, velocities relative to the transducer were rotated to a geographical coordinate system using the gyro compass heading, but assuming pitch and roll to be zero. The single-ping velocities were then vector-averaged over the 5-minute ensemble. The ensemble- averaging was done separately for the vertical average from bins 2 through 10 and for the deviation of each bin from this vertical subset; the two parts were then added back together and stored. The conversion from Doppler shift to velocity was done using sound-speed calculated from the temperature measured by a sensor in the transducer, assuming a constant salinity of 35 psu. When a velocity estimate in one of the four beams was missing, velocity was calculated from the remaining three beams. In regions of shallow water, the ADCP was configured to track the bottom with one bottom-tracking ping for each water-tracking ping. This was effective to depths of 600 m or more. From the time the ship left Woods Hole to the last station of the present cruise, approximately 100 hours of underway bottom tracking data were collected. This is significant for the calibration calculations discussed below. The user exit program integrated the GPS position and attitude information into the ADCP data stream. Position fixes were recorded at the start and end of each ADCP averaging interval (5-minute ensemble). Attitude from the 3DF was sampled at each ping and edited within each ensemble. The mean, standard deviation, minimum, and maximum values of pitch, roll, and compass heading error were calculated and recorded. The compass error is the quantity of primary interest: for each ping, the compass reading used by the ADCP was subtracted from the most recent 3DF heading (updated once per second), and this difference was taken as the time-variable compass error plus some constant misalignment of the 3DF antenna array. The 3DF attitude information was not used for the real-time vector-averaging of velocity because it is not quite reliable enough; dropouts and outliers do occur. Velocity, position, and attitude measurements were post-processed using the University of Hawaii CODAS software package, generally as described by Firing in WHP Office Report WHPO 91-1, WOCE report 68/91. The essential modification since then is the rotation of the velocity measurements relative to the ship to correct for the gyro compass error as measured by the 3DF. After this correction, and a small but varying sound speed correction (not yet made at the time of this writing), standard water and bottom tracking calibration methods (Joyce, 1989; Pollard and Read, 1989) should yield two constants: a velocity scale factor, and a horizontal angular offset between the transducer and the 3DF antenna array. The angular offset is particularly important; an error of 0.1 degree leads to a cross- track bias of 1 cm/s for a ship speed of 11 kts. For the onboard data processing, these calibration factors were calculated based on bottom tracking from the transit from Woods Hole prior to the cruise and the transits to and from Cork. Water track calibration calculations based on the entire cruise (all stations--water track calibration requires ship accelerations, such as stops for stations) indicate an overall error of only 0.05 degree relative to the preliminary calibration. At present this small correction has not been applied. Closer inspection of all available calibration information indicates that the "constant" factors are measurably not constant. The angle offset factor may vary within a range of up to plus or minus 0.2 degrees. A possible cause is under investigation; it is not clear whether it will be possible to reduce this uncertainty in the present or future data sets. The quality of the shipboard ADCP data set from this cruise is exceptionally good. No instrument problems were detected; weather was mostly good and never very bad; there was an abundance of acoustic targets on the entire cruise track. The depth range was typically 400 m or more, sometimes a full 500 m, and only occasionally less than 300 m. There were no known compass failures and no long dropouts of 3DF data. The upper ocean velocity field during the cruise is summarized in a map of shipboard ADCP velocity vectors averaged from 100 to 300 m (Figure 2.0); vertical shear was weak on most of the cruise track, so this layer average is representative. The overall impression is of weak currents--usually under 50 cm/s, and mostly in the form of ubiquitous small-scale squirts and eddies. The contribution from tides and near-inertial motions has not yet been estimated quantitatively, but I believe it is a small part of what we see in Figure 2.0. The East Greenland Current stands out as a narrow jet flowing southwestward along the Greenland coast, particularly off Cape Farewell. On the northern crossing, however, it appears to have been highly convergent in the cross-track direction. The eddy field was relatively strong in the Rockall Trough and in the Iceland and Irminger basins on the section from Scotland to Greenland. Currents were mostly weak on the section from the Azores to Ireland on leg 1, and between the sub-polar front (about 50°N) and the East Greenland Current on leg 4. At and south of the sub-polar front the currents are stronger, but much of the pattern is not easy to interpret. There seem to be four main zones of eastward flow north of 40°N, some of them very narrow. There is a major southward component in the sub-polar front and at other spots between there and the Azores. Figure 2.0: A24 Shipboard ADCP velocity vectors. LOWERED ADCP To measure velocity throughout the water column at each station, a self- contained ADCP was mounted on the rosette; this is referred to as the lowered ADCP (LADCP). The LADCP includes a magnetic compass and a tilt sensor, so the velocity profiles can be rotated into the local east-north-up coordinate system. Because the motion of the rosette over the ground is not measured, the LADCP measurements of current relative to the instrument cannot be used directly to infer the current over the ground. Instead, the single- ping velocity profiles are differentiated vertically to remove the package motion (which changes only slightly between the time a ping is transmitted and the time the back-scattered return is received). The vertical shear estimates from all pings are then interpolated and averaged on a single uniform depth grid covering the whole water column. This full-depth shear profile is integrated vertically to yield a velocity profile with an unknown constant of integration; and the constant is calculated from the known displacement of the instrument between beginning and end of the cast, together with the shape of the relative velocity profile and the measured current past the instrument as a function of time during the cast. The method is explained in detail by Fischer and Visbeck (1993). The instrument used on this cruise was a new 150-kHz coded pulse ("Broadband") profiler made by RD Instruments (a specially modified Phase-III DR-BBADCP), with four beams angled 30 degrees from the vertical. All but four of the 154 profiles were made with the following instrument parameters: blanking interval, pulse length, and processing bin length were all set to 16 m (projected on the vertical). Sixteen depth bins were recorded. Pings were transmitted alternately at 1 and 1.5 or 1.6 second intervals. Data from each ping was recorded individually, with no averaging. Ambiguity resolution mode 1 (no automatic resolution) was used, with an ambiguity interval of either 3 m/s or 3.6 m/s--the smaller value was used when weather was exceptionally calm. Medium bandwidth was selected. Three-beam velocity solutions were not used, and solutions with an error velocity exceeding 15 cm/s were rejected. Bin-mapping based on tilt was selected. Immediately after each station the data were dumped from the LADCP to a PC via a serial line (RS-422), and transferred to a Sun workstation for archiving and processing. The profile was processed using the University of Hawaii system, a mixture of C, Matlab, and Perl programs. Velocity and shear data are automatically edited based on several criteria including correlation magnitude (typically 70- count minimum), error velocity (10 cm/s maximum), deviation of vertical velocity in a given bin from its vertical average (5 cm/s maximum), and deviation of individual shear estimates from a mean shear profile (3.5 standard deviations). These parameters are subject to change in later processing, but the values quoted seemed reasonable and adequate for the present data set. Additional editing is done on the upcast: the top two depth bins are rejected if the current, profiler vertical velocity, and profiler orientation are such that one beam may be intersecting the profiler's wake. Depth bins subject to contamination from the side-lobe return from the bottom, or from the return of the previous ping from the bottom, are also automatically rejected. Critical to this part of the editing is accurate knowledge of the depth of the bottom and the depth of the profiler. Therefore we have an automated routine for matching the time series of vertical velocity measured by the LADCP with the time series of vertical velocity calculated from the CTD pressure record, and then assigning the corresponding CTD-derived depths to the LADCP. With these instrument depths in the LADCP database, another program scans the LADCP back-scatter amplitude profiles in the near-bottom region; the LADCP depth plus the vertical range to the amplitude maximum is the bottom depth. With a high quality and continuous CTD time series available from ODF immediately after each cast, we were able to complete the LADCP processing about 20 minutes after the end of the data transfer. Accurate position fixes at the start and end of the LADCP profile are essential to the calculation of absolute velocities. We log the PPS GPS fixes at the full 1 Hz sampling rate. The processing software accesses these files and extracts the subsets needed for each profile. Magnetic variation is needed to calculate true direction from the compass readings; we calculate the variation from a standard model of the earth's magnetic field. To date we have not, however, performed any calibration of the compass in the instrument, but have taken the compass headings at face value. As with the shipboard ADCP, and for the same reasons, the LADCP quality on this cruise is excellent. Package motion was moderate and scattering levels were good, particularly at the higher latitudes. The only instrument problem was a bizarre incident early in the cruise: at stations 2 and 3 the program usually used to communicate with the LADCP (BBSC) gradually ceased working with it. (It turns out that a similar problem was encountered by Doug Wilson at about the same time. As of this writing, no one understands what happened, given that both failures occurred with profiler/PC/program combinations that had been working normally.) A simpler alternative program (BBTALK) was completely unaffected, and was used for the remainder of the cruise. In the scramble to switch to BBTALK for station 4, the setup commands were entered by hand and something seems not to have been right-the profiler returned garbage during about the first third of the cast, then inexplicably started recording normal-looking profiles. The result is that profile 4 is incomplete at best, and probably will be neglected henceforth. A map of LADCP current vectors averaged over the full depth range of the profile (Figure 2.1) shows some characteristics of the currents as observed on this cruise. As in the shipboard ADCP data, the East Greenland Current stands out as a prominent feature amid the welter of eddies. The barotropic component of the eddy field is weakest on the Azores-Ireland section and strongest on the Scotland-Greenland section, where vertically averaged velocities of 10 cm/s or more are common. The eddy field is not well resolved by the station spacing; the velocity profiles typically change radically from one station to the next. The tidal fraction of the velocity field measured by the LADCP has not yet been estimated, but is not expected to dominate the observations in any of the more energetic regions. REFERENCES Fischer, J., and M. Visbeck, 1993. Deep velocity profiling with self-contained ADCPs. J. Atmos. Oceanic Technol., 10, 764-773. Joyce, T. M., 1989. On in situ "calibration" of shipboard ADCPs. J. Atmos. Oceanic Technol., 6, 169-172. Pollard, R., and J. Read, 1989. A method for calibrating shipmounted Acoustic Doppler Profilers, and the limitations of gyro compasses. J. Atmos. Oceanic Technol., 6, 859-865 Figure 2.1: A24 Map of LADCP current vectors. 3. CFC-11 and CFC-12 SAMPLE COLLECTION Water samples were collected using 10 liter Niskin bottles which were cleaned for CFC analysis. All O- rings of the Niskin bottles (end cap O-rings and spigot O- rings) were baked in a vacuum oven to remove CFCs. CFC samples were drawn from 10 to 31 Niskin bottles per station, depending on bottom depth or station spacing. 100 ml precision groundglass syringes with Luer-lock fittings were used to draw water samples from the Niskin bottles. Vacuum-baked syringe valves were used, and were replaced whenever there was a suspicion of contamination or leakage. In general, sampling for CFC analysis was done at every station alternating fulldepth sampling and partial-depth sampling depending on the measurement progress of the previous station's samples. The partial depth sampling was planned according to the CFCs results readily available from previous stations as well as from the CTD profiles. A total of 2085 water samples from 132 CTD stations were measured, including approx. 70 duplicate pairs used to estimate measurement precisions. The shipboard CFC values will be finalized after a few minor blank corrections and a stripper efficiency correction for CFC-11 in the lab. Typical stripping efficiency of CFC-11 in various water temperature during this cruise is approx. 99.3%. Air samples were collected by Air Cadet pump through intake lines of 3/8" OD Decabon tubing from inlets at the bow and stern of the vessel. The bow side air intake was mostly used during this cruise. 107 air samples were measured to estimate current atmospheric CFC concentrations and to calculate the surface water CFC saturation conditions. Three or four replicate air samples were measured at each location to obtain reliable numbers. EQUIPMENT AND TECHNIQUE The chlorofluorocarbons CFC-11 and CFC-12 were measured by an ECD-GC (electron capture detector equipped gas chromatograph system), as described by Bullister and Weiss (1988), with slight modifications. Gas samples, dry air or standard gas, were injected onto a cold trap (-30°C) for concentration. Approximately 30 cc of seawater from collected samples was introduced into a glass stripping chamber where the dissolved gases were purged with purified gas, and the evolved CFCs were concentrated using the same cold trap. The trap was subsequently isolated and heated (100°C), so that the evolved CFCs could be transferred into a pre-column (15 cm of Porasil-C) and then a chromatographic separating column (3 m of Porasil C) held at 70°C in the GC oven. The ECD was operated at 250°C. The analysis of all water samples was completed within 3 to 7 hours of the water coming on board. Typical standard gas and water sample chromatograms are shown in Figures* 1a and 1b. The data acquisition, peak integration and calculation were carried out by a Sun Microsystems computer with an HP35900 chromatographic interface. CALIBRATION The CFC-11 and CFC-12 analyses were calibrated over the concentration range of the samples, using calibration curves made by injections of fixed volumes of standard gas filled to various pressures as measured by a precision quartz pressure transducer (Paro-scientific 740). Using polynomial curves fitted to the calibration points, the corrected peak areas were converted into molar concentrations. The standard gas was prepared at the Scripps Institution of Oceanography (SIO) and was calibrated on the SIO 1993 scale. PRELIMINARY RESULTS CFC-11 and CFC-12 were near saturation in surface waters, and deep and bottom waters of the North Atlantic Ocean basins are in general well ventilated unlike the Indian or Pacific Ocean where deep basins are mostly filled with low CFC or CFC- free waters. The lowest CFC content water was observed in the North-Eastern Atlantic Basin in the LEG-1 (Azores to Ireland) toward the north below 3000-4000 m (CFC- 11: less than 0.04 pmol/kg). Typical CFCs profiles from different basins are shown in Figures* 2a, 2b and 2c to show dynamic and spatially heterogeneous features of the North Atlantic Ocean. Well known bottom and deep water features such as overflow waters and the Labrador Sea Water were clearly resolved by CFCs distributions. High CFC-content Denmark Strait Overflow Water (DSOW) was observed in the Irminger Basin (LEG-3) and on the Eirik Ridge south of Greenland (LEG-4). The other high CFC-content overflow water, Iceland-Scotland Overflow Water (ISOW), was observed on the eastern flank of the Reykjanes Ridge in the Iceland Basin and on the western side of the ridge in the Irminger Basin (LEG- 3). The low salinity, high CFC and high oxygen content Labrador Sea Water (LSW) was observed at about 1500-2000 m depth range in nearly every survey section. The CFC concentration of the LSW core layer was highest (CFC-11: ^-4 pmol/kg) on the Eirik Ridge, Greenland (LEG-4) and in the Irminger Basin, and progressively became lower toward the west and south. The CFC-11 concentration of the LSW core layer observed in the North- Eastern Atlantic Basin (LEG-1) was as low as 1.5- 2.0 pmol/kg. The mid-depth low CFCs, low oxygen and high salinity water originated from the Mediterranean Sea was observed in the Azores-Ireland (LEG-1) section, in the southern Rockall Trough (LEG-2) section, and the southern part of the Greenland-Azores (LEG-4) section at approx. 1000 m depth. Thick and relatively homogeneous Subpolar Mode Water with high CFC concentration was well developed in the upper few hundred meters in the northern part of the survey area. The highest CFC concentration surface water was generally found in the Eastern Greenland Current area. Near 0 C cold surface water near the Angmassalik, Greenland (LEG-3) showed the highest CFC concentration (CFC- 11: as high as 6.83 pmol/kg). The CFC-11 contour sections from the four legs of this expedition in the subpolar North Atlantic Ocean are shown in Figures* 3a-d. REFERENCE Bullister, J. L., and R. F. Weiss. 1988. Determination of CCl3F and CCl2F2 in seawater and air. Deep-Sea Research, 35: 839-853. 4. HELIUM, TRITIUM AND 18O SAMPLE COLLECTION Water samples for later analysis of helium, tritium and 18O were collected from 10 litre Niskin bottles. The strategy was to sample the entire water column with emphasis on Labrador Sea Water and the Overflow waters. In particular, we extensively sampled the east Greenland Shelf and Slope. 607 Helium samples, 596 Tritium samples, and 367 18O samples were collected at 43, 42 and 37 stations respectively. Since samples for 18O measurement will also be drawn from the tritium samples, the total number of samples available for 18O analysis is 963. Water samples for Helium analysis were collected in stainless steel cylinders with rotating plug valves on both ends. The cylinder was attached to the spigot on the Niskin by tygon tubing. When not in use, the tubing was kept soaked in a bucket of seawater to keep it conditioned. Tritium samples were collected in 1 litre glass bottles. The bottle caps were then secured using insulation tape. 18O samples were collected in 30 ml glass bottles. Bottle caps were secured similarly. EQUIPMENT Samples collected in the cylinders were processed on board for Helium. This was done using the "at sea extraction system" provided by W.J. Jenkins of the WHOI Helium Isotope Lab (Jenkins, 1992). The extracted Helium was collected in 30 ml glass bulbs, which were subsequently flame-sealed. All samples will be analysed mass-spectrometrically at the Lamont-Doherty Earth Observatory. Helium and Tritium samples will be analyzed in the Noble Gas Lab using techniques described in Bayer (1989). 18O samples will be analyzed in the Stable Isotope Lab. REFERENCES Bayer, R., Schlosser, P., Bonisch, G., Rupp, H., Zaucker, F., and Zimmek, G., 1989. Performance and blank components of a mass spectrometric system for routine measurement of helium isotope and tritium by the 3He ingrowth method. Sitzungsberichte der heidelberger Akademie der Wissenschaften, Mathematisch-naturwissenschaftliche Klasse. Jenkins, W. J., 1992. ASEX User's Manual: Documentation on procedures, software and hardware for the At Sea Extraction System, version 2.0. Woods Hole Oceanographic Institution. ___________________________________________________________________________________________________________ ___________________________________________________________________________________________________________ CARBON DIOXIDE, HYDROGRAPHIC, AND CHEMICAL DATA OBTAINED DURING THE R/V KNORR CRUISES IN THE NORTH ATLANTIC OCEAN ON WOCE SECTIONS AR24 (NOVEMBER 2 - DECEMBER 5, 1996) AND A24, A20, AND A22(MAY 30 - SEPTEMBER 3, 1997) Contributed by Kenneth M. Johnson,1 Robert M. Key,2 Frank J. Millero,3 Christopher L. Sabine,4 Douglas W. R. Wallace,5 Christopher D. Winn,6 Linda Arlen,7 Kenneth Erickson,8 Karsten Friis,5 Meridith Galanter,3 Jamie Goen,3 Richard Rotter,2 Carrie Thomas,2 Richard Wilke,8 Taro Takahashi,9 and Stewart C. Sutherland9 1 Department of Applied Science, Brookhaven National Laboratory, Upton, NY, U.S.A. Retired, now at P.O. Box 483, Wyoming, RI, U.S.A. 2 Department of Geosciences, Princeton University, Princeton, NJ, U.S.A. 3 Rosenstiel School of Marine and Atmospheric Science, University of Miami, Miami, FL, U.S.A. 4 Pacific Marine Environmental Laboratory, NOAA, Seattle, WA, U.S.A. 5 Institute for Marine Sciences, Kiel, Germany 6 Hawaii Pacific University, Kaneohe, HI, U.S.A. 7 James J. Howard Laboratory, NOAA, Sandy Hook, NJ, U.S.A. 8 Department of Applied Science, Brookhaven National Laboratory, Upton, NY, U.S.A. 9 Lamont-Doherty Earth Observatory, Palisades, NY, U.S.A. Prepared by Alexander Kozyr Carbon Dioxide Information Analysis Center Oak Ridge National Laboratory Oak Ridge, Tennessee, U.S.A. Date Published: September 2003 Prepared for the Climate Change Research Division Office of Biological and Environmental Research U.S. Department of Energy Prepared by the Carbon Dioxide Information Analysis Center OAK RIDGE NATIONAL LABORATORY Oak Ridge, Tennessee 37831-6335 Budget Activity Numbers: KP 12 04 01 0 and KP 12 02 03 0 managed by UT-BATTELLE, LLC for the U.S. DEPARTMENT OF ENERGY under contract DE-AC05-00OR22725 ORNL/CDIAC-143 NDP-082 ACRONYMS ACCE Atlantic Circulation and NDP numeric data package Climate Change Experiment NOAA National Oceanic and A/D analog-to-digital Atmospheric Administration ADCP acoustic Doppler current nm nautical mile profiler NSF National Science Foundation ALACE autonomous Lagrangian ODF Ocean Data Facility circulation explorer ODV Ocean Data View BOD biological oxygen demand ORNL Oak Ridge National Laboratory BNL Brookhaven National Laboratory OSU Oregon State University 14C radiocarbon PC personal computer CALFAC calibration factor PDF Portable Document Format CDIAC Carbon Dioxide Information PI principal investigator Analysis Center PU Princeton University CFC chlorofluorocarbon QA quality assurance CMDL Climate Monitoring and QC quality control Diagnostics Laboratory R/V research vessel CO2 carbon dioxide RSMAS Rosenstiel School of Marine CTD conductivity, temperature, and and Atmospheric Sciences depth sensor SIO Scripps Institution of CRM certified reference material Oceanography DOE U.S. Department of Energy SOMMA single-operator multipara- emf electro-magnetic fields meter metabolic analyzer EXPOCODE expedition code SSW standard seawater FTP file transfer protocol TALK total alkalinity GMT Greenwich mean time TCO2 total carbon dioxide GPS global positioning system TD to-deliver IAPSO International Association for the UH University of Hawaii Physical Sciences of the Ocean UM University of Miami I/O input-output UW University of Washington IR infrared VFC voltage to frequency converter JGOFS Joint Global Ocean Flux Study WHOI Woods Hole Oceanographic kn knots Institution LADCP lowered ADCP WHPO WOCE Hydrographic Program LDEO Lamont-Doherty Earth Office Observatory WOCE World Ocean Circulation MATS Miami University alkalinity Experiment titration systems WHP WOCE Hydrographic Program NBIS Neil Brown Instrument system ABSTRACT Johnson K., R. Key, F. Millero, C. Sabine, D. Wallace, C. Winn, L. Arlen, K. Erickson, K. Friis, M. Galanter, J. Goen, R. Rotter, C. Thomas, R. Wilke, T. Takahashi, and S. Sutherland. 2003. Carbon Dioxide, Hydrographic, and Chemical Data Obtained During the R/V Knorr Cruises in the North Atlantic Ocean on WOCE Sections AR24 (November 2-December 5, 1996) and A24, A20, and A22 (May 30-September 3, 1997) A. Kozyr (ed.) ORNL/CDIAC-143, NDP-082. Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, U.S. Department of Energy, Oak Ridge, Tennessee, 41 pp. This documentation describes the procedures and methods used to measure total carbon dioxide (TCO2) total alkalinity (TALK), and partial pressure of CO2 (pCO2) at hydrographic stations on the North Atlantic Ocean sections AR24, A24, A20, and A22 during the R/V Knorr Cruises 147-2, 151-2, 151-3, and 151-4 in 1996 and 1997. Conducted as part of the World Ocean Circulation Experiment (WOCE), the expeditions began at Woods Hole, Massachusetts, on October 24, 1996, and ended at Woods Hole on September 3, 1997. Instructions for accessing the data are provided. A total of 5,614 water samples were analyzed for discrete TCO2 using two single-operator multiparameter metabolic analyzers (SOMMAs) coupled to a coulometer for extracting and detecting CO2. The overall accuracy of the TCO2 determination was ± 1.59 µmol/kg. The TALK was determined in a total of 6,088 discrete samples on all sections by potentiometric titration using an automated titration system developed at the University of Miami. The accuracy of the TALK determination was ± 3 µmol/kg. A total of 2,465 discrete water samples were collected for determination of pCO2 in seawater on sections A24, A20, and A22. The pCO2 was measured by means of an equilibrator-IR system by scientists from Lamont-Doherty Earth Observatory. The precision of the measurements was estimated to be about ± 0.15%, based on the reproducibility of the replicate equilibrations on a single hydrographic station. The North Atlantic data set is available as a numeric data package (NDP) from the Carbon Dioxide Information Analysis Center. The NDP consists of 12 ASCII data files, one Ocean Data View-formatted data file, a NDP-082 ASCII text file, a NDP-082 PDF file, and this printed documentation, which describes the contents and format of all files, as well as the procedures and methods used to obtain the data. Keywords: carbon dioxide; TCO2; total alkalinity; partial pressure of CO2; coulometry; gas chromatography; World Ocean Circulation Experiment; North Atlantic Ocean; hydrographic measurements; carbon cycle. 1. BACKGROUND INFORMATION The World Ocean Circulation Experiment (WOCE) Hydrographic Program (WHP) was a major component of the World Climate Research Program. The primary WOCE goal was to understand the general circulation of the global ocean well enough to be able to model its present state and predict its evolution in relation to long- term changes in the atmosphere. The impetus for the carbon system measurements arose from concern over the rising atmospheric concentrations of carbon dioxide (CO2). Increasing atmospheric CO2 may intensify the earths natural greenhouse effect and alter the global climate. Although CO2-related measurements [total CO2 (TCO2), total alkalinity (TALK), partial pressure of CO2 (pCO2), and pH] were not an official WOCE measurements, a coordinated effort to make the carbon measurements was supported as a core component of the Joint Global Ocean Flux Study (JGOFS). This effort received support in the United States from the U.S. Department of Energy (DOE), the National Oceanic and Atmospheric Administration (NOAA), and the National Science Foundation (NSF) for WOCE cruises through 1998 to measure the global spatial and temporal distributions of CO2 and related parameters. Goals were to estimate the meridional transport of inorganic carbon in a manner analogous to the oceanic heat transport (Bryden and Hall 1980; Brewer, Goyet, and Drysen 1989; Holfort et al. 1998; Roemmich and Wunsch 1985), and to build a data base suitable for carbon-cycle modeling and the estimation of anthropogenic CO2 increase in the oceans. The CO2 survey took advantage of the sampling opportunities provided by the WOCE cruises during this period, and the final data set was expected to cover on the order of 23,000 stations. Wallace (2002) recently reviewed the goals, conduct, and initial findings of the survey. This report discusses the results of the research vessel (R/V) Knorr expedition along the WOCE Sections AR24, A24, A20, and A22 [cruises 147-2, 151-2, 151-3, and 151-4, respectively (Fig. 1)]. The latter three cruises not only were part of WOCE but also were a component of the Atlantic Circulation and Climate Change Experiment (ACCE). The ACCE was intended to improve the understanding of the entrainment and transformation of warm saline subtropical water into the subpolar North Atlantic waters, with special emphasis on sampling the North Atlantic Current region. This region plays an important role in the exchange of CO2 between the subtropical and subpolar gyres. The exchange between these gyres affects the magnitude and direction of air-sea CO2 exchange in the North Atlantic and is therefore an important factor in the global carbon cycle. By 1997 the goal of high-quality measurements of chemical and physical parameters had been completed in all of the major oceans except the North Atlantic. Hence the cruises documented here also represent the concluding phase of the DOE- sponsored Global CO2 Survey. The expedition (section AR24) started at Woods Hole, Massachusetts, USA, on October 24, 1996, with a transit to the Azores; the station work began on November 2, 1996. The 1997 cruises started from Ponta Delgada, Azores, on May 30, 1997, and ended in Woods Hole on September 3, 1997, after stops in Halifax, N.S., Canada, and Port of Spain, Trinidad. The large-scale three-dimensional distribution of temperature, salinity, and chemical constituents, including the carbonate system parameters measured on these cruises (TCO2, and TALK on the AR24 section and TCO2, TALK, and pCO2 on A24, A20, and A22 sections), will be plotted using the data from these sections. Knowledge of these parameters and their initial conditions will enable researchers to determine heat and water transport, as well as carbon transport, which will contribute to the understanding of processes affecting climate change. The sections described in this report include WOCE Section A22, the only Caribbean transect of the WOCE program. In addition, the stations occupied on these cruises repeated some sections sampled in previous years during the International Geophysical Year during the 1950s. They also included measurements from the eastern subpolar gyre of source and overflow waters from the Labrador, Norwegian, Greenland, and Iceland Seas. They give good coverage of boundary currents, particularly the Deep Western Boundary Current; and repeating AR24 and A24 provides some insight into seasonal variation in the North Atlantic. This data documentation is the result of the cooperative efforts of chemical oceanographers from Brookhaven National Laboratory (BNL), the University of Hawaii (UH), Lamont-Doherty Earth Observatory (LDEO), and the University of Miamis Rosenstiel School of Atmospheric and Marine Science (RSMAS), U.S.A. The work aboard the R/V Knorr was supported by the U. S. Department of Energy under contract DE-ACO2-76CH00016 and DE-FG02-93ER61540. The authors are also especially grateful to the Sonderforschungsbereich 460 at the University of Kiel (Dr. F. Schott, Leader), funded by the Deutsche Forschungsgemeinschaft, for their support and assistance in completing the written documentation. 3.2. Total CO2 Measurements As on previous cruises, TCO2 was determined using automated dynamic headspace sample processors (SOMMA) with coulometric detection of the CO2 extracted from acidified samples. A description of the SOMMA-Coulometry System and its calibration can be found in Johnson et al., (1987), Johnson and Wallace, (1992), and Johnson et al., (1993). A schematic diagram of the SOMMA analytical sequence may be found in earlier cruise reports (see Johnson et al. 1995;,1996), and further details concerning the coulometric titration can be found in Huffman (1977) and Johnson, King, and Sieburth (1985). The methods used for discrete TCO2 on WOCE sections have been extensively dealt with in previous reports (Johnson et al., 1998a) and only need onlyto be briefly summarized. The AR24 section required modification of the usual sampling procedures. As noted in Section 3.1.2 above, 4-L sampling bottles were employed on the rosette, which limitinged the amount of sample available for the carbonate system analysts to one 500-mL bottle. Hence, the TCO2 coulometric titration analysis had to be completed before the partially empty 500-mL bottle was passed to the TALK group for the potentiometric alkalinity titration. There was enough sample to complete both measurements, but not enough time or sample for TCO2 replicate analyses from the same 500-mL sample bottle. The 4- L sampling bottles also made it impossible to draw duplicate samples from the same sampling bottle. Without duplicate samples from the hydrographic stations, standard measures of sample precision (DOE, 1994; Johnson, et al., 1998b) could not be completed on the AR24 section. Samples were poisoned with 100 µL of a 50% solution of HgCl2, and analyzed for TCO2 within 24 hours of collection (DOE, 1994). For sections A24, A20, A224, single or duplicate samples were collected in 300-mL biological oxygen demand (BOD) bottles, poisoned with 100 µL of a 50% solution of HgCl2, and analyzed for TCO2 within 24 hours of collection, according to standard operating procedures (DOE, 1994). The samples were stored in a dark refrigerator at 46°C until approximately 12 hours before analysis, when they were removed and placed in a temperature bath at 18-20°C and thermally equilibrated. The SOMMA sample pipette and sample bath were also kept at approximately 20°C. Duplicate samples were usually collected on each cast at the surface and from the bottom waters. For some casts, three sets of duplicates were taken. The duplicates were analyzed within the run of cast samples from which they originated souch that the time elapsed between duplicate analyses was 3-12 hours. As per standard operating procedure (DOE 1994), Certified Reference Material (CRM) was routinely analyzed according to DOE (1994) guidelines. The CRM was supplied by Dr. Andrew Dickson of the SIO, and for the North Atlantic cruises, batches 33, 36, and 37 were used. The certified values for these batches were: TCO2 = 2009.85 µmol/kg @ salinity = 33.781 for batch 33; TCO2 = 2050.21 µmol/kg @ salinity = 35.368 for batch 36; and TCO2 = 2044.15 µmol/kg @ salinity = 34.983 for batch 37. The CRM TCO2 concentration was determined by vacuum-extraction/manometry in the laboratory of C. D. Keeling at SIO. An accurately known volume of seawater was injected from an automated to- deliver (TD) pipette into a stripping chamber. Following acidification, the resultant CO2 from continuous gas extraction was dried, and coulometrically titrated on a model 5011 UIC Ccoulometer with a maximum titration current of 50 mA in the counts mode (the number of pulses or counts generated by the coulometers VFC during the titration was displayed). In the coulometer cell, the acid (hydroxyethylcarbamic acid) formed from the reaction of CO2 and ethanolamine is titrated coulometrically (electrolytic generation of OH-) with photometric endpoint detection. The product of the time and the current passed through the cell during the titration (charge in coulombs) is related by Faradays constant to the number of moles of OH- generated and thus to the moles of CO2 whichthat reacted with ethanolamine to form the acid. The age of each titration cell is logged from its birth (time that electrical current is applied to the cell) until its death (time when the current is turned off). The age is measured in minutes from birth (chronological age) and in mgC titrated since birth (carbon age). Each system was controlled with an IBM -compatible PC equipped with two RS232 serial ports (coulometer and barometer), a 24-line digital input/output card (solid state relays and valves), and an analog -to -digital (A/D) card (temperature, conductivity, and pressure sensors). Real Time Devices (located in State College, PA 16803) manufactured the cards. The SOMMA temperature sensors (model LM34CH, National Semiconductor, Santa Clara, CA) with a voltage output of 10 mV/F were calibrated against thermistors certified to 0.02°F prior to the cruise using a certified mercury thermometer. These sensors monitored the temperature of SOMMA components, including the pipette, gas sample loops, and the coulometer cell. The SOMMA software was written in GWBASIC Version 3.20 (Microsoft Corp., Redmond, WA), and the instruments were driven from an options menu appearing on the PC monitor. With the coulometers operated in the counts mode, conversions and calculations were made using the SOMMA software rather than the programs and the constants hardwired into the coulometer circuitry. The SOMMA-coulometry systems were calibrated with pure CO2 (calibration gas) using hardware consisting of an 8-port gas sampling valve (GSV) with two sample loops of known volume [determined gravimetrically by the method of Wilke, Wallace, and Johnson et al., (1993)] connected to the calibration gas through an isolation valve; with the vent side of the GSV was plumbed to a barometer. When a gas loop was filled with CO2 at known temperature and pressure, the mass (moles) of CO2 contained therein was calculated, and the ratio of the calculated mass to that determined coulometrically iwas the calibration factor (CALFAC); the CALFAC which was used to correct the subsequent sample titrations for small departures from 100% recoveries (DOE, 1994). The standard operating procedure was to make gas calibrations daily for each newly prepared titration cell ([normally, one cell per day and three sequential calibrations per cell at a carbon age of 39 mgC (mean age @ 6 mgC), with the result of the third calibration taken as the CALFAC if it was consistent with the second, (i.e., agreement to ± 0.1% or better)]. Daily gas calibrations were made on both systems throughout the cruises. The "to-deliver" volume (Vcal) of the sample pipettes was determined (calibrated) gravimetrically prior to the cruise to ± 0.02% or better in October of 1996. The calibration was checked periodically during all cruises by collecting aliquots of deionized water dispensed from the pipette into pre-weighed serum bottles. The serum bottles were crimp-sealed and weighed immediately during the on-shore laboratory calibrations, or returned to shore where they were reweighed on a model R300S balance (Sartorius, Gttingen, Germany) balance as soon as possible. The apparent weight (g) of water collected (Wair) was corrected to the mass in vacuum (Mvac) with the to- deliver volume being Mvac divided by the density of the calibration fluid at the calibration temperature. After the AR24 section in 1996, the system pipettes were dismounted and replaced with chemically cleaned pipettes in March, 1997. For the 1997 sections, the calibration volumes (Vcal) at the calibration temperature (tcal) of the sample pipettes were redetermined to ± 0.01% from a set of calibration samples taken on July 3, 1997, on aboard the Knorr at the completion of section A24 and were weighed on September 17. The TCO2 pipette volumes for the four North Atlantic sections are summarized in Table 2. Table 2: The "to-deliver" pipette volume (Vcal) and calibration temperature (tcal) for the discrete SOMMA-Coulometer Systems (S/N 004 and 030) used on WOCE Section AR24 (1996) and Sections A24, A20, and A22 (1997) ______________________________________________________ Section System S/N Vcal (mL) tcal (C) ------------------- ---------- --------- -------- AR24 (1996) 004 21.8927 19.91 A24/A20/A22 (1997) 004 21.2630 19.19 AR24 (1996) 030 21.3733 20.91 A24/A20/A22 (1997) 030 25.8544 19.52 ______________________________________________________ The sample volume (Vt) at the pipette temperature was calculated from the expression: Vt = Vcal [1 + av (t - tcal)] where av is the coefficient of volumetric expansion for pyrex-type glass (1 X 10^-5/°C), and t is the temperature of the pipette at the time of a measurement. The mean pipette temperature on the AR24 section in 1996 was 20.32 ± 0.51°C (n = 948), and on the 1997 North Atlantic Sections it was 19.55 ± 0.52°C (n = 4666). The factory-calibrated coulometers were electronically calibrated independently in the laboratory before the cruise as described in Johnson et al. (1993, 1996) and DOE (1994), and the terms INTec and SLOPEec were obtained and entered into the software for each system. The micromoles of carbon titrated (M), whether extracted from water samples or the gas loops, was: M = [Counts/4824.45-(Blank X Tt )-(INTec X Ti)]/SLOPEec where 4824.45 (counts/µmol) is a scaling factor obtained from the factory calibration; Tt wais the length of the titration in minutes; Blank is the system blank in µmol/min; INTec is the intercept from electronic calibration in µmol/min; Ti is the time in minutes during the titration where current flow was continuous; and SLOPEec is the slope from electronic calibration. Note that the slope obtained from the electronic calibration procedure applied for the entire length of the titration, but the intercept correction applied only for the period of continuous current flow (usually 34 min) because the intercept can only be calculated only from calibrated levels of current flowing continuously. Unfortunately, the coulometer system 030, which was electronically calibrated prior to the AR24 cruise and again in March 1997, had to be replaced at the start of section A24 in May 1997. However, the replacement coulometer (S/N CBE-9010-V) was calibrated at the factory on March 20, 1997. Hence we assumed that the replacement coulometer was properly calibrated, and we entered the default calibration coefficients into the software (SLOPEec = 1.0 and INTec = 0.0). The system 004 was also recalibrated in March 1997 following the AR24 cruise with nearly identical results to those obtained in October 1996, and it was not recalibrated during the 1997 WOCE sections. The electronic calibration coefficients, along with the mean gas calibration factors determined for the North Atlantic section discrete TCO2 coulometers, are given in Table 3. Table 3 illustrates an advantage of the independent laboratory electronic calibration procedure. The mean CALFAC for systems 004 and 030 using the laboratory-determined electronic calibration coefficients was approximately 1.0036 (or 99.64% recovery of the theoretical mass of CO2 calibration gas measured coulometrically) vs 1.0053 (99.47% recovery) for the factory- calibrated coulometer. Hence, a small percentage (0.17%) of the less than 100% recovery for known masses of CO2 coulometrically titrated can be explained by a factory-calibration procedure whichthat is apparently slightly less accurate than the laboratory calibration. This difference has been consistent throughout the CO2 survey. Table 3: The electronic calibration and the mean gas calibration coefficients for the discrete TCO2 systems on WOCE Section AR24 (1996) and Sections A24, A20, and A22 (1997) __________________________________________________________________________ Section System SLOPE INT(ec) CALFAC(n) St. dev. Rel. st. S/N (ec) µmol/min dev. (%) ----------- ------ -------- -------- ------------ -------- -------- AR24 004 0.999372 0.002528 1.003892(9) 0.000650 0.06 A20/A22/A24 004 0.998905 0.001466 1.003361(63) 0.000740 0.07 AR24 030 0.999306 0.003550 1.003780(26) 0.000497 0.05 A20/A22/A24 030* 1.000000 0.000000 1.005344(59) 0.001369 0.13 ------------------------------------------------------------------------ *Factory-calibrated coulometer installed at the beginning of the A24 section in May 1997. __________________________________________________________________________ For water samples, the discrete TCO2 concentration in µmol/kg was calculated from: TCO2 = M X CALFAC X [1/(Vt X P)] X dHg where P is the density of sea water in g/mL at the measurement temperature and sample salinity calculated from the equation of state given by Millero and Poisson (1981), and dHg is the correction for sample dilution with bichloride solution (for the AR24 section in 1996 dHg = 1.0002 and for the 1997 sections dHg = 1.000333). One of the SOMMA-Coulometry Systems (S/N 004) was equipped with a conductance cell (Model SBE-4, Sea-Bird Electronics, Inc., Bellevue, WA) for the determination of salinity measurement as described by Johnson et al. (1993). Whenever possible SOMMA and CTD salinity were compared to identify mistrips or other anomalies, but the bottle salinity (furnished by the chief scientist) was used to calculate TCO2. Quality control-quality assurance (QC-QA) was assessed from the results of the 275 CRM analyses made using systems 004 and 030 during the four North Atlantic sections. These data are summarized in Table 4, and the temporal distribution of the differences is plotted in Fig. 2 for section AR24 (1996) and in Fig. 3 for sections A24, A20, and A24 (1997). Table 4: The mean analytical difference (?TCO2 = measured ? certified) and the standard deviation of the differences between measured and certified TCO2 on WOCE Sections AR24, A24, A20, and A22 _______________________________________________ Section System ∆ TCO2 St. dev. n S/N (µmol/kg) (µmol/kg) ---------- ------ --------- --------- --- AR24 004 1.42 2.10 16 AR24 030 1.54 1.88 49 Mean/total 1.51 1.92 65 A24 004 0.04 1.10 49 A20 004 0.23 1.20 42 A22 004 0.06 0.69 17 Mean/total 0.10 1.08 108 A24 030 0.79 1.00 48 A20 030 0.44 1.43 35 A22 030 0.26 1.22 19 Mean/total 0.57 1.21 102 Overall mean/total 0.61 1.47 275 _______________________________________________ The overall accuracy of the CRM analyses was better than 1 µmol/kg on both systems for the four North Atlantic sections, with a combined overall mean difference of + 0.61 µmol/kg (n = 275). However, Table 4 shows that on the AR24 section (1996), the mean difference and the standard deviation of the differences were noticeably larger for both systems compared towith the 1997 sections (A24/A20/A22). This may be due in part to mechanical problems experienced by the AR24 measurement group, operator procedures, and possibly the relatively short time available to service and re-calibrate the systems prior to the AR24 section. The latter was brought about by the fact that the system 004 had been used in the Indian Ocean from 1994-1996, and was only returned to BNL for service, repair, and re-calibration in the fall of 1996. System 030, which was a newly built system returned to the laboratory after a test cruise in the North Atlantic, also was not returned until the summer of 1996. For the 1997 sections, both systems were available in the laboratory for servicing from January through May of 1997. Indeed, the 1997 WOCE sections represented the only opportunity during the CO2 survey for the BNL measurement group to thoroughly service and test the systems, reagents, and analytical gases in the laboratory with real samples and CRM prior to shipment. As a result, the accuracy and precision of the CRM analyses made in 1997 (see Table 4) probably represents the highest quality possible for these systems under field conditions. All CRM analyses made on the discrete systems (004 and 030) during the 1997 sections are reported in Table 4. However, for section AR24, two CRM analyses were classified as outliers and dropped from the data set. These were CRM No. 206 run on system 030 on November 23 (difference = + 10.17 µmol/kg) at a cell carbon age of 39.5 mgC, and CRM No. 600 on system 030 on November 28 (difference = + 7.99 µmol/kg) at a carbon age of 35.7 mgC. One CRM analysis (CRM No. 352) run on system 004 on December 1 is not included in the data set because the titration did not attain an endpoint. The second phase of the QC-QA procedure was an assessment of precision. As described in the text, duplicate samples could not be taken during the AR24 section in 1996. Hence the only estimate of AR24 sample precision was the standard deviation of the differences between the measured and certified TCO2 on both systems (see Table 4). Because differences from both systems have been combined, the CRM measurements are analogous to the sample duplicates analyzed on each system and should reflect both random and systemic error (bias). The decrease in precision for the CRM analyzed on the AR24 section in 1996 (± 1.92 µmol/kg) compared towith the CRM analyzed in 1997 (± 1.20 µmol/kg) was consistent with the problems described for the 1996 leg. The good agreement in TCO2 between systems in 1996 (see Table 4) suggests that the analyzingsis of duplicate seawater samples on each system, as was the casedone in 1997, might have yielded a higher precision than the precision of the CRM differences. Nevertheless, without sample duplicates, the AR24 sample precision must be based on the CRM analyses. Hence the precision of the TCO2 determination for the AR24 section in 1996 was ± 1.92 µmol/kg (n = 65). Because procedures and performance varied from 1996 to 1997, separate estimates of sample precision were required for each year; and the data for 1997 are given in Table 5. By 1997 the deployment of two independent SOMMA systems side-by-side was routine, and the conventions employed for the estimation of precision in the earlier WOCE data reports are retained in Table 5. For sections A24, A20, and A22 in 1997, the single-system precision was determined from samples with duplicates analyzed on the same system (either 004 or 030). The sample precision was calculated using duplicates that were analyzed on both systems (004 and 030). Table 5: Precision of the discrete TCO2 analyses on WOCE Sections A24, A20, and A22 ___________________________________________________________________ Section | Mean absolute difference | Pooled standard deviation |--------------------------|-----------|----------------- | σbs | ± St. | K | Sp^2 | K | n | d.f. | (µmol/kg) | dev. | | (µmol/kg) | | | --------|-------------------------------------------------------- | Single-system precision --------|-------------------------------------------------------- A24 | 1.08 | 1.01 | 175 | 1.04 | 175 | 350 | 175 A20 | 0.95 | 1.14 | 84 | 1.04 | 84 | 168 | 84 A22 | 0.99 | 0.93 | 71 | 0.96 | 71 | 142 | 71 --------|-------------------------------------------------------- | Sample precision --------|-------------------------------------------------------- All | 1.76 | 1.41 | 56 | 1.59 | 61 | 122 | 61 ___________________________________________________________________ Single-system and sample precision have been separately assessed in Table 5 as: • "between-sample" precision (σbs), which is the mean absolute difference between duplicates (n=2) drawn from the same Niskin bottle; and • the pooled standard deviation (Sp^2) calculated according to Youden (1951), where K was the number of samples with duplicates analyzed, n was the total number of replicates analyzed from K samples, and n - K was the degrees of freedom (d.f.). Single-system precision provided a measure of drift in system response during a sequence of sample analyses. This is because the time elapsed between duplicate analyses on the same system using the same coulometer cell was deliberately kept at from 3 to 12 hours on the assumption that drift or change in response would be reflected in the single-system precision by an increase in the imprecision of the duplicate analyses. Sample precision, on the other hand, was measured because TCO2 measurements were made on two separate systems and an estimate of overall sample precision for the section (s), independent of which analytical system was used, was required. Sample precision is the most conservative estimate of precision, incorporating several sources of random or systematic (bias) error. As on other sections in the Atlantic Ocean (e.g., A8 and A10) where SOMMA- Ccoulometer systems have been run in parallel, the sample precision was slightly less precise than the single-system precision. This indicated that changes in system response during the coulometer cell lifetime in 1997 were clearly within the precision of the method (± 1.59 µmol/kg), while the slight but consistent decrease in sample precision compared towith single-system precision was probably due at least in part to a small bias between the 004 and 030 systems. Although the precision was equivalent for both systems, system 030 gave on average slightly higher results than system 004. For example, the mean ∆TCO2 for system 004 CRM was +0.10 µmol/kg, but it was +0.57 µmol/kg for system 030 CRM (see Table 4); while the mean of the seawater samples (n = 56, Table 5) analyzed on 030 was +1.17 µmol/kg higher than the mean for the same samples analyzed on system 004. Hence the uniformly excellent single-system precisions for 1997 can not be used for sample precision, and analyzing duplicate replicates on each system remains the definitive measure of the overall precision of the 1997 data set and the TCO2 calibration procedures. The two discrete systems should give the same result for the same sample, and the extent to which they differ is a measure of the overall precision of the data set obtained with two independent systems. For TCO2 on the 1997 North Atlantic WOCE sections, the precision of the TCO2 determination was ± 1.59 µmol/kg (K= 56). The North Atlantic sample precision for all four sections in 1996 and 1997 (± 1.92 and ± 1.59 µmol/kg, respectively) is in good agreement with the published and unpublished sample precision for other WOCE sections where systems were run in parallel: AE1, 1991 (± 1.65 µmol/kg); P6, 1992 (± 1.65 µmol/kg); A10, 1993 (± 1.92 µmol/kg); A8, 1994 (± 1.17 µmol/kg); Indian Ocean, 1995 (± 1.20 µmol/kg). During the 1997 North Atlantic sections, a limited number of duplicate samples (K = 6) were analyzed from two different Niskin bottles closed at the same depth, and the mean absolute difference and standard deviation was 0.77 ± 0.50 µmol/kg, which was consistent with earlier findings (e.g., Johnson et al., 1998a,; Johnson et al. 2001) that there were likely no significant analytical effects due to gas exchange with the overlying headspace of the Niskin bottles during sampling. Tables 4 and 5 show an internally consistent data set of high quality with excellent accuracy (< or = 2.0 µmol/kg), high single-system precision (< or = ± 1.0 µmol/kg), and a slightly higher imprecision for the sample precisions (± 1.59 - 1.92 µmol/kg). Based on these data, the TCO2 data clearly meet survey criteriaon for accuracy (< or = 4.0 µmol/kg) and precision, and as with previous data submissions, no correction for instrumental bias or CRM analytical differences has been applied to the TCO2 data. 3.3. Total Alkalinity Measurements TALK and pH, were measured using an automated potentiometric titration system developed at the University of Miami (hereafter designated as MATS). The MATS is described by Millero et al. (1993a). It consisted of two parts: a Metrohm model 665 Dosimat titrator and a pH meter (Orion, Model 720A) which are interfaced with a PC. A water-jacketed, fixed -volume (~200 mL), closed Plexiglass sample cell, of greater volume than but otherwise similar to those used by Bradshaw and Brewer (1988), was used to increase the precision of the measurements. The cell, titrant burette, and sample cell were theromstatted at 25 ± 0.05°C using a constant temperature bath (Neslab, Model RTE 221). A Lab Windows/CVI program was used to run the titrators, record the volume of titrant added, and to record the measured electromagnetic frequency (emf) of the electrodes through RS232 serial interfaces. The electrodes for measuring the emf during the titration consisted of a ROSS glass pH electrode (Orion, Model 810100) and a double-junction Ag/AgCl reference electrode (Orion, Model 900200). Seawater samples were titrated by adding enough HCl to exceed the carbonic acid end point of the titration. During a typical titration, the electro- magnetic frequency (emf) readings were recorded until stable (± 0.05 mV). Normally, at this point, a fixed volume of acid would be added,; however, the MATS were designed to add enough acid to increase the voltage by a pre- assigned increment (13 mV). This was done to give an even distribution of data points over the course of a full titration, which consists of 25 data points and takes about 20 minutes. With two systems, approximately 7 hours was required to run a 31-bottle station cast. As noted in Sections 3.1 and 3.2 above, a 4-L Niskin sampling bottles were employed on the rosette, which limited the amount of sample available for the carbonate system analysts to one 500-mL bottle. Hence there was not enough sample to complete duplicate alkalinity analyses from the same bottle or to draw duplicate samples from the same sampling bottle. The titrant (acid) used throughout the cruises was prepared, standardized, and stored in 500-mL borosilicate glass bottles for use in the field. A single 55- gallon batch of 0.25-m HCl acid was prepared by dilution of concentrated HCl (AR Select Mallinckrodt). The acid was prepared in 0.45 m NaCl to yield a total ionic strength similar to that of seawater salinity 35.0 (I = ~ 0.7 M). The acid was standardized by coulometry (Taylor and Smith, 1959; Marinenko and Taylor, 1968). The acid molality was also checked by titration on seawaters with known alkalinities, and sub samples were sent to the laboratory of A. Dickson at SIO for an independent laboratory determination of the molality. The calibrated molality of the acid used for the North Atlantic WOCE Sections was 0.24892 ± 0.00003 m HCl. The consistency of the method was checked for each cast using low -nutrient surface seawater, and the accuracy of the method was checked by analyzing CRM Batches 33 (1996), 36, and 37 (1997) and comparing the analyzed values with the certified TALK in the same manoner as for TCO2 (see also Section 3.2 for batch data). The mean differences between at-sea measurements and the certified TALK values are given in Table 6. The TALK of each batch was also determined in the laboratory by weight titrations, which were found to agree with the certified values to ± 2 µmol/kg. In addition, the pH of the CRM batches was also determined in the laboratory spectrophotometrically according to the methods of Clayton and Byrne (1993) prior to the cruise. The at-sea titration pH measurements were also compared towith the pre-cruise spectrophotometric values, and and the reader is referred to Millero et al. (1999) for further details. Table 6: The mean analytical difference between analyzed and certified TALK for the MATS on WOCE Section AR24 (1996), and Sections A24, A20, and A22 (1997) __________________________________________________________ CRM TALK Measured TALK ∆TALK Section Cells n µmol/kg µmol/kg µmol/kg ------ --------- --- -------- ------------- ------- AR24 2, 19, 17 59 2234.9 2233.3 -1.6 A24 2, 18, 12 148 2283.9 2283.3 -0.6 A20 2, 18, 12 96 2314.1 2217.1 3.0 A22 2, 12 65 2314.1 2215.4 1.3 __________________________________________________________ The mean differences between the at -sea measurements and the certified TALK were within 3.0µmol/kg (Table 6). Hence the measured and certified TALK were in good agreement. For pH and TCO2, the corresponding results were 0.021 and 9 µmol/kg, respectively, with the larger deviation in pH attributable to the non-Nernstian behavior of the electrodes near a pH of 8 (Millero et al., 1993b). The at -sea sample alkalinity titrations were corrected using the results for the CRM. For TALK, the CALFAC used to correct the at sea measurements was: CALFAC = CRM (certified value)/(at- sea value), and for pH the CALFAC was: pH = pH (CRM)/pH (at-sea). Duplicate samples were usually taken for each station in the same manner as for TCO2 (surface and deep) and analyzed to determine and monitor the precision of the MATS. The average difference between replicates was ± 1.0, ±1.1, and ± 1.1 µmol/kg for sections A24, A20, and A22, respectively, which demonstrated the high precision of the MATS throughout the study. A preliminary description of the major trends in the data and the behavior of alkalinity over time in the North Atlantic is given by Millero et al. (1999). 3.4. Discrete pCO2 Measurements The discrete measurements of pCO2 were performed by the LDEO group on three of four sections of the North Atlantic survey. During the WOCE sections A24, A20, and A22, a total of 2,465 samples were analyzed onboard the R/V Knorr (1,103, 595, and 767 samples respectively). On the earlier WOCE section AR24, discrete pCO2 was not measured. An automated equilibrator-infrared (IR) gas analyzer system was used during the expedition for the determination of partial pressure of CO2 in the seawater samples. Its design is similar to that described by Chipman et al., Marra, and Takahashi (1993) with the exception that the gas chromatograph was replaced with an infraredIR gas analyzer. The equilibrator-IR system is shown schematically in Fig. 4. The system consists of a circulation pump plumbed to re-circulate air in a closed system through porous plastic gas dispersers immersed in a 250 -mL seawater sample. The seawater sample is contained in a 250-mL Pyrex reagent bottle with a standard taper-ground glass stopper whichthat serves as an equilibration vessel. A Pyrex extension tube (~ 20 mL), thatwhich has a standard taper-ground glass male-joint to form an air-tight seal with the reagent bottle, is connected to the mouth of the reagent bottle to provide an extra headspace forto preventing seawater from entering the gas circulation line. Four sets of flasks and circulation pumps are used so that four water samples can be processed concurrently. Because the partial pressure of CO2 is sensitive to temperature, the equilibration flasks are kept immersed in a water bath maintained at 20°C. The temperature at which the water sample is equilibrated with circulating gas is measured with a precision of ± 0.01°C and is recorded. An electrically driven Valco 10-port valve (the equilibrator selection valve in Fig. 4) is used to isolate each of the equilibrators during the initial equilibration. Manually operated 2-way and 3-way Whitey valves allow the headspace in each equilibrator to be filled with a calibration gas of known CO2 concentration, creating a known initial condition for the headspace (about 40 mL) before equilibration. The equilibrator is open to the laboratory air through isolation coils attached to the low-pressure side of the equilibrator, keeping the total pressure of equilibration the same as the ambient atmospheric pressure. The atmospheric pressure is measured with a high- precision electronic barometer with an accuracy of better than 0.05%, and is recorded. It takes about 20 minutes for each water sample to be thermally equilibrated with the constant-temperature water bath, and the headspace gas is re-circulated through the water sample throughout the period to iensure CO2 equilibration. An electrically driven Valco 6-port valve (the sample selection valve in Fig. 4) is connected to the equilibrator election valve and to the calibration gas selection valve. This allows toselection of the gas sample to be analyzed for CO2: the equilibrated sample gas or one of the four calibration gases. A 2-way normally-closed Skinner solenoid valve on the output of the calibration gas selection valve controls the flow of the calibration gases to the sample selection valve. It also providesd a necessary second means of stopping the flow of the calibration gases to prevent their accidental loss in case of a control malfunction. The concentration of CO2 in the gas equilibrated with the seawater sample is determined using IR gas analyzer (LICOR Model 6125) in a flow-through mode. A 0.5-mL aliquot of equilibrated headspace gas, representing less than 1% of the circulating gas, is isolated using a gas pipette (attached to the sampling valve in Fig. 4), and swept with CO2-free air (or pure nitrogen gas) flowing at a constant rate of about 50 mL/min. For low-pCO2 samples, a 1-mL gas pipette (attached to the sampling valve) is used. The sample gas is passed through a permeation drying tube for the removal of water vapor, and injected into the infraredIR gas analyzer cell (about 7 mL in volume) filled previously with CO2-free air. The displaced CO2-free air is discharged out of the cell into the laboratory. The small volume of the gas sample iensures that all of the CO2 from the gas pipette areis found in the analyzer cell at the same time, so that the peak height is proportional to the amount of CO2 present in the gas pipette. Drying of the sample gas avoids the effects of pressure-broadening of the CO2 absorption spectra and of dilution caused by water vapor. The amount of CO2 in the sampling pipette is a function of the loop volume, temperature, and pressure. The temperature is held constant and measured, and the pressure of the sample gas is same as the barometric pressure, which is measured with an accuracy of better than 0.05%. The peak height, which represents the number of moles of CO2 in the sample gas, is calibrated every 1.5 hours using a quadratic equation fitted to three calibration gas mixtures (366.52, 788.8 and 1211.4 ppm mole fraction in dry air). The analytical procedure begins with water samples being drawn from the 10-L Niskin bottles off a rosette directly into 250-mL Pyrex reagent bottles. These served as both sample containers and equilibration vessels. The samples were immediately inoculated with 100 µL of 50% saturated mercuric chloride solution, sealed airtight with ground glass stoppers to prevent biological modification of the pCO2, and stored in the dark until analysis. Measurements were normally performed within 24 hours of sampling. A headspace of 3 to 5 mL was left above the water to allow for thermal expansion during storage. Prior to analysis, the sample flasks were brought to the water bath temperature of 20°C in the constant -temperature bath. The equilibrator headspace, including the extension tube and the gas circulation tubings, wasere filled with a calibration gas of known CO2 concentration. The gas in the equilibrators, and in the tubing that connects them to the gas pipette loop, was re circulated continuously for about 20 minutes through a gas disperser immersed in the water. This provided a large surface area for gas exchange between the sample water and circulating gas, and equilibrium for CO2 was attained in 15 minutes. The temperature of the bath water was assumed to be that forf the sample water, and was measured at the time of equilibration with a precision of ±0.01°C using a thermometer calibrated against a NIST-certified thermometer. This temperature is reported in the data tables as TEMP_PCO2 and showed no variation at a limit of ±0.01°C. The equilibrated air samples awere saturated with water vapor at the temperature of equilibration and had the same pCO2 as the water. By injecting the air aliquot into the infraredIR analyzer after the water vapor iswas removed, the concentration of CO2 was measured. Therefore, the effect of water vapor must be taken into consideration for computing pCO2 as follows: pCO2 (µatm) = [Cmeas (ppm)] X [total press. of equilibration (atm) - water vapor press. (atm)] where Cmeas is the mole fraction concentration of CO2 in dried equilibrated air. The total pressure of equilibrated air is measured by having the headspace in the equilibrator flask always at atmospheric pressure. The latter was measured with an electronic barometer at the time each equilibrated air sample iwas injected into the IR analyzer for CO2 determination. The water vapor pressure was computed at the equilibration temperature, and salinity of the seawater. Cmeas was determined by using a quadratic equation fit to three of the calibration gas mixtures. The concentrations for standard gases used are traceable to the WMO reference scale through analysis in the laboratories of C. D. Keeling of SIO (La Jolla, California) and of Pieter P. Tans of NOAA/CMDL (Boulder, Colorado). The values of the standard gas mixtures used during this cruise were: 366.52 ppm CO2, 788.0 ppm CO2, and 1211.4 ppm CO2. Corrections were made to account for the change in pCO2 of the sample water due to the transfer of CO2 between the water and circulating air during equilibration. We know the pCO2 in equilibrated, perturbed water and the TCO2 by coulometry before the equilibration. We can also calculate the change in TCO2 in the water based on the change in pCO2 between the post-equilibrium value and the known concentration in the pre-equilibrium condition. With the pre-equilibrium TCO2 plus the perturbation in TCO2 during equilibration, the post-equilibrium TCO2 value was obtained. Using the post-equilibrium TCO2 and measured pCO2 values, TALK at the end of the equilibration was calculated, knowingbased ousing the temperature, salinity, phosphate, and silicate data. Since the perturbation does NOT change the TALK, the pre-equilibrium pCO2 from the pre-equilibrium TCO2 was calculated, the calculated TALK, and the temperature, salinity, etc., were calculated. This is the value that was reported as pCO2, the pre-equilibrium calculated value. The magnitude of this correction is generally less than 2 µatm. Details of the computational scheme are presented in a DOE technical report by Takahashi, et al. (1998). The pCO2 values reported in this data set are expressed as micro-atmospheres at the temperature of equilibration. The precision of the pCO2 measurement for a single hydrographic station was estimated to be about ±0.15% based on the reproducibility of replicate equilibrations. The station-to-station reproducibility was estimated to be about ±0.5%. 4. DATA CHECKS AND PROCESSING PERFORMED BY CDIAC An important part of the numeric data packaging 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 Knorr cruise along WOCE Sections AR24, A24, A20, and A22 in the North Atlantic Ocean. • The final carbon-related data were provided to CDIAC by the ocean carbon measurement PIprincipal investigators listed in Section 2. 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 90 retrieval code was written and used to merge and reformat all data files. • Every measured parameter for each station was plotted vs depth (pressure) to identify questionable data points using the Ocean Data View (ODV) software (Schlitzer 2001) Station Mode (Fig. 5). • Section plots for every parameter were generated using ODVs Section Mode in order to map a general distribution of each property along all North Atlantic Ocean sections (Fig. 6). • To identify noisy data and possible systematic, methodological errors, property-property plots were generated (Fig. 7) for all parameters, carefully examined, and compared with plots from previous expeditions in the North Atlantic. • All variables were checked for values exceeding physical limits, such as sampling depth values that are greater than the given bottom depths. • Dates, times, and coordinates were checked for bogus values (e.g., values of MONTH < 1 or > 12; DAY < 1 or > 31; YEAR < 1996 or > 1997; TIME < 0000 or > 2400; LATITUDE < 7.000 or > 67.000; LONGITUDE < -68.000 or > -8.000. • Station locations (latitudes and longitudes) and sampling times were examined for consistency with map and cruise information supplied by PIprincipal investigators. • The designation for missing values, given as -9.0 in the original files, was changed to -999.9 for the consistency with other oceanographic data sets. 5. HOW TO OBTAIN THE DATA AND DOCUMENTATION (frrom CDIAC) This data base (NDP-082) is available free of charge from CDIAC. The complete documentation and data can be obtained from the CDIAC oceanographic Web site (http://cdiac.ornl.gov/oceans/doc.html), through CDIAC's online ordering system (http://cdiac.ornl.gov/pns/how_order.html), or by contacting CDIAC (see below). The data are also available from CDIACs anonymous file transfer protocol (FTP) area via the Internet. Please note that, to access these files, your computer needs tomust have FTP software loaded on it (this is built in to most newer operating systems). Use the following commands to obtain the data base. ftp cdiac.ornl.gov or >ftp 160.91.18.18 Login: anonymous or ftp Password: your e-mail address ftp> cd pub/ndp082/ ftp> dir ftp> mget (files) ftp> quit 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 E-mail: cdiac@ornl.gov Internet: http://cdiac.ornl.gov/ 6. REFERENCES Armstrong, F. A. J., C. R. Stearns, and J. D. H. Strickland. 1967. The measurement of upwelling and subsequent biological processes by means of the Technicon AutoAnalyzer and associated equipment. Deep-Sea Research 14:381-9. Atlas, E. L., S. W. Hager, L. I. Gordon, and P. K. Park. 1971. A Practical Manual for Use of the Technicon AutoAnalyzer in Seawater Nutrient Analyses (revised). Technical Report 215, Reference 71-22, Oregon State University, Department of Oceanography, Oregon. Bernhardt, H. and A. Wilhelms. 1967. The continuous determination of low- level iron, soluble phosphate and total phosphate with the AutoAnalyzer. Technicon Symposia 1:385-9. 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 28:69-86. Brewer, P. G., C. Goyet, and D. Dyrssen. 1989. Carbon dioxide transport by ocean currents at 25° N latitude in the Atlantic Ocean. Science 246:477-79. Bryden, H. L., and M. M. Hall. 1980. Heat transport by ocean currents across 25° N latitude in the North Atlantic Ocean. Science 207:884. Carpenter, J. H. 1965. The Chesapeake Bay Institute technique for the Winkler dissolved oxygen method. Limnology and Oceanography 10:141-3. Chipman, D. W., J. Marra, and T. Takahashi. 1993. Primary production at 47° N and 20° W in the North Atlantic Ocean: A comparison between the 14C incubation method and the mixed layer carbon budget. Deep-Sea Research 40:151-69. Clayton, T. and R. H. Byrne. 1993. Calibration of m-cresol purple on the total hydrogen ion concentration scale and its application to CO2-system characteristics in seawater. Deep-Sea Research 40:2115-29. Culberson, C. H., G. Knapp, M. Stalcup, R. T. Williams, and F. Zemlyak. 1991. A Comparison of Methods for the Determination of Dissolved Oxygen in Seawater. WHP Office Report, WHPO 91-2. WOCE Hydrographic Program Office, Woods Hole, Mass. U.S.A. DOE (U.S. Department of Energy). 1994. Handbook of Methods for the Analysis of the Various Parameters of the Carbon Dioxide System in Seawater. Version 2.0. ORNL/CDIAC-74. A.G.Dickson and C. Goyet (eds.). Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, Oak Ridge, Tenn., U.S.A. Gordon, L. I., J. C. Jennings, Jr., A. A. Ross, and J. M. Krest. 1992. A Suggested Protocol for Continuous Flow Automated Analysis of Seawater Nutrients (Phosphate, Nitrate, Nitrite and Silicic Acid) in the WOCE Hydrographic Program and the Joint Global Ocean Fluxes Study. Grp. Tech. Rpt. 92-1. Chemical Oceanography Group, Oregon State University, College of Oceanography, Oregon, U.S.A. Gordon, L. I., J. C. Jennings, Jr., A. A. Ross, and J. M. Krest. 1994. A Suggested Protocol for Continuous Flow Automated Analysis of Seawater Nutrients (Phosphate, Nitrate, Nitrite Aand Silicic Acid) in the WOCE Hydrographic Program and the Joint Global Ocean Fluxes Study. In WOCE Operations Manual. WHP Office Report WHPO 91-1. WOCE Report No. 68/91. Revision 1. Woods Hole, Mass., U.S.A. Hager, S. W., E. L. Atlas, L. I. Gordon, A. W. Mantyla, and P. K. Park. 1972. A comparison at sea of manual and autoanalyzer analyses of phosphate, nitrate, and silicate. Limnology and Oceanography 17:931-7. Holfort, J., K. M. Johnson, B. Schneider, G. Siedler, and D. W. R. Wallace. 1998. Meridional transport of dissolved inorganic carbon in the South Atlantic Ocean. Global Biogeochemical Cycles 12:479-499. Huffman, E. W. D., Jr. 1977. Performance of a new automatic carbon dioxide coulometer. Microchemical Journal 22:567-73. Johnson, K. M., A. E. King, and J. McN. Sieburth. 1985. Coulometric TCO2 analyses for marine studies: An introduction. Marine Chemistry 16:61-82. Johnson, K. M., P. J. Williams, and L. Brandstroem, and J. McN. Sieburth. 1987. Coulometric TCO2 analysis for marine studies: Automation and calibration. Marine Chemistry 21:117-33. Johnson, K. M., and D. W. R. Wallace. 1992. The Single-operator Multiparameter Metabolic Analyzer for Total Carbon Dioxide with Coulometric Detection. DOE Research Summary No. 19. Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, Oak Ridge, Tenn., U.S.A. Johnson, K. M., K. D. Wills, D. B. Butler, W. K. Johnson, and C. S. Wong. 1993. Coulometric total carbon dioxide analysis for marine studies: Maximizing the performance of an automated gas extraction system and coulometric detector. Marine Chemistry 44:167-87. Johnson, K. M., D. W. R. Wallace, R. J. Wilke, and C. Goyet. 1995. Carbon Dioxide, Hydrographic, and Chemical Data Obtained During the R/V Meteor Cruise 15/3 in the South Atlantic Ocean (WOCE Section A9, February-March 1991). ORNL/CDIAC-82, NDP-051. Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, Oak Ridge, Tenn. Johnson, K. M., B. Schneider, L. Mintrop, and D. W. R. Wallace. 1996. Carbon Dioxide, Hydrographic, and Chemical Data Obtained During the R/V Meteor Cruise 18/1 in the North Atlantic Ocean (WOCE Section A1E, September 1991). NDP-056. Carbon Dioxide Information Analysis Center (CDIAC), Oak Ridge National Laboratory, Oak Ridge, Tenn. Johnson, K. M., B. Schneider, L. Mintrop, and D. W. R. Wallace. 1998a. Carbon Dioxide, Hydrographic, and Chemical Data Obtained During the R/V Meteor Cruise 22/5 in the South Atlantic Ocean (WOCE Section A10, December 1992- January 1993). ORNL/CDIAC-113, NDP-066. Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, Oak Ridge, Tenn. 49 pp. Johnson, K. M., A. G. Dickson, G. Eischeid, C. Goyet, P. R. Guenther, R. M. Key, F. J. Millero, D. Purkerson, C. L. Sabine, R. G. Schotle, D. W. R. Wallace, R. J. Wilke, and C. D. Winn. 1998b. Coulometric total carbon dioxide analysis for marine studies: Assessment of the quality of total inorganic carbon measurements made during the U.S. Indian Ocean CO2 Survey 1994-1996. Marine Chemistry 63:21-37. Johnson, K. M., M. Haines, R. M. Key, C. Neill, B. Tilbrook, R. Wilke, and D.W.R. Wallace. 2001. Carbon Dioxide, Hydrographic, and Chemical Data Obtained During the R/V Knorr Cruises 138-3, -4, and -5 in the South Pacific Ocean (WOCE Sections P6E, P6C, and P6W, May 2 - July 30, 1992). ORNL/CDIAC-132, NDP-077. Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, Oak Ridge, Tenn. 53 pp. Knapp, G. P., M. C. Stalcup, and R. J. Stanley. 1990. Automated Oxygen and Salinity Determination. Woods Hole Oceanographic Institution Technical Report No. WHOI-90-35. Woods Hole Oceanographic Institution, Woods Hole, Mass., U.S.A. Marinenko, G. and J. K. Taylor. 1968. Electrochemical equivalents of benzoic and oxalic acid. Analytical Chemistry 40:1645-51. Millard, R. C. and K. Yang. 1993. CTD Calibration and Processing Methods Used at Woods Hole Oceanographic Institution. Woods Hole Oceanographic Institution Technical Report. WHOI 93-44. Woods Hole Oceanographic Institution, Woods Hole, Mass., U.S.A. Millero, F. J., and A. Poisson. 1981. International one-atmosphere equation of state for seawater. Deep-Sea Research 28:625-29. Millero, F. J., J. Z. Zhang, S. Fiol, S. Sotolongo, R. Roy, K. Lee, and S. Mane. 1993a. The use of buffers to measure the pH of seawater. Marine Chemistry 44:143-152. Millero, F. J., J. Z. Zhang, K. Lee, and D. M. Campbell. 1993b. Titration alkalinity of seawater. Marine Chemistry 44:153-156. Millero, F. J., F. Huang, M. Galanter, J. Goen, C. Sabine, C. Thomas, and R. Rotter. 1999. The Total Alkalinity of North Atlantic Waters. University of Miami Technical Report, No. RSMAS-99-002. University of Miami, Miami, Florida. Roemmich, D., and C. Wunsch. 1985. Two transatlantic sections: Meridional circulation and heat flux in the subtropical North Atlantic Ocean. Deep- Sea Research 32:619-64. Schlitzer, R. 2001. Ocean Data View. http://www.awi-bremerhaven.de/GEO/ODV. Online publication. Alfred-Wegener-Institute for Polar and Marine Research. Bremerhaven, Germany. Strickland, J. D. H. and T. R. Parsons. 1972. The Practical Handbook of Seawater Analysis. Bulletin 167, Fisheries Research Board of Canada, 310 pp. Takahashi, T., D. W. Chipman, S. Rubin, J. Goddard, and S. C. Sutherland. 1998. Measurements of the Total CO2 Concentration and Partial Pressure of CO2 in Seawater during WOCE Expeditions P-16, P-17 and P-19 in the South Pacific Ocean, October, 1992 - April, 1993. Final Technical Report of Grant No. DE-FGO2-93ER61539 to U. S. Department of Energy, Lamont-Doherty Earth Observatory, Palisades, N.Y. 10964, pp. 124. Taylor, J. K. and S. W. Smith. 1959. Precise coulometric titration of acids and bases. Journal of Research of the National Bureau of Standards 63A:153-9. UNESCO (United Nations Educational, Scientific, and Cultural Organization). 1981. Background papers and supporting data on the practical salinity scale, 1978. UNESCO Technical Papers in Marine Science 37:144. Wallace, D. W. R. 2002. Storage and transport of excess CO2 in the oceans: The JGOFS/WOCE Gglobal CO2 survey. In J. Church, G. Siedler, and J. Gould (eds.). Ocean Circulation and Climate, Academic Press, 489-521. Wilke, R. J., D. W. R. Wallace, and K. M. Johnson. 1993. A water-based, gravimetric method for the determination of gas sample loop volume. Analiytical Chemistry 65:2403-2406 Youden, W. J. 1951. Statistical Methods for Chemists. Wiley, New York. ___________________________________________________________________________________________________________ ___________________________________________________________________________________________________________ APPENDIX A WOCE97-A24: CTD TEMPERATURE AND CONDUCTIVITY CORRECTIONS SUMMARY PRT Response Time used for all casts: 0.34 secs ITS-90 Temperature Coefficients Conductivity Coefficients Sta/ corT = t2*T**2 + t1*T + t0 corC = cp2*corP**2 + cp1*corP + c2*C**2 + c1*C + c0 Cast t2 t1 t0 cp2 cp1 c2 c1 c0 001/01 1.2241e-05 -7.5330e-04 -1.5033 0.00000e+00 0.00000e+00 0.00000e+00 -3.74944e-03 0.09374 002/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03246 003/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03350 004/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03398 005/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03393 006/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03495 007/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03454 008/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03381 009/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03426 010/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03409 011/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03534 012/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03542 013/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03552 014/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03613 015/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03570 016/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03531 017/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03564 018/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03558 019/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03547 020/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03619 021/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03677 022/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03638 023/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03634 024/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03698 025/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03716 026/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03785 027/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03693 028/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03707 029/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03691 030/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03714 031/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03736 032/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03726 033/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03785 034/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03829 035/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03694 036/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03794 037/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03734 038/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03805 039/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03811 040/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03819 ITS-90 Temperature Coefficients Conductivity Coefficients Sta/ corT = t2*T**2 + t1*T + t0 corC = cp2*corP**2 + cp1*corP + c2*C**2 + c1*C + c0 Cast t2 t1 t0 cp2 cp1 c2 c1 c0 041/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03809 042/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03900 043/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04006 044/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03933 045/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03992 046/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03974 047/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03902 048/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03975 049/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03847 050/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04019 051/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03999 052/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04016 053/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03875 054/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03911 055/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04046 056/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03975 057/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04061 058/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03984 059/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03995 060/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04087 061/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04034 062/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04061 063/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04042 064/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03841 065/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03977 066/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03971 067/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03935 068/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03997 069/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04048 070/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03903 071/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04090 072/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04110 073/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04050 074/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04004 075/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04144 076/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03950 077/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04104 078/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04151 079/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04096 080/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04193 ITS-90 Temperature Coefficients Conductivity Coefficients Sta/ corT = t2*T**2 + t1*T + t0 corC = cp2*corP**2 + cp1*corP + c2*C**2 + c1*C + c0 Cast t2 t1 t0 cp2 cp1 c2 c1 c0 081/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04070 082/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04040 083/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04025 084/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04090 085/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04025 086/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04049 087/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03971 088/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03990 089/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03934 090/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04007 091/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04039 092/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04100 093/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04146 094/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04187 095/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04197 096/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04209 097/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04146 098/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04079 099/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04060 100/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03966 101/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04027 102/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03936 103/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03857 104/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03918 105/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03871 106/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03992 107/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03938 108/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03872 109/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03922 110/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03903 111/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04009 112/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03918 113/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03814 114/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03874 115/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03901 116/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03797 117/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03837 118/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03879 119/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03859 120/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04025 ITS-90 Temperature Coefficients Conductivity Coefficients Sta/ corT = t2*T**2 + t1*T + t0 corC = cp2*corP**2 + cp1*corP + c2*C**2 + c1*C + c0 Cast t2 t1 t0 cp2 cp1 c2 c1 c0 121/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03937 122/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03872 123/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03836 124/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03916 125/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03978 126/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03979 127/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04023 128/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.03985 129/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04156 130/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04107 131/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04132 132/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04115 133/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04072 134/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04123 135/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04130 136/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04162 137/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04227 138/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04041 139/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04121 140/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04196 141/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04179 142/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04180 143/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04120 144/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04098 145/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04038 146/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04059 147/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04237 148/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04111 149/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04157 150/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04163 151/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04213 152/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04280 153/01 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04221 153/02 1.6032e-05 -3.6366e-04 -1.4962 -9.13543e-11 1.80848e-07 1.47071e-05 -1.76569e-03 0.04220 APPENDIX B SUMMARY OF WOCE97-A24 CTD OXYGEN TIME CONSTANTS (time constants in seconds) | Temperature | Pressure | O2 Gradient Station | Fast(TauTf) | Slow(TauTs) | (Taup) | (Tauog) -----------+-------------+-------------+----------+------------ 061 | 10.0 | 400.0 | 16.0 | 16.0 All Others | 32.0 | 515.0 | 6.0 | 16.0 Note: used station 61 shipboard corrections as better fit for very shallow cast. WOCE97-A24: Conversion Equation Coefficients for CTD Oxygen (refer to Equation 8.4.0) Sta/ OcSlope Offset Plcoeff Tfcoeff Tscoeff dOc/dtcoeff Cast (c1) (c2) (c3) (c4) (c5) (c6) ------ ----------- ------------ ------------ ------------ ------------ ------------ 001/01 1.59155e-04 1.80606e-01 -1.67936e-05 -2.42667e-02 -1.05835e-03 -2.04542e-04 002/01 3.29530e-04 -1.69661e-01 1.06956e-05 -3.94112e-03 -5.56021e-02 -5.59454e-04 003/01 2.20195e-04 2.67266e-01 -8.59507e-06 2.27063e-02 -6.71860e-02 -1.14262e-04 004/01 2.08158e-04 4.58399e-02 9.28639e-05 -1.09227e-02 -3.01051e-02 -6.54384e-04 005/01 2.03459e-04 1.25688e-01 6.74639e-05 -1.17646e-03 -3.93739e-02 -3.67590e-04 006/01 2.03284e-04 9.99630e-02 7.91762e-05 1.98649e-03 -4.11089e-02 -4.26553e-04 007/01 1.99903e-04 3.86616e-02 1.11502e-04 -2.43107e-03 -3.41172e-02 -6.34835e-04 008/01 1.96544e-04 2.41953e-02 1.21763e-04 4.07521e-03 -3.71913e-02 -1.62776e-04 009/01 2.15291e-04 -5.36765e-02 1.40467e-04 2.21202e-03 -3.85272e-02 -1.81221e-04 010/01 2.09784e-04 3.41741e-02 1.02138e-04 -3.54145e-03 -3.65743e-02 -3.96415e-04 011/01 2.22733e-04 -8.70568e-03 1.07363e-04 1.37323e-02 -5.09050e-02 -2.43484e-04 012/01 2.10327e-04 -6.71762e-02 1.44093e-04 -4.03790e-03 -3.26629e-02 -2.73662e-04 013/01 2.35427e-04 1.54534e-01 1.14679e-05 1.00860e-02 -6.24270e-02 -6.75866e-04 014/01 2.20314e-04 1.07755e-01 4.26790e-05 1.54560e-03 -4.91234e-02 -5.99597e-04 015/01 2.15297e-04 1.26329e-02 9.02960e-05 1.27057e-02 -5.16387e-02 -1.12151e-04 016/01 1.84136e-04 9.49351e-02 8.66736e-05 -7.04758e-03 -3.23125e-02 -4.95509e-04 017/01 1.89372e-04 -4.13260e-02 1.42300e-04 -2.24965e-03 -3.12172e-02 -9.46711e-04 018/01 1.73978e-04 -2.15571e-03 1.39843e-04 -1.17417e-02 -2.26272e-02 7.38213e-07 019/01 1.62492e-04 1.08743e-01 9.42972e-05 -1.19787e-02 -2.53778e-02 -2.46025e-06 020/01 1.74190e-04 1.83679e-02 1.17258e-04 -7.37559e-04 -3.51708e-02 1.39682e-06 021/01 1.70363e-04 -3.33210e-02 1.46005e-04 3.67402e-03 -3.64047e-02 -2.15345e-04 022/01 1.67833e-04 8.20616e-03 1.27974e-04 -5.82974e-03 -3.13278e-02 7.37800e-08 023/01 1.69521e-04 2.52103e-02 1.16119e-04 -1.22881e-02 -2.90536e-02 2.61161e-07 024/01 1.67831e-04 -1.59422e-02 1.35863e-04 -1.43772e-02 -2.31590e-02 -1.15078e-06 025/01 9.74036e-04 2.74161e-02 1.38260e-04 1.13660e-02 -3.74159e-02 1.35937e-04 026/01 1.57765e-04 -1.96677e-03 1.38479e-04 -1.43833e-02 -2.08002e-02 -2.74488e-04 027/01 1.56240e-04 6.41501e-02 1.08874e-04 -6.80935e-03 -3.09823e-02 -3.38017e-04 028/01 1.56613e-04 6.57770e-02 1.07595e-04 -1.28844e-02 -2.47557e-02 -1.70818e-04 029/01 1.54641e-04 -3.41163e-02 1.61835e-04 -1.40613e-02 -1.86196e-02 -7.93446e-04 030/01 1.57645e-04 6.78776e-02 1.02978e-04 -1.60396e-02 -2.24801e-02 -3.64876e-04 Sta/ OcSlope Offset Plcoeff Tfcoeff Tscoeff dOc/dtcoeff Cast (c1) (c2) (c3) (c4) (c5) (c6) ------ ----------- ------------ ------------ ------------ ------------ ------------ 031/01 1.80078e-04 1.43807e-01 3.31975e-05 -1.54686e-02 -3.48746e-02 -3.79686e-04 032/01 2.62701e-04 -1.39345e-01 1.26039e-04 3.96602e-02 -1.02436e-01 -5.00108e-04 033/01 8.53791e-05 5.02634e-02 2.72122e-04 -4.76358e-03 8.91434e-03 -6.56397e-05 034/01 6.32460e-05 2.53628e-01 3.17185e-04 3.19715e-02 -2.44634e-02 -2.38888e-05 035/01 5.13115e-05 8.11760e-01 -8.77855e-05 1.68051e-02 -3.86008e-02 -2.41569e-05 036/01 5.32958e-05 1.06826e-01 1.99469e-04 -5.10487e-02 8.01151e-02 2.39381e-04 037/01 1.47180e-04 -1.11558e-01 1.93362e-04 -3.30723e-02 4.26096e-03 -4.77214e-04 038/01 1.78402e-04 -1.24014e-02 8.22548e-05 -1.21045e-02 -3.59573e-02 -3.22818e-04 039/01 1.73511e-04 4.02025e-02 7.37872e-05 -3.07540e-03 -4.37149e-02 -3.48811e-04 040/01 1.68455e-04 2.76831e-02 9.01043e-05 5.98810e-03 -4.80168e-02 -5.06492e-04 041/01 1.48302e-04 5.80631e-01 -8.09000e-05 -1.70292e-02 -4.98590e-02 3.73003e-05 042/01 1.81649e-04 1.33321e-01 2.47216e-05 -7.70114e-03 -4.89017e-02 1.82620e-07 043/01 1.84280e-04 -1.17431e-01 1.29382e-04 -1.47953e-04 -4.26872e-02 -6.14003e-04 044/01 2.22596e-04 2.39913e-01 -5.66631e-05 8.65999e-03 -8.09534e-02 -2.77091e-04 045/01 1.99890e-04 5.97511e-01 -1.19629e-04 1.53675e-02 -9.40520e-02 1.76438e-04 046/01 1.64375e-04 3.21820e-01 -8.95318e-06 4.01608e-03 -6.19019e-02 5.16775e-05 047/01 1.38712e-04 2.13737e-01 3.29168e-05 -1.09980e-02 -2.88248e-02 1.66050e-06 048/01 1.16646e-04 -1.55556e-01 3.06793e-04 -4.93577e-02 4.06853e-02 1.55321e-06 049/01 6.51004e-05 5.38463e-01 3.64842e-04 2.65331e-02 -4.62661e-02 -2.45320e-08 050/01 1.46803e-05 5.79445e-01 8.78170e-05 4.76692e-02 -1.86353e-02 3.20479e-05 051/01 2.21550e-04 -2.22787e-01 1.10075e-04 -2.91259e-02 -3.17552e-02 -2.69001e-04 052/01 1.57911e-04 2.31671e-01 2.76457e-05 3.74426e-03 -5.24188e-02 -1.97205e-06 053/01 1.90199e-04 1.75495e-01 -6.83434e-07 -1.69616e-02 -4.47097e-02 -4.31444e-05 054/01 1.53884e-04 2.49577e-01 1.94185e-05 -6.65853e-03 -4.20702e-02 2.18828e-06 055/01 1.47946e-04 2.66047e-01 3.09519e-05 3.94468e-03 -5.01139e-02 -3.03193e-06 056/01 2.00052e-04 1.70718e-01 -3.34300e-05 -2.16987e-02 -4.63603e-02 -5.84131e-04 057/01 1.40257e-04 -9.24808e-02 2.22813e-04 -7.96132e-03 -1.76007e-02 1.83640e-05 058/01 3.62386e-04 3.91253e-01 -9.58735e-05 2.79407e-02 -1.49356e-01 -4.02783e-04 059/01 3.18965e-04 1.77058e+00 -2.65215e-04 3.88343e-02 -1.77461e-01 -1.47914e-04 060/01 4.75255e-06 4.67242e-01 1.35183e-04 2.99944e-02 3.18173e-02 5.25432e-07 061/01 1.17016e-05 3.68093e-01 7.83863e-05 7.42281e-02 6.24189e-04 -3.19465e-06 062/01 -2.11599e-05 9.10071e-01 -3.08415e-04 1.02234e-01 -6.04671e-02 -9.69222e-07 063/01 3.05587e-04 6.13982e+00 -4.56691e-04 1.78191e-02 -2.25350e-01 4.93646e-06 064/01 9.44448e-05 -4.21474e-04 1.78401e-04 -3.35232e-02 4.15171e-02 -3.55106e-04 065/01 2.55248e-04 2.22077e-01 -2.46706e-05 7.30396e-03 -1.00220e-01 -3.47292e-04 066/01 5.78257e-05 1.74586e-01 2.09361e-04 5.03461e-02 -1.87118e-02 -3.07015e-04 067/01 1.35920e-04 -5.80805e-02 2.29970e-04 -1.08813e-03 -2.30935e-02 -3.17104e-04 068/01 1.65333e-04 2.09512e-01 2.83571e-05 4.00289e-03 -5.82649e-02 -1.94853e-05 069/01 1.62541e-04 7.82076e-02 7.92763e-05 5.65559e-03 -5.01923e-02 -1.99766e-04 070/01 1.54127e-04 2.33048e-02 1.22218e-04 -1.48401e-02 -2.42903e-02 -1.70699e-05 Sta/ OcSlope Offset Plcoeff Tfcoeff Tscoeff dOc/dtcoeff Cast (c1) (c2) (c3) (c4) (c5) (c6) ------ ----------- ------------ ------------ ------------ ------------ ------------ 071/01 1.55263e-04 7.45321e-02 8.48367e-05 -1.54318e-02 -2.47681e-02 -1.95415e-04 072/01 1.52123e-04 1.26169e-01 7.52181e-05 9.65746e-03 -4.85348e-02 1.06806e-05 073/01 1.64175e-04 3.48164e-02 1.07172e-04 -1.60265e-02 -3.54140e-02 6.89268e-04 074/01 1.58162e-04 1.01610e-01 8.62109e-05 -1.56577e-02 -3.66920e-02 -1.29237e-04 075/01 1.68999e-04 8.84703e-02 6.46341e-05 -2.35657e-03 -5.01491e-02 1.44827e-05 076/01 1.79874e-04 1.72598e-01 1.64208e-05 3.69450e-03 -6.52063e-02 -3.19630e-04 077/01 1.29119e-04 3.08484e-02 1.75418e-04 -1.15002e-02 -1.24011e-02 7.04111e-06 078/01 1.13134e-04 -6.55551e-02 2.95307e-04 -2.14336e-02 1.96644e-02 -4.37889e-05 079/01 4.58113e-05 2.70100e-01 1.80287e-04 -4.36710e-03 4.28503e-02 6.69965e-04 080/01 7.57419e-05 1.08042e-01 2.62841e-04 -1.97040e-02 3.92492e-02 -7.86440e-05 081/01 3.27396e-05 9.15137e-01 -5.30475e-05 1.10495e-01 -1.21634e-01 9.35778e-04 082/01 1.38660e-04 1.97146e-01 8.11011e-05 -1.90118e-02 -3.27376e-02 5.05819e-06 083/01 1.48679e-04 1.27713e-01 7.88931e-05 1.69040e-02 -5.91502e-02 1.65829e-04 084/01 1.96761e-04 -1.96238e-01 1.32466e-04 7.59467e-02 -1.09398e-01 -9.54481e-04 085/01 1.62806e-04 -1.72652e-02 1.21975e-04 6.72395e-03 -4.87194e-02 -9.51015e-04 086/01 1.72915e-04 -6.16161e-02 1.33338e-04 3.09092e-03 -5.55399e-02 -1.26539e-03 087/01 1.56336e-04 1.85493e-01 8.25054e-05 1.38158e-03 -7.60130e-02 8.99418e-05 088/01 1.58864e-04 1.40157e-01 7.76994e-05 -3.02280e-03 -5.80744e-02 1.84770e-04 089/01 1.20414e-04 2.58597e-01 8.06108e-05 7.62351e-03 -4.33346e-02 -3.19876e-05 090/01 2.00251e-04 3.67408e-01 -6.61006e-05 1.41834e-02 -1.17829e-01 -2.08241e-03 091/01 1.43998e-04 1.94743e-01 5.24192e-05 -2.45385e-02 -2.89370e-02 -6.62329e-06 092/01 1.61620e-04 9.76973e-01 -1.91280e-04 -1.79680e-03 -1.17447e-01 2.98634e-05 093/01 -1.65003e-04 3.91744e+00 -2.48761e-04 2.21957e-01 -3.39978e-01 -3.57263e-06 094/01 1.08367e-04 1.69701e-01 4.16802e-04 1.02182e-02 -6.67263e-02 1.81922e-05 095/01 7.51653e-05 3.67382e-01 1.98314e-05 -5.29865e-03 2.66220e-02 8.79974e-06 096/01 1.24127e-04 -1.93243e-01 2.23659e-04 7.88128e-03 6.54977e-02 1.09028e-06 097/01 5.47117e-05 5.58920e-01 2.93238e-04 -1.09596e-03 -5.03112e-02 9.70853e-05 098/01 3.12625e-05 8.53141e-01 -3.34854e-04 3.84201e-02 -5.98532e-02 -1.56960e-06 099/01 3.37798e-05 3.46385e-01 -9.00466e-05 3.21554e-02 7.81963e-02 -3.68971e-06 100/01 4.26540e-05 8.66048e-01 -1.15063e-05 4.42543e-02 -8.38593e-02 -6.46673e-07 101/01 9.07370e-05 3.33641e-01 9.67244e-05 1.08855e-02 -2.71796e-02 -3.23032e-04 102/01 1.84932e-04 1.15484e-03 9.66055e-05 -3.20852e-02 -4.74004e-02 -8.84131e-04 103/01 1.56815e-04 1.47773e-01 9.24281e-05 1.00206e-02 -7.79217e-02 -3.74967e-04 104/01 1.23664e-04 2.98271e-01 7.13968e-05 1.78710e-03 -5.32447e-02 1.77077e-04 105/01 1.28922e-04 2.60560e-01 8.13513e-05 5.77435e-04 -5.69865e-02 2.73079e-06 106/01 1.42386e-04 1.10183e-01 1.12841e-04 -2.10571e-02 -2.71002e-02 -5.97384e-04 107/01 1.32868e-04 1.54122e-01 1.06468e-04 5.98032e-03 -4.10264e-02 -2.72775e-04 108/01 1.34774e-04 1.80867e-01 9.61094e-05 8.09162e-03 -4.99175e-02 -5.56872e-06 109/01 1.42966e-04 1.77125e-01 9.63899e-05 -2.35271e-02 -3.55805e-02 -1.44229e-04 110/01 1.45825e-04 1.19449e-01 1.02176e-04 -9.05651e-03 -3.75279e-02 6.51619e-07 Sta/ OcSlope Offset Plcoeff Tfcoeff Tscoeff dOc/dtcoeff Cast (c1) (c2) (c3) (c4) (c5) (c6) ------ ----------- ------------ ------------ ------------ ------------ ------------ 111/01 1.61166e-04 3.22019e-02 1.17763e-04 -1.16368e-02 -3.75473e-02 -1.09855e-06 112/01 1.46859e-04 1.92283e-01 6.97896e-05 1.02282e-03 -5.14137e-02 2.27189e-05 113/01 1.46172e-04 1.92891e-01 7.60365e-05 -4.92483e-03 -4.35036e-02 -7.33963e-07 114/01 1.42122e-04 1.53444e-01 9.24123e-05 -4.79629e-03 -3.40317e-02 -6.45711e-06 115/01 1.45679e-04 5.95846e-02 1.43276e-04 -1.94852e-02 -1.60951e-02 7.68975e-07 116/01 1.48160e-04 1.64595e-01 9.12673e-05 -9.60357e-03 -3.69956e-02 -7.10422e-04 117/01 1.66033e-04 -2.76941e-02 1.63852e-04 -2.67531e-02 -1.76373e-02 -1.92720e-04 118/01 1.68243e-04 4.37283e-02 1.18478e-04 -2.01420e-02 -2.90367e-02 -7.80007e-07 119/01 1.32027e-04 2.32281e-01 8.25727e-05 -1.56361e-03 -3.44465e-02 5.64620e-06 120/01 1.24547e-04 2.70178e-01 7.46909e-05 7.03492e-03 -3.91348e-02 -5.67454e-04 121/01 1.54770e-04 1.42463e-01 9.35302e-05 -6.01811e-03 -3.69751e-02 1.91892e-06 122/01 1.57475e-04 1.89691e-01 8.13860e-05 -1.42671e-03 -4.65195e-02 -4.70624e-07 123/01 8.93644e-05 5.79771e-01 2.11988e-05 1.45019e-02 -4.53449e-02 3.18052e-04 124/01 1.21482e-04 4.36304e-01 3.26018e-05 2.32352e-02 -5.36848e-02 -3.28635e-06 125/01 1.47437e-04 3.32449e-01 5.40093e-05 7.30531e-03 -4.91376e-02 3.54980e-06 126/01 2.01320e-04 6.17173e-02 9.08394e-05 2.07185e-03 -4.55805e-02 2.69658e-06 127/01 1.82328e-04 1.05672e-01 8.35850e-05 -2.64706e-03 -3.82617e-02 -2.80159e-04 128/01 1.98000e-04 1.25553e-01 6.65753e-05 -3.84737e-03 -4.88685e-02 1.20005e-05 129/01 1.72876e-04 1.36979e-01 7.86024e-05 -8.53686e-03 -3.66286e-02 -1.60125e-04 130/01 1.67146e-04 8.16034e-02 9.74321e-05 -3.80420e-04 -3.66838e-02 -2.07910e-04 131/01 1.52707e-04 1.59369e-01 8.09513e-05 -1.55165e-03 -3.50838e-02 -8.11806e-07 132/01 1.66998e-04 1.17860e-01 7.96167e-05 -4.29171e-03 -3.69767e-02 8.47650e-07 133/01 1.73625e-04 3.55268e-02 1.03040e-04 -8.85905e-03 -3.16113e-02 1.33115e-06 134/01 1.48204e-04 2.52858e-01 4.86067e-05 1.72511e-03 -3.81002e-02 -6.53886e-06 135/01 1.92096e-04 -2.74505e-02 1.27536e-04 -1.09422e-02 -2.95040e-02 -1.78041e-04 136/01 1.94472e-04 4.13933e-03 1.12769e-04 -7.62069e-03 -3.14675e-02 1.43475e-07 137/01 2.17106e-04 -3.01978e-02 1.12942e-04 -4.50373e-03 -4.02500e-02 4.96301e-06 138/01 2.22311e-04 -5.00321e-02 9.76468e-05 -1.58724e-02 -3.02823e-02 -4.36295e-06 139/01 1.52422e-04 2.02737e-02 1.97108e-04 -1.97796e-02 -1.13464e-02 1.36054e-04 140/01 1.46617e-04 -3.19478e-03 2.16811e-04 -2.17866e-02 -5.33996e-03 1.31272e-05 141/01 2.37081e-04 1.55902e-01 -3.40032e-05 1.13998e-02 -6.07683e-02 -6.54744e-07 142/01 1.98213e-04 -4.97505e-02 1.08182e-04 -8.69091e-03 -2.86842e-02 -1.41580e-06 143/01 2.17161e-04 -3.33819e-02 6.98944e-05 -1.13934e-02 -3.28713e-02 -5.48273e-04 144/01 2.33652e-04 2.05512e-04 4.31696e-05 -3.03195e-03 -4.66079e-02 -9.74762e-05 145/01 2.09580e-04 7.65830e-02 4.24723e-05 -3.11430e-03 -4.12493e-02 -1.52486e-04 146/01 2.17548e-04 7.38263e-02 5.38163e-05 3.85039e-03 -4.89278e-02 -1.12781e-06 147/01 1.77841e-04 -1.04150e-01 1.99303e-04 -4.48221e-02 4.56913e-03 -2.28104e-04 148/01 2.00754e-04 1.39430e-01 2.36437e-05 6.89890e-03 -4.75024e-02 -1.89062e-04 149/01 2.35974e-04 1.21863e-02 2.76438e-05 -1.12256e-03 -4.67145e-02 -3.54931e-04 150/01 1.97150e-04 6.36631e-02 6.66619e-05 -8.44385e-03 -3.31962e-02 9.23139e-07 151/01 4.53928e-04 1.72824e-01 -2.87270e-04 -1.44757e-03 -8.07508e-02 -4.24021e-06 152/01 1.99191e-04 -5.74273e-02 9.76922e-05 -2.54269e-02 -1.61357e-02 -9.68688e-06 153/01 1.99191e-04 -5.74273e-02 9.76922e-05 -2.54269e-02 -1.61357e-02 -9.68688e-06 153/02 9.61249e-05 6.94877e-02 3.30551e-04 1.43364e-02 -1.59927e-02 4.32862e-06 APPENDIX C TABULATION OF WOCE97-A24 PROBLEM CTD CASTS Cast Problems Solutions ---------+--------------------------------------------------------+--------------------------------------------- <001/01- | Conductivity discontinuity at | Software changed to detect/fix, 022/01> | raw value 32767/32768 | first 22 casts re-averaged. 001/01 | CTD #3 temp offsets (water in turret). | Switch to CTD #5 for rest of cruise. 001/01 | Temperature drift on down cast. | Use upcast. 004/01 | 10.5-min. winch stop for maintenance at | Offset raw CTDO from stop to bottom. | 2374-2384db downcast, CTDO signal drifted/dropped. | Filtered near/after stop. 005/01 | -0.015 sigma theta drop 1134-1190db | No action, down+up CTD features in T/C/S/O2 005/01 | Acquisition crashed on upcast, restarted. | CTD time offset to match. 011/01 | Switched to SBE32 pylon. Bottles tripped | Fixed CTD trip info. | out-of-order after pylon reset. | 013/01 | CTDO spiking/drift near bottom. | Filtered. 014/01 | Installed SBE35 T sensor prior to cast. | 014/01 | Deck Unit blew fuse at 1836db upcast | Stopped for repairs at 1800db 015/01 | -0.022 sigma theta inversion top 10db | No action, S stable and T rising. 018/01 | -0.10 sigma theta drop 16-22db | No action, down+up CTD features in T/C/S/O2 019/01 | Deck Unit blew fuse at 1720db downcast, not | First + repeat downcasts spliced at 1668db | noticed until 2100+db. Power restored, returned from | where TC matched best and after CTDO had | 2486db to 1514db, then continued down (30 mins. | time to adjust after reversing direction. | time elapsed). Fuse blew again at 4740db upcast. | 019/01 | CTDO spiking/drift near bottom. | Filtered. 020/01 | -0.025 sigma theta drop 1020-1044db | No action, down+up CTD features in T/C/S/O2 020/01 | -0.03 sigma theta inversion 1262-1402db | No action, down+up CTD features in T/C/S/O2 025/01 | CTDO sensor cover left on. | CTDO signal useless, not reported. 027/01 | SBE32 pylon triggered time spikes in CTD | Time source changed in software. | signal and false-confirms at multiple trips. | 028/01 | CTDO spike near 3100db downcast. | Filtered. 038/01 | -0.87PSU Salinity spike 20-28db. | Filtered. | Small-scale salinity spiking throughout cast. | 040/01 | -0.39PSU Salinity spike at 74-78db downcast. | Filtered. 040/01 | Cast touched bottom, cond. spiking. | Press-sequencing cut off just above spikes. 053/01 | CTDO spiking/drift near bottom. | Filtered. 055/01 | -1.0PSU Salinity spike 6-11db downcast. | Filtered. 068/01 | CTDO signal very low at surface. | No action. Code bad. 069/01 | CTDO signal very low at surface. | No action. Code bad. 070/01 | CTDO signal very low at surface. | No action. Code bad. 071/01 | Cond. dropout 30-75m downcast, T+C problems | Use upcast. | top 300db: inversions do not look real. | 071/01 | Time spike/jump 446db upcast | Shift time back to improve CTDO fit. 071/01 | -.30PSU Salinity spike 4-6db upcast, just before trip. | Filtered. 072/01 | CTDO signal very low at surface. | Filtered to improve CTDO fit. 073/01 | CTDO signal very low at surface. | No action. Code bad. 074/01 | CTDO signal very low at surface. | No action. Code bad. 076/01 | CTDO signal very low at surface. | Filtered to improve CTDO fit. 076/01 | CTDO spiking/drift near bottom. | Filtered. 079/01 | CTDO signal very low at surface. | Filtered to improve CTDO fit. 081/01 | CTDO signal very low at surface. | Filtered to improve CTDO fit. Cast Problems Solutions ---------+--------------------------------------------------------+--------------------------------------------- 082/01 | CTDO signal very low at surface. | Filtered to improve CTDO fit. 082/01 | -0.08PSU Salinity spike 1000-1002db downcast. | Filtered. 083/01 | CTDO signal low, top 40-50db. | Filtered to improve CTDO fit. 083/01 | Time spike/jump 24db downcast | Shift time back to improve CTDO fit. 086/01 | CTDO signal very low at surface. | No action. Code bad. 086/01 | Salinity spiking on upcast at | Filtered. | 4 deepest rosette trips. | 088/01 | Transmissometer signal intermittent. | Washed prior to cast 089/01 | Discovered W. Gardner's transmissometer log. | Switched to instrument #266AD (from #265AD). 089/01 | CTDO signal very low top 12db. | Filtered to improve CTDO fit. 090/01 | CTDO signal very low top 140db. | No action. Code bad. 090/01 | Salinity spiking on upcast at rosette trips. | Filtered. 095/01 | CTDO signal very low at surface. | Filtered to improve CTDO fit. 096/01 | CTDO spiking/drift near bottom. | Filtered. 097/01 | -0.02 sigma theta inversion at 6db | No action, down+up CTD features in T/C/S/O2 097/01 | +0.02 sigma theta rise 128-156db | No action, down+up CTD features in T/C/S/O2 109/01 | CTDO signal very low at surface. | No action. Code bad. 111/01 | CTDO spiking/drift near bottom. | Filtered. 118/01 | CTDO spiking/drift near bottom. | Filtered. 123/01 | CTDO spiking/drift near bottom. | Filtered. <124/01- | Intermittent cond offsetting on upcasts. | Shift calibration as needed. 152/01> | | 128/01 | CTDO signal very low at surface. | Filtered to improve CTDO fit. 132/01 | -0.38PSU Salinity spike 567-570db downcast. | Filtered. 133/01 | -0.01 sigma theta drop 18-20db | No action, down+up CTD features in T/C/S/O2 141/01 | CTDO signal very low at surface. | Filtered to improve CTDO fit. 145/01 | CTDO signal very low at surface. | Filtered to improve CTDO fit. 147/01 | CTDO signal very low at surface. | No action. Code bad. 147/01 | -0.08PSU Salinity spike 608-610db downcast. | Filtered. 153/01 | Special cast for LADCP bottom tracking test, | | minimal sampling: only 4 btls | 153/01 | No bottle data for CTDO fit | Used sta.152 corrections for | | fit closest to cast 2 CTD/bottles. APPENDIX D BOTTLE QUALITY COMMENTS All data comments per PI's request from WOCE A24 ACCE. Investigation of data may include comparison of bottle salinity and oxygen data with CTD data, review of data plots of the station profile and adjoining stations, and rereading of charts (i.e., nutrients). Comments from the Sample Logs and the results of ODF's investigations are included in this report. Units stated in these comments are degrees Celsius for temperature, Practical Salinity Units for salinity, and unless otherwise noted, milliliters per liter for oxygen and micromoles per liter for Silicate, Nitrate, and Phos- phate. The first number before the comment is the cast number (CASTNO) times 100 plus the bottle number (BTLNBR). STATION 001 Cast 1 Salinity samples are all from rerunning the samples. An error was made in transferring the data. No printouts were made of the data before the transfer. NO3 appeared low, shallow, when plotted vs. pressure. Bottom NO3 appeared high, O2 high compared with adjoining stations. No analyti- cal problem found. N:P ratio acceptable. 107 Salinity is low compared to CTD. No analytical problem found. Salinity is acceptable. 106 Sample Log: "Leak from bottom end cap." Oxygen as well as other samples are acceptable. Salinity was lost, see Cast 1 salinity comment. 104 Salinity was lost, see Cast 1 salinity comment. Pressure is 808db. 103 Sample Log: "Bottom endcap leak when vent cracked." Oxygen is high. Other samples appear to be acceptable. Footnote O2 bad. Pressure is 908db. 102 Salinity is high compared to CTD. No analytical problem found. Salinity is acceptable. 101 Salinity is high compared to CTD. No analytical problem found. Salinity is acceptable. STATION 002 Cast 1 Console Ops: "Changed to CTD 5, because of prim temp offset on sta 001." Salinity file was lost during computer trans- fer. Fortunately, a duplicate set of salinity samples were drawn and eventually run. The data that is reported is the second drawn samples. 124 Oxygen: "Flask 1453 may have a calibration problem." Oxygen data is acceptable. 114 Salinity is high, nutrients are low, oxygen appears to be okay. Footnote bottle leaking, samples bad. 107 Oxygen: "Flask 1408 may have a calibration problem." Oxygen is acceptable. 103 Sample Log: "Bottom cap leaking." Oxygen is low. Other data are acceptable. Footnote bottle leaking and oxygen bad. STATION 003 124-125 Sample Log: "Not closed, pylon is advanced 2 places as it should be." So the first attempt at tripping bottle 14 did not work. These bottles were not suppose to be closed. Com- ments on Sample Log confirm suspicion of proper bottle clo- sure. Cast 1 Sample Log: "Tripping problem." Console Ops: "No confirm, 1 push on 14, 2 No confirms." One level was missed (600 desired depth), but that was because of an operator error. Console operator did not realize the No confirm message and had the winch operator come up to next tripping depth. Data are correct as pressure assigned. 123 Sample Log: "Vent not closed." Oxygen as well as other sam- ples are acceptable. 121-123 Footnote CTDO questionable 0-90db. 116 PO4 appears 0.04 high. Nutrient analyst could not find any analytical problems. PO4 is acceptable. 114-123 Bottles did not trip as scheduled. Data appear acceptable as trip levels reassigned. See Cast 1 comments. 112 Salinity indicates a large ∆S with CTD. Gradient area, salinity appears to be okay. No analytical problem found. 108 Sample Log: "Vent not closed." O2 is high. Other samples are acceptable. Footnote bottle leaking, oxygen bad. 105 Oxygen is low compared to adjoining stations and CTDO. No analytical problems noted. Feature is not seen in other parameters. Footnote oxygen questionable. 103 Sample Log: "Bottom seal leaks." Salinity is ~0.020 low. Footnote salinity bad. Oxygen as well as other samples are acceptable. 101-102 Sample Log: "May have bubbled nitrogen through the valve." Oxygen as well as other samples are acceptable. STATION 004 123 Sample Log: "Vent was open." Oxygen as well as other sam- ples are acceptable. 120 O2 is high, nutrients are low. Salinity agrees with the CTD. Data are acceptable. O2 does not agree with adjoining sta- tions. Footnote o2 bad. 114 Oxygen minimum, but nutrients are also low. Nutrient Ana- lyst: "No analytical problems found." 111 ∆S at 1122db is -0.0062. No analytical problems noted. Salinity is acceptable. 108 Sample Log: "Leaker." O2 appears to be acceptable. ∆S at 1536db is 0.006. Salinity is high. No analytical prob- lems noted. Footnote salinity bad. 105 Salinity is ~0.006 high. No analytical problems found. Footnote salinity bad per PI review notes. 103 Sample Log: "New bottle." O2 as well as other samples are acceptable. STATION 005 111 Salinity large delta with CTD. Gradient area. Other samples are acceptable. Density inversion with this salinity, therefore salinity probably not real. Footnote salinity bad. 106 Salinity high compared with CTD. Autosal diagnostics indi- cate 4 tries to get a good reading. Gradient area, salinity minimum. Variation in CTD trace. Salinity is acceptable. 103 Sample Log: "Vent left open." O2 as well as other data are acceptable. STATION 006 128 Sample Log: "Not closed." Okay, not suppose to be. Cast 1 Console Ops: "Duplicate No Confirm on 11, No confirm, retrip on 22." One level was missed (1500 desired depth). Data are correct as pressure assigned. 125-126 Footnote CTDO questionable 52-110db. 124 Oxygen is high and nutrients low, salinity is acceptable when compared to adjoining stations. N:P ratio is good. Data are acceptable. 113 Salinity is low, oxygen and nutrients high. N:P ratio is good. Data are acceptable. 111-127 See Cast 1 comments. Footnote bottle did not trip as sched- uled. Data are acceptable as pressure for trip levels assigned. 109 Sample Log: "Salt bottle thimbles don't fit." Salinity is acceptable. 104 Oxygen: "Late start." Oxygen is acceptable. 103 Salinity bottle had a loose thimble. Salinity is a little low. Footnote salinity questionable, out of WOCE spec. 101 Sample Log: "Vent not closed." Oxygen as well as other data are acceptable. Autosal diagnostics indicate 4 tries before getting readings to agree. The first readings gave better results and are used in this salinity calculation. Salinity is acceptable. STATION 007 Cast 1 Console Ops: "2 No confirms, 1 push on 2, 2 No confirm 1 confirm on 12, 2 No confirm 1 confirm on 19, 2 No confirm 1 confirm on 20. One level was missed (3800 desired depth). Data appear acceptable as trip levels reassigned. 127 Footnote CTDO questionable 0-78db. 119 Sample Log: "Vent open." Oxygen as well as other data are acceptable. 117 PO4 ~0.06 high, so is SiO3 high. Nutrient analyst: "No ana- lytical problem found, peaks, calcs look okay, normal n:p." 111 SiO3 a little high. Nutrient analyst: "No analytical prob- lem found, peaks, calcs look okay." 110 SiO3 ~1.0 high. Nutrient analyst: "No analytical problem found, peaks, calcs look okay." 102-127 See Cast 1 comment. Footnote bottle did not trip as sched- uled. STATION 008 Cast 1 No comments on the Sample Log. Console ops: "2 No confirm, 1 confirm on 12, 2 No confirm, 1 confirm on 17. No levels were missed and bottles tripped on the confirm signal. 127-128 Footnote CTDO questionable 0-100db. 125 Nutrients low, O2 high, salinity agrees with adjoining sta- tions. Nutrient analyst: "N:P normal, no analytical problem found." 109-110 Oxygen appears low compared to adjoining stations, agrees with CTDO. Oxygen is acceptable. STATION 009 Cast 1 No comments on the Sample Log. Console Ops: "Retripped 5." No levels were missed and bottles tripped on the confirm signal. 126-128 Footnote CTDO questionable 0-110db. 116 O2 looks high, but is okay, agrees with CTDO. Salinity gra- dient area acceptable. NO3 maybe 0.4 high, PO4 0.04 high. Nutrient Analyst: "Peaks okay, calculation okay. No problem noted. This peak is higher than adjacent peaks. Could be real." 106 Autosal diagnostics had the sample run 6 times. This bottle gave analyst trouble last time it was used. This time it caused a problem with the data. Footnote salinity bad. Salinity bottle removed from box and replaced with a new bottle. 105 Oxygen is ~0.04 low. No analytical problems noted. Footnote oxygen questionable. 102-105 PO4 slightly low. Nutrient analyst: "No analytical problems found, N:P same as Sta 008." 101 SiO3 high. Nutrient analyst: "No analytical problems found." STATION 010 Cast 1 No comments on the Sample Log. 128 Sample Log indicates that no salinity was drawn, but there is a sample and it appears to be acceptable. 129 No salinity sample drawn, only TCO2. 126 Sample Log indicates that no salinity was drawn, but there is a sample and it appears to be acceptable. 125 Had trouble getting two reading to agree, but agrees fairly well for shallow value with the CTD. 124 Oxygen appears high, flask 1308. Data are acceptable. 116 Salinity low compared with CTD. No analytical problem found. Gradient area. Agrees fairly well with adjoining stations. 101 Salinity about 0.003 high. No analytical problem found. Footnote salinity bad. STATION 011 Cast 1 Console Ops: "SBE pylon changed into rosette trip 1: 3 false confirms, manually fired after resetting." No levels were missed and bottles tripped on the confirm signal. Bottles were tripped as console operator had expected. 126 Nutrients high, oxygen low. Data are acceptable. Salinity agrees with adjoining stations. 121 Nutrients were not drawn. This was an error in sampling, they should have been drawn. Footnote nutrients lost. 116 Nutrients were not drawn. This was an error in sampling, they should have been drawn. Footnote nutrients lost. 105 Sample Log: "Anomalous O2 draw temp." salt way high. Sus- pect bottle tripped on the way down between 300 and 400 db. Footnote bottle did not trip as scheduled, samples bad. 104 Bottle tripped at deepest level by request of console opera- tor through the pylon trip box. 101 O2 is a little low. SiO3 high. Nutrient analyst: "No ana- lytical problem found." STATION 012 120 Salinity is high compared with CTD. PI: "Okay." 116 Oxygen: "During titration, PC froze up, sample lost." 115-120 PO4 low, NO3 low in this range. Nutrient analyst: "Could be low, N:P a little high, but hard to tell. No analytical problem noted." 114 Salinity has a large difference with the CTD agrees with adjoining stations. Salinity is acceptable. 111 O2 high, nutrients low. Data is acceptable. 108 Sample Log: "Leaky vent." Oxygen as well as other data are acceptable. STATION 013 119 Sample log: "Vent not closed." Oxygen as well as other data are acceptable. 110 PO4 appears high. Nutrient analyst: "NO3 higher here, too. N:P looks about right. 107 Salinity does not agree with CTD. No analytical problem found. Oxygen appears slightly low. Gradient area. Other samples appear to be acceptable. 101 SiO3 low. Nutrient analyst: "No analytical problem found." STATION 014 Cast 1 Tripping problem. CTD tripping diagnostics indicated that bottle 5 did not trip, console operator then tried to fire the bottle but instead bottle 6 closed. Data are correct as pressure is assigned. 108 Sample log: "Leaking from vent." Oxygen as well as other samples are acceptable. 105 Console Ops: "Retripped, confirmed." Sample log: "Didn't close." Bottle did not close, but CTD data the same as bot- tle 6 is included to give users an additional flag that there was a slight problem, but it has been properly resolved. 102 Salinity ran 4 times, loose thimble. The first readings gave better results and are used in this salinity calcula- tion. Salinity is acceptable. STATION 015 Cast 1 Sample Log: " No surface sample." 132 Surface CTD data included for data users convenience. 130-131 Bottles did not trip as scheduled. They tripped one level shallower than planned. 128 Console Ops: "One no confirm, then confirm." Bottle tripped as scheduled. 129 Sample Log: "Didn't close." Only the CTD data is included. 110 Salinity is a little high compared with CTD. No analytical problems found. Different water from adjoining stations. 109 Salinity is a little high compared with CTD. No analytical problems found. Different water from adjoining stations. Oxygen high and nutrients low (NO3, SiO3, PO4) 108 Salinity is a little high compared with CTD. No analytical problems found. Different water from adjoining stations. Oxygen is low; could be Labrador Sea waters. 102-108 The oxygen appears lower than adjoining stations. However SiO3 seems to follow that same pattern. STATION 016 Cast 1 No comments on the Sample Log. Nutrient analyst double checked entire SiO3 profile. 128-131 Footnote CTDO questionable 0-230db. 126 Autosal diagnostics indicate 4 tries to get a good reading. Salinity is high compared with CTD. Variation is CTD trace, difference between the down and up. PI: "Salinity is acceptable." 123 Salinity is high compared with CTD. No analytical problem noted. Salinity is acceptable. 118 Salinity is low compared with CTD. No analytical problem noted. Salinity is acceptable. PI: "High gradient region." 114 Salinity is high compared with CTD. Autosal diagnostics indicate 4 tries to get a good reading, indicating a problem with the samples. Footnote salinity bad. 112 Oxygen may be low as compared to CTDO. No analytical reason noted for low oxygen. Feature does not show in other prop- erties or adjoining stations. PI: "This is okay, just the most extreme Labrador Sea water in the section." 111 Oxygen appears high. No analytical reason noted. Feature does not show in other properties or adjoining stations. Oxygen agrees with CTDO. Oxygen is acceptable. See 112 PI comment. 110 Salinity is high compared with CTD. No analytical problem noted. Gradient area. Salinity is acceptable. 101 Salinity is high compared with CTD. Autosal diagnostics indicate 4 tries to get a good reading, indicating a problem with the samples. Footnote salinity bad. STATION 017 131 Footnote CTDO questionable 0-60db. 120 Sample Log: "Lanyard hung, leaking." Salinity is high com- pared with CTD. No analytical problems found. Oxygen as well as other parameters appear to be acceptable. There is a large change in salinity between the down up, salinity may also be acceptable. 119 Sample Log: "O2 flask 1403 broke, replaced by 1515." 112 Sample Log: "Lanyard hung, leaking." Salinity is high com- pared with CTD. No analytical problems found. Nutrients and oxygen are a little low. Footnote bottle leaking, sam- ples bad. 109 Console Ops: "10th light on." 107 Console ops: "No FF08, 7 light on." 108 Sample Log: "Was open, didn't close." Console Ops: "FF10 9th light on." Bottle did not close, but CTD data the same as bottle 7 is included to give users an additional flag that there was a slight problem, but it has been properly resolved. 106-111 NO3 appears low, SiO3 low and O2 high. Nutrient Analyst: "No analytical problem noted, different water perhaps." STATION 018 124 Oxygen high and nutrients (NO3, SiO3,PO4) low 119 Salinity is higher than CTD. No analytical problem found. Feature in CTD which gives a large ∆S. Salinity is acceptable. Other data also okay. 109 Console Ops: "Off by 1." Bottle tripped after 10, footnote bottle did not trip as scheduled. Data are acceptable. Bottle tripped before 09, the pylon was manually positioned and the bottle tripped as planned. 110 Console Ops: "Manual position." Sample Log: "Leaking from end cap." Oxygen as well as other data are acceptable. Bottle tripped before 09, the pylon was manually positioned and the bottle tripped as planned. 108 Console Ops: "No confirm, then confirm." STATION 019 Cast 1 No comments on the Sample Log. 127 Oxygen: "PC locked up, lost sample." 120 NO3 and PO4 appear high. Nutrient Analyst: "Gradient here, probably real." 119 Salinity is high compared with CTD. No analytical problem found. Oxygen is high. NO3 and PO4 also appear high. Nutrient Analyst: "Gradient here, probably real." 107 Salinity analyst switched to 8 before finishing 7. All con- ductivity ratios were remembered and written down. 101 SiO3 low. Nutrient analyst: "No analytical problem found. Agrees with 102 and 103 which it should." Data are accept- able. STATION 020 128-131 Footnote CTDO questionable 0-164db. 124 Salinity is high compared with the CTD. Autosal diagnostics indicate 4 tries to get a good reading, indicating a problem with the samples. Salinity agrees with adjoining stations. Offset as much as station profile 100-700 db. 121 Salinity is high compared with the CTD. Autosal diagnostics indicate 4 tries to get a good reading, indicating a problem with the samples. Salinity agrees with adjoining stations. 119 Salinity is high compared with the CTD. Autosal diagnostics indicate 4 tries to get a good reading, indicating a problem with the samples. PI: "Could be okay, high variability region." CTD profile indicates changing area. Down/up dif- ferences. Salinity is acceptable. 116 Salinity is low compared with the CTD Autosal diagnostics indicate 4 tries to get a good reading, indicating a problem with the samples. Agrees with Station 019. Salinity is acceptable. 108 Sample Log: "Vent not fully closed." Oxygen as well as other samples appear to be acceptable. 104 Salinity is high compared with the CTD. Autosal diagnostics indicate 3 tries to get a good reading, indicating a problem with the samples. Also high compared with adjoining sta- tions. Footnote salinity bad. 101 Oxygen high. No analytical problem noted. Footnote oxygen bad. STATION 021 Cast 1 SiO3 ~0.6 high. Nutrient analyst: "No analytical problem noted." SiO3 is acceptable. 104 Console Ops: "Manually positioned with software to 4, no affect. Dialed up 4 on deck unit and pushed button, bottle closed. This occurred with the rosette at the surface." Sample Log: "Surface bottle." 125 Footnote CTDO bad 492-626db. 112 Salinity is high compared with the CTD. Autosal diagnostics indicate 3 tries to get a good reading. Variation in CTD trace. PI: "Salinity is acceptable." 107 Salinity is high compared with the CTD. Autosal diagnostics indicate 3 tries to get a good reading, indicating a problem with the samples. Footnote salinity bad. STATION 022 Cast 1 No comments on the Sample Log. 130 PO4 ~0.4 high. Nutrient analyst:" High surface gradient here." Data are acceptable. 124 Oxygen ~0.2 high. No analytical problems noted. Footnote oxygen bad. 123 Oxygen ~0.3 high on station profile. No analytical problems noted. Oxygen agrees with CTDO. Oxygen is acceptable. 122-124 Nutrients appear low, oxygen appears high. Salinity agrees with CTD. Suspect this is real feature. Data are acceptable. 105-108 Nutrients appear low, oxygen appears high. Salinity agrees with CTD. Suspect this is real feature. Data are accept- able. 102 Several tries to get two readings to agree. The first read- ings gave better results and are used in this salinity cal- culation. Salinity is acceptable. STATION 023 Cast 1 No comments on the Sample Log. 116 Salinity is low compared to CTD. Salinity, oxygen and nutrients low. Salinity and O2 would be higher if the bot- tle leaked. Data are acceptable. 110 Salinity is high compared to CTD. Oxygen is a little high, nutrients are a little low. Oxygen agrees with CTDO. Data are acceptable. 105-110 SiO3 low. Nutrient Analyst: "Data are acceptable." STATION 024 Cast 1 No comments on the Sample Log. 129 Oxygen is high. Other data are acceptable. Flask 1149. No analytical problems noted. Footnote oxygen questionable. Footnote CTDO questionable 80-104db. 116 Salinity appears low compared to CTD. But, plotted vs Pot.Temp., it agrees with Station 023 025 and 022. Salinity is acceptable. 113 Oxygen appears low compared with adjoining stations. No analytical problem noted. Compared vs. SiO3, oxygen appears acceptable. 109 Salinity is a little high. No analytical problem noted. PI: "High gradient." Salinity is acceptable. There is a feature in the CTD trace and a slight difference between the down and up trace. STATION 025 Cast 1 Sample Log: "Forgot to remove O2 sensor cover." No CTDO reported. 122 SiO3 appears low. Nutrient Analyst: "Large gradient in nutrients." Data are acceptable. 118 Salinity is slightly high. No analytical problem found. PI: "High gradient." Salinity is acceptable. 117-120 NO3 and PO4 are high. Nutrient Analyst: "Large gradient in nutrients." Data are acceptable. 101 Salinity is high. Autosal diagnostics indicate 4 tries to get a good reading, indicating a problem with the samples. The first readings gave better results and are used in this salinity calculation. Salinity is acceptable. 101-131 Oxygen sensor cover left on. CTDO lost. STATION 026 Cast 1 No comments on the Sample Log. 130 Oxygen appears high vs. CTDO, but agrees with adjoining sta- tions. Oxygen is acceptable. 129 Oxygen appears low, agrees with CTDO, gradient area. Fea- ture not seen in other data. PI: "Checked with Freon ana- lysts, data are acceptable." 125 Oxygen appears high, agrees with CTDO, gradient area. Fea- ture not seen in other data. PI: "Checked with Freon ana- lysts, data are acceptable." 117 Oxygen appears high, agrees with CTDO, gradient area. Fea- ture not seen in other data. PI: "Checked with Freon ana- lysts, data are acceptable." 107 Salinity is high. Autosal diagnostics indicate 4 tries to get a good reading, indicating a problem with the samples. The first readings gave better results and are used in this salinity calculation. Salinity is acceptable. Oxygen is high. Oxygen overtitrated, no endpoint. Overtitration pro- cess evidently was not done correctly. Footnote oxygen bad. 104 Oxygen is 0.02 high. No analytical problem noted, within WOCE specs. Oxygen is acceptable. STATION 027 Cast 1 No comments on the Sample Log. 129-131 Footnote CTDO questionable 0-126db. STATION 028 Cast 1 No comments on the Sample Log. 117 ∆S at 1415db is -0.0064. Salinity also high compared with adjoining stations. No analytical problem noted. Gra- dient and "spike" feature in CTD trace. PI: "Salinity is acceptable." 115 ∆S at 1720db is 0.0048. Salinity agrees with adjoining stations. STATION 029 127-128 Footnote CTDO questionable 0-104db. 121 Oxygen appears low. Feature does not show in other data. No analytical problem noted. Footnote oxygen questionable. Also appears low vs. CTDO. 119 Sample Log: "Vent left open." Oxygen as well as other data are acceptable. 118 Salinity had a large difference as compared with the CTD. Autosal diagnostics indicate 5 tries to get a good reading. The first readings gave better results and are used in this salinity calculation. 109 Oxygen appears low. Feature shown in high nutrients. No analytical problem noted. Oxygen is acceptable. 101 ∆S at 4035db is 0.0025. Salinity agrees with adjoining stations. 101-109 NO3 and PO4 appear high. Feature does not show in S, O2, or SiO3. Nutrient analyst: "F1s look high a bit compared to adjacent stations. Adjusted F1s to match adjacent stations." STATION 030 Cast 1 No comments on the Sample Log. 123 Oxygen appears ~0.1 high. No analytical problem found. Oxygen agrees with CTDO. PI: "Oxygen is acceptable." STATION 031 Cast 1 No comment on the Sample Log. 117 Oxygen low and nutrients (NO3, PO4 SiO3) high. 109 ∆S at 1110db is -0.0076. No analytical problem noted. STATION 032 Cast 1 No comments on the Sample Log. 115-117 Footnote CTDO questionable 0-74db. 108 Oxygen low, nutrients high. Salinity appears to be accept- able. Feature probably real. 107 Oxygen low, nutrients high. Salinity appears to be accept- able. Feature probably real. 102 ∆S at 1261db is -0.0067. No analytical problem found. Salinity lower than adjoining stations. Other data are acceptable. Gradient area. PI: "Salinity is acceptable." 101 ∆S at 1509db is 0.004. No analytical problem found. Salinity higher than adjoining stations. Other data are acceptable. Gradient area. PI: "Salinity is acceptable." STATION 033 116 Sample Log: "Leak from bottom end cap when vent cracked." Oxygen as well as other data are acceptable. 101 Salinity was ~.01 high. Autosal diagnostics indicate 4 tries to get a good reading. The first readings gave better results and are used in this salinity calculation. Salinity is acceptable. STATION 034 Cast 1 No comments on the Sample Log. Duplicate salts were drawn and analyzed by third salinity analyst. Bottle 8 had no water left in it, but the other salts agreed except 6 which was 0.001 high and 1 was .003 high. STATION 035 Cast 1 No comments on the Sample Log. 106 PO4 is ~0.03 high. Nutrient analyst: "No analytical problem found, data is acceptable." STATION 036 Cast 1 No comments on the Sample Log. 106 Oxygen appears low compared with adjoining stations. PI: "NO3, PO4, but not silicate show similar (high) feature, low CFC-11-12 also, likely real." Nutrient Analyst: "SiO3 higher on chart, no problem." Oxygen is acceptable. 102 Oxygen appears high compared with adjoining stations. No complimentary feature in nutrients. Oxygen agrees with CTDO. Oxygen is acceptable STATION 037 Cast 1 No comments on the Sample Log. 122 Salinity had a large difference as compared with the CTD. Autosal diagnostics indicate 5 tries to get a good reading. The first readings gave better results and are used in this salinity calculation. Other data are acceptable. Salinity is acceptable. 115 Oxygen appears low, nutrients high. Data are acceptable. 111 Oxygen: "PC hung up, sample lost." Salinity had a large difference as compared with the CTD. Autosal diagnostics indicate 5 tries to get a good reading. The original read- ing gave better results. Salinity is acceptable. Other data are acceptable. 106 Oxygen appears high, nutrients low. Data are acceptable. 103 Salinity had a large difference as compared with the CTD. Autosal diagnostics indicate 5 tries to get a good reading. The original reading gave better results. Salinity is acceptable. Other data are acceptable. 101 ∆S at 1272db is 0.0133. Autosal diagnostics indicate 5 tries to get a good reading. First reading was higher than the next set of readings. Footnote salinity bad. Other data are acceptable. STATION 038 Cast 1 No comments on the Sample Log. 118 Oxygen low, nutrients (NO3, PO4, SiO3) high; Salinity low as well. 110 ∆S at 1054db is 0.008. Autosal diagnostics indicate 5 tries to get a good reading. Autosal operator did not write down the first reading. Gradient area. Salinity and other data are acceptable. 106 Autosal diagnostics indicate 3 tries to get a good reading. First reading is a little better, but still high. Gradient area. Salinity and other data are acceptable. STATION 039 Cast 1 No comments on the Sample Log. 107 Oxygen low. No problems noted during analysis. Footnote oxygen bad. Flask 1509. 105 Salinity had a large difference as compared with the CTD. Autosal diagnostics indicate 5 tries to get a good reading. The first readings gave better results and are used in this salinity calculation. Salinity is acceptable. 104 Salinity had a large difference as compared with the CTD. Autosal diagnostics indicate 5 tries to get a good reading. The first readings gave better results and are used in this salinity calculation. Salinity is acceptable. STATION 040 Cast 1 No comments on the Sample Log. 124 Footnote CTDO questionable 0-32db. 120-121 Nutrients appear to be switched on NO3 vs. PO4 plot. N:P ratios are low. Salinity agrees with the CTD and it is unlikely that the bottle leaked, since the salinity is at the salinity max. Nutrient analyst can find no problem with the data. Oxygen for 120 appears low on the station profile, vs. pressure, but not so low, compared to previous stations, that it could be considered questionable. These are in the appropriate order, they were not switched. 104 Salinity had a large difference as compared with the CTD. Autosal diagnostics indicate 4 tries to get a good reading. The first readings gave better results and are used in this salinity calculation. Salinity is acceptable. STATION 041 124 Sample Log: "Closed partly out of water." No water for salinity sample. 122-124 Footnote CTDO questionable 0-62db. 111-112 Oxygen is low and nutrients are high. salinity is a little low compared to CTD, but acceptable for gradient area. Fea- ture must be real. 105 ∆S at 2073db is 0.0179. No analytical problem indi- cated. Other data are acceptable. Footnote salinity bad. 103 Salinity had a large difference as compared with the CTD. Autosal diagnostics indicate 4 tries to get a good reading. The first readings gave better results and are used in this salinity calculation. The salinity is still too high. ∆S at 2481db is 0.0056. Footnote salinity bad. 102 ∆S at 2632db is 0.0027. Autosal diagnostics indicate 3 tries to get a good reading. The first reading gave better results and are used in this salinity calculation, but still out of WOCE specs. Variation in the CTD trace. PI: "Salin- ity is acceptable." 101 ∆S at 2824db is 0.0092. No analytical problem indi- cated. Other data are acceptable. Footnote salinity bad. STATION 042 124 Sample Log: "Closed partly out of water." 112 ∆S at 1060db is -0.0065. Autosal diagnostics do not indicate a problem with the analyses. Other samples are acceptable. Agrees fairly well with adjoining stations for this gradient. Salinity is acceptable. 106 ∆S at 1714db is 0.0261. Autosal diagnostics indicate 7 tries to get a good reading, indicating a problem with the samples. Other samples are acceptable. Footnote salinity bad. 101 ∆S at 2518db is 0.0026. The first readings gave better results and are used in this salinity calculation. Salinity is out of WOCE specs. Footnote salinity questionable. STATION 043 Cast 1 No comments on the Sample Log. 110 Oxygen: "OT (No EP)." ∆S at 1213db is 0.0072. Autosal diagnostics indicate 3 tries to get a good reading, indicat- ing a problem with the samples. Salinity operator did not annotate the first reading. PI: "Doesn't look so far off on the plot, salinity is acceptable." 109 Large salinity difference. Suppression switch was set incorrectly. After correcting the data, the agreement is much better. Salinity is acceptable. STATION 044 106 Sample Log: "Vent not tightly closed." Oxygen as well as other data are acceptable. STATION 045 Cast 1 No comments on the Sample Log. 118 Oxygen is high on station profile, nutrients are low. Salinity agrees with CTD and adjoining stations. Data is acceptable. 115 Oxygen is high on station profile, nutrients are low. Salinity agrees with CTD and adjoining stations. Data is acceptable. 113 Salinity ran out of water before reading could be obtained during analysis. Footnote salinity lost. Other data are acceptable. 107 ∆S at 1606db is 0.0065. No analytical problem found. Salinity is acceptable, feature also seen in CTD trace. 105 SiO3 high, Oxygen low. Data are acceptable. STATION 046 Cast 1 No comments on the Sample Log. 119 Footnote CTDO questionable 0-36db. 103 ∆S at 1662db is 0.0065. Autosal diagnostics indicate 5 tries to get a good reading, indicating a problem with the samples. The first readings gave better results and are used in this salinity calculation. Salinity still appears slightly high. Footnote salinity questionable. 101 ∆S at 1831db is 0.0057. Autosal diagnostics indicate 5 tries to get a good reading, indicating a problem with the samples. The first readings gave better results and are used in this salinity calculation. Salinity still appears slightly high. Footnote salinity questionable. STATION 047 Cast 1 No comments on the Sample Log. 114 The first readings gave better results and are used in this salinity calculation. STATION 048 Cast 1 No comments on the Sample Log. 104 The first readings gave better results and are used in this salinity calculation. Oxygen appears low, nutrients appear high. Data is acceptable. PI: "Likely okay, matches CTD." STATION 049 Cast 1 No comments on the Sample Log. 106-107 Oxygen flasks changed during sampling. Data recorded prop- erly and is acceptable. STATION 050 Cast 1 No comments on the Sample Log. 108 Low N:P, the NO3 and PO4 stations profiles looked good. Nutrient Analyst: "No analytical problem, gradient." STATION 051 108 Sample Log: "Vent not closed." Oxygen as well as other data are acceptable. 105 Oxygen high, nutrients (NO3, SiO3,PO4) low. Data are acceptable. 103 The first readings gave better results and are used in this salinity calculation. Salinity is acceptable. STATION 052 Cast 1 No comments from the Sample Log. 118 SiO3 low ~0.9. Nutrient analyst: "Looks the same as Sta 051, in mixed layer." 102-103 SiO3 0.4 low, within specs of the measurement. Nutrient analyst: "No problem noted." 101 PO4 0.05 high, O2 low. PO4 agrees with Station 055. STATION 053 122 High on N:P plot. Nutrient analyst: "Gradient, data is acceptable." 108 Sample Log: "Vent is open." Oxygen as well as other data are acceptable. SiO3 is low. Nutrient analyst: "Probably bad, code questionable." 105 ∆S at 1618db is -0.0035. No analytical problems noted. Salinity agrees with adjoining stations. Gradient area, salinity is acceptable. 103 O2 high. PI: "Doesn't fit in CTDO. Freon did not measure to assist in this. Doesn't match CTDO, but similar to Stas. 054 & 055. Oxygen is acceptable." 102 Oxygen: "PC lock-up, lost sample. STATION 054 123-124 Footnote CTDO questionable 0-38db. 117 Oxygen: "PC locked up, sample lost." 114 Oxygen low, nutrients (NO3, PO4, SiO3) high. Data are acceptable. 108 Sample Log: "Leaking when valve opened." Oxygen and other data are acceptable. ∆S at 1159db is 0.0064. No ana- lytical problem noted. Feature in CTD trace produced by bottle stop. Gradient area. Salinity agrees with adjoining stations. Salinity is acceptable. 104 ∆S at 1565db is 0.0029. No analytical problem noted. Gradient area. Salinity is acceptable. 101 Footnote CTDO questionable 2066-2104db. STATION 055 Cast 1 No comments on the Sample Log. 110 O2 maybe high. PI: "No freon sample, oxygen appears to be okay compared with plots of several stations." 109 PI: "Oxygen low, maybe match the upcast CTD, probably simi- lar to 056. 108 Footnote CTDO bad 1098-1140db. STATION 056 Cast 1 No comments on the Sample Log. 119-121 Footnote CTDO questionable 0-80db. 118 Oxygen is a little high, but nutrients are low. Salinity looks good on station profile. Nutrient Analyst: "Almost looks like sample 19 & 18 are reversed or reversal of trip." 114 Salinity appears high vs. CTD and adjoining stations. Gra- dient area. Salinity analyst had trouble getting readings to agree. First reading is better, but still high. Foot- note salinity questionable. 108 O2 low. PI: "Or 109 O2 high? but both match upcast. Freon not sampled at all bottles. Oxygen is acceptable." STATION 057 Cast 1 No comments on the Sample Log. 116-117 Footnote CTDO questionable 140-240db. 102 ∆S at 1513db is 0.0027. No analytical problem noted. Gradient area. Feature in CTD trace produced by ship roll during sampling may cause the difference in salinity values. Salinity is acceptable. STATION 058 Cast 1 No comments on the Sample Log. 111 Oxygen appears a little low, but nutrients appear a little high. Salinity agrees with the CTD and adjoining stations. Data are acceptable. 104 The first readings gave better results and are used in this salinity calculation. Salinity is acceptable. STATION 059 Cast 1 Sample Log: "Battery died on O2 thermometer." 113-115 Footnote CTDO questionable 0-152db. 110 Oxygen appears a little high, but nutrients appear a little low. Salinity agrees with the CTD and adjoining stations. Data are acceptable. 104 Oxygen appears a little high, but nutrients appear a little low. Salinity agrees with the CTD and adjoining stations. Data are acceptable. 101 The first readings gave better results and are used in this salinity calculation. STATION 060 Cast 1 No comments on the Sample Log. 106 N:P ratio low. Nutrient Analyst: "N:P gradient, data are acceptable." STATION 061 Cast 1 No comments on the Sample Log. STATION 062 Cast 1 No comments on the Sample Log. STATION 063 Cast 1 No comments on the Sample Log. 102 Oxygen appears low but nutrients are high. Data are accept- able. STATION 064 Cast 1 No comments on the Sample Log. 113-115 N:P high. NO3 and PO4 look okay on property plots and the N:P plot agrees with Station 068. Footnote CTDO questionable 0-100db. STATION 065 Cast 1 No comments on the Sample Log. 102 ∆S at 1011db is 0.006. No analytical problem noted. Salinity is not any higher than bottles 3-5 compared with 064 and 067. Does not appear high when plotted on CTD trace. Salinity is acceptable. Oxygen is high and nutrients are low except SiO3 which is also high. Oxygen also agrees with CTDO trace. STATION 066 Cast 1 No comments on the Sample Log. 101-102 PO4 and SiO3 appear a little high. Oxygen is lower than Stations 065 and 067, but higher than Station 068. Data are acceptable. STATION 067 Cast 1 No comments on the Sample Log. 101 ∆S at 1518db is 0.0039. No analytical problem noted. CTD trace shows a mass of features which are created from the bottle trip. Salinity is acceptable. STATION 068 Cast 1 No comments on the Sample Log. 122-124 Footnote CTDO bad 0-106db. 115 Oxygen high and nutrients low, salinity agrees with CTD. Data are acceptable. 107 ∆S at 1617db is 0.0029. No analytical problems noted. Gradient area. Salinity is acceptable. 104 ∆S at 2072db is 0.0031. No analytical problems noted. Gradient area. Salinity is acceptable. STATION 069 123 Sample Log: "Low on water for tritium; no water left for salts." 121-123 Footnote CTDO questionable 0-134db. 119-120 Console Ops: "20 tripped first then 19." This was done through the software, no levels were missed. 118 Console Ops: "No confirm, then confirm." 102 ∆S at 2628db is 0.0025. The first readings gave better results and are used in this salinity calculation. 101 Footnote CTDO bad 2806-2840db. STATION 070 121-124 Footnote CTDO bad 0-192db. 108 Sample Log: "Vent not quite closed." Oxygen as well as other data are acceptable. 102 Oxygen is low, nutrients are high. Salinity agrees with adjoining stations. Data are acceptable. STATION 071 Cast 1 No comments on the Sample Log. Console Ops: "Down trace 30-75m, something stuck in conductivity cell?" 122 Oxygen high, nutrients low, salinity agrees with CTD. 103 Autosal diagnostics indicate 4 tries to get a good reading, indicating a problem with the samples. The first readings gave better results and are used in this salinity calcula- tion. Salinity is acceptable. STATION 072 120 ∆S at 3db is 0.0296. Autosal diagnostics do not indi- cate a problem. Salinity as well as other data are accept- able. 119-120 Footnote CTDO bad 0-42db. 104 ∆S at 1717db is -0.0026. Autosal diagnostics do not indicate a problem. Gradient area. Salinity is acceptable. 101 Sample Log: "Vent open." Oxygen as well as other data are acceptable. STATION 073 Cast 1 No comments on the Sample Log. 118-120 Footnote CTDO bad 0-100db. 115 No nutrients drawn, sampling error. 112 ∆S at 567db is 0.0227. Autosal diagnostics do not indicate a problem. Salinity agrees with adjoining stations and CTD down trace. Oxygen is low and nutrients are high. Data are acceptable. STATION 074 121 Sample Log: "Closed partially out of water." Oxygen as well as other data are acceptable compared to adjoining stations. 119-121 Footnote CTDO bad 0-138db. 114 Low Oxygen, nutrients are a little high and overlay the adjoining stations, salinity is a little low compared to adjoining stations and CTD. Data are acceptable. 113 ∆S is -0.0583. Salinity is low compared with adjoining stations and CTD down trace as well as up. Autosal diagnos- tics do not indicate a problem. Footnote salinity question- able. Other data are acceptable. 101 Footnote CTDO questionable 2240-2272db. STATION 075 Cast 1 No comments on the Sample Log. 108 Nutrients low, O2 high, salinity agrees with CTD. Data are acceptable. STATION 076 Cast 1 No comments on the Sample Log. 115 Oxygen low, corresponding high feature not in nutrients. Low oxygen shown in CTDO trace. 103 SiO3 appears low compared with following stations, it agrees with previous stations. Data are acceptable. STATION 077 Cast 1 No comments on the Sample Log. 119-120 Footnote CTDO questionable 0-48db. STATION 078 Cast 1 No comments on the Sample Log. 113-116 Footnote CTDO bad 0-160db. STATION 079 Cast 1 No comments on the Sample Log. 114 Footnote CTDO bad 0-26db. 109 Oxygen: "Sample lost." No further explanation. STATION 080 Cast 1 No comments on the Sample Log. 119-120 Footnote CTDO bad 0-64db. 113 Oxygen high, feature is also in nutrients-low. CTDO also indicates high O2. Oxygen is acceptable. 106 Oxygen appears low, corresponding high feature not seen in nutrients. CTDO also indicates high O2. 101 Oxygen appears high, corresponding low feature not seen in nutrients. CTDO also indicates high O2. 101-104 NO3 and PO4 a little higher than previous stations, looks okay on N:P plot. STATION 081 121 Footnote CTDO bad 0-30db. 113 Oxygen appears high. Feature does not show in nutrients. Could possibly show in CTDO, but difficult to tell. Does agree with Sta. 083. 111 Salinity appears high, O2 low, but salinity and O2 agree with CTD. 108 Sample Log: "Vent leaking." Oxygen as well as other data are acceptable. 108-113 SiO3 slightly higher than adjoining stations, NO3 too. PO4 appears low. Nutrient Analyst: "PO4 okay, N:P's look nor- mal. STATION 082 Cast 1 No comments on the Sample Log. 120-122 Footnote CTDO bad 0-122db. STATION 083 128 Sample Log: "3 micro-rinses on salinity." Salinity is acceptable. 124-128 Footnote CTDO questionable 0-280db. 113-116 Problem with the run, it appears to have shifted according to the data, but the shift does not show in the peaks. SiO3 is questionable. STATION 084 Cast 1 No comments on the Sample Log. 119-125 Footnote CTDO bad 0-510db. 103 PO4 too high. Nutrient Analyst: "Higher on trace as well- doesn't look right-maybe contaminated? PO4 is questionable." PI: "Code PO4 bad." STATION 085 Cast 1 No comments on the Sample Log. 121-125 Footnote CTDO bad 0-312db. 117 Duplicate O2 drawn. SiO3 1.0 low. Nutrient Analyst: "Okay on chart, peak okay. Agrees with Station 084 as well. Gradi- ent area. SiO3 is acceptable." 101 ∆S at 2959db is 0.0078. Bottle salinity is acceptable. Large spikes in CTD data. STATION 086 Cast 1 No comments on the Sample Log. 122-127 Footnote CTDO bad 0-288db. 119 Triplicate O2 drawn. 104 ∆S at 2751db is 0.0025. PI: "Noisy CTD profile, so okay." Footnote CTD salinity despiked. 103 ∆S at 2821db is 0.0057. PI: "Noisy CTD profile, so okay." Footnote CTD salinity despiked. 102 ∆S at 2862db is 0.0044. PI: "Noisy CTD profile, so okay." Footnote CTD salinity despiked. 101 ∆S at 2908db is -0.0073. PI: "Noisy CTD profile, so okay." Footnote CTD salinity despiked. STATION 087 Cast 1 No comments on the Sample Log. 103 ∆S at 2702db is 0.0037. PI: "Noisy CTD profile, bottle salinity okay." Footnote CTD salinity questionable. No CTDO is calculated because the CTD Salinity is coded ques- tionable. 102 ∆S at 2754db is -0.003. PI: "Noisy CTD profile, bottle salinity okay." Footnote CTD salinity questionable. No CTDO is calculated because the CTD Salinity is coded ques- tionable. STATION 088 Cast 1 No comments on the Sample Log. 116 Salinity is higher than CTD profile. Autosal diagnostics do not indicate a problem. Salinity appears higher than adjoining stations, but not too much more than other salin- ity values in this gradient. It looks like it could be a drawing error. Footnote salinity questionable. 114 Salinity is higher than CTD profile. Autosal diagnostics do not indicate a problem. Salinity appears higher than adjoining stations, but not too much more than other salin- ity values in this gradient. It looks like it could be a drawing error. Footnote salinity questionable. 109 ∆S at 1967db is 0.0066. Autosal diagnostics do not indicate a problem. Gradient. Salinity is acceptable. PI: "Code salinity as questionable." 108 ∆S at 2068db is 0.0025. Autosal diagnostics do not indicate a problem. Gradient. Salinity is acceptable. STATION 089 127 Sample Log: "Running out of water." Salinity is acceptable. 125-127 Footnote CTDO bad 0-102db. 119 Oxygen: "Sample is lost, thio tube was bent and not dispens- ing properly. Footnote oxygen lost. 109 ∆S at 1639db is 0.003. Autosal diagnostics do not indicate a problem. Gradient area. Salinity is acceptable. 101 Footnote CTDO questionable 2170-2182db. STATION 090 Cast 1 No comments on the Sample Log. 118-123 Footnote CTDO bad 0-444db. 105 The first readings gave better results and are used in this salinity calculation. 102 ∆S at 1745db is 0.0059. Autosal diagnostics do not indicate a problem. There is a "spike" in the CTD trace which is probably giving the large difference. This is real data at a bottle stop and is showing the difference in just a few seconds of sampling. Salinity is acceptable. 101 Footnote CTDO bad 1786-1798db. STATION 091 Cast 1 No comments on the Sample Log. STATION 092 Cast 1 No comments on the Sample Log. 118 Footnote CTDO questionable 0-34db. STATION 093 Cast 1 No comments on the Sample Log. 101 Footnote CTDO questionable 506-516db. STATION 094 Cast 1 No comments on Sample Log. STD dial 5 units higher than previous and next runs. This would only be a difference if 0.001 PSU and is negligible on this shallow station. 110 ∆S at 4db is 0.0455. CTD trace has a large "spike" in it. Footnote CTD salinity questionable. No CTDO is calcu- lated because the CTD Salinity is coded bad. 109-110 Footnote CTDO questionable 0-44db. 109 ∆S at 32db is 0.0431. CTD trace has a large "spike" in it. Footnote CTD salinity questionable. No CTDO is calcu- lated because the CTD Salinity is coded bad. STATION 095 Cast 1 No comments on the Sample Log. 111 ∆S at 3db is 0.0375. Autosal diagnostics do not indi- cate a problem. Lots of variation in CTD trace at the time of bottle trip. Footnote CTD salinity questionable, just not good for bottle trip. No CTDO is calculated because the CTD Salinity is coded bad. Footnote CTDO bad 0-18db. 109 ∆S at 103db is -0.044. Autosal diagnostics do not indicate a problem. Footnote CTD salinity questionable, just not good for bottle trip. No CTDO is calculated because the CTD Salinity is coded bad. STATION 096 114 ∆S at 4db is -0.0297. Autosal diagnostics do not indi- cate a problem. 113 The first readings gave better results and are used in this salinity calculation, but made a 0.005 difference. 108 Sample Log: "Leaking when vent opened." Oxygen as well as other data are acceptable. 102 Triplicate O2 drawn. Footnote CTDO questionable 748-772db. STATION 097 Cast 1 No comments on the Sample Log. 110 ∆S at 2db is 0.0409. Autosal diagnostics do not indi- cate a problem. Salinity is acceptable. Footnote CTDO bad 0-40db. 109 ∆S at 44db is 0.049. Autosal diagnostics indicate 3 tries to get a good reading. Used the first reading The first readings gave better results and are used in this salinity calculation. Salinity is a little lower than adjoining stations. Salinity is acceptable. 108-109 N:P low. Nutrient Analyst: "NO3 and PO4 are acceptable." 101 Footnote CTDO questionable 426-448db. STATION 098 Cast 1 No comments on the Sample Log. 108 Footnote CTDO questionable 0-12db. STATION 099 Cast 1 No comments on the Sample Log. 109-110 Footnote CTDO questionable 0-66db. STATION 100 Cast 1 No comments on the Sample Log. 103 ∆S at 1042db is -0.0167. No analytical problem. Large spike in CTD data. STATION 101 117 Oxygen appears low, however, it is higher than 100 and lower than 102. Lower nutrients show that the feature is real. 108 Sample Log: "Vent loose." Oxygen as well as other data are acceptable. STATION 102 119-121 Footnote CTDO questionable 0-78db. 106 PO4 low, NO3 low vs other stations, but SiO3 is not. Nutri- ent analyst: "Yes, SiO3 is lower, just not as pronounced. No analytical problem." 105 Sample Log: "oxygen redrawn." Oxygen as well as other data are acceptable. ∆S at 1809db is 0.0028. Salinity is a little high Lots of variation seen in CTD profile. No ana- lytical problem noted. PI: "Salinity is acceptable." 103 ∆S at 2038db is -0.0051. Gradient area. No analytical problem noted. lots of variation seen in CTD profile at bottle trip. Salinity is acceptable. STATION 103 128 Sample Log: "No water for surface salts." Footnote CTDO questionable 0-40db. STATION 104 129 O2 appears high compared to adjoining stations, PO4 and NO3 are lower. Data are acceptable. 114 ∆S at 1570db is 0.0052. Autosal diagnostics do not indicate a problem. Salinity minimum, data is acceptable. 110 ∆S at 2378db is 0.0027. Autosal diagnostics do not indicate a problem. Salinity maximum, salinity is accept- able. 109 ∆S at 2530db is 0.0032. Autosal diagnostics do not indicate a problem. Salinity maximum, salinity is acceptable. 108 ∆S at 2631db is 0.0037. Autosal diagnostics do not indicate a problem. Lots of features in the salinity pro- file. Data are acceptable. 106 ∆S at 2774db is -0.0052. Autosal diagnostics do not indicate a problem. Lots of features in the salinity pro- file. Data are acceptable. 104 Triplicate O2 drawn. 103 ∆S at 2957db is -0.0035. Autosal diagnostics do not indicate a problem. Lots of features in the salinity pro- file. Data are acceptable. 102 Triplicate O2 drawn. STATION 105 Cast 1 No comments on the Sample Log. 129 Oxygen: "OT (No EP)." Oxygen as well as other data are acceptable. 126 O2 low, high feature also seen in nutrients. Data are acceptable. 122 Salinity high compared to the CTD. The first readings gave better results and are used in this salinity calculation. The salinity is acceptable after the correction. O2 high, feature is also seen in lower nutrients. Data are accept- able. 115 ∆S at 1468db is 0.0086. Autosal diagnostics do not indicate a problem. Salinity appears high. Other data are acceptable. Footnote salinity questionable. PI: "Code salinity bad." 111-125 NO3 low. Nutrient Analyst: "Reanalyzed data and made a cor- rection to NO3. Data are now acceptable." 107 ∆S at 2786db is 0.0044. Autosal diagnostics do not indicate a problem. Lots of variation in CTD profile at bottle trip. Salinity as well as other data are acceptable. 105 ∆S at 3010db is -0.0028. Autosal diagnostics do not indicate a problem. Lots of variation in CTD profile at bottle trip. Salinity as well as other data are acceptable. 104 ∆S at 3070db is -0.0029. Autosal diagnostics do not indicate a problem. Lots of variation in CTD profile at bottle trip. Salinity as well as other data are acceptable. 103 ∆S at 3132db is -0.0028. Autosal diagnostics do not indicate a problem. Lots of variation in CTD profile at bottle trip. Salinity as well as other data are acceptable. 102 ∆S at 3194db is -0.0043. Autosal diagnostics do not indicate a problem. Lots of variation in CTD profile at bottle trip. Salinity as well as other data are acceptable. STATION 106 Cast 1 No comments on the Sample Log. 127-128 Footnote CTDO questionable 0-36db. STATION 107 126-128 Footnote CTDO questionable 0-68db. 108 Sample Log: "Vent open." Vent is not as tight as the oth- ers. Oxygen as well as other data are acceptable. STATION 108 Cast 1 No comments on the Sample Log. 128 ∆S at 35db is -0.046. Autosal diagnostics do not indi- cate a problem. CTD profile indicates a lot of mixing "spikes". Salinity is acceptable. 126-129 Footnote CTDO questionable 0-166db. 122 Triplicate O2 drawn. 111 ∆S at 2119db is 0.0027. Autosal diagnostics do not indicate a problem. Gradient area. Salinity is acceptable. 110 Triplicate O2 drawn. STATION 109 Cast 1 No comments on the Sample Log. 130 Nutrients not analyzed, no reason noted, suspect drawing problem. Footnote nutrients lost. 129 Oxygen: "Sample lost, PC Hung up during titration." 128-130 Footnote CTDO bad 0-62db. 123 Oxygen: "Sample lost, PC glitch." 109 ∆S at 2499db is 0.0027. Autosal diagnostics do not indicate a problem. Salinity agrees with adjoining sta- tions. 108 Salinity appears high compared with CTD. Autosal diagnos- tics do not indicate a problem. Salinity agrees with adjoining stations. 101-102 Footnote CTDO questionable 3010-3086db. 101 NO3 low. Nutrient Analyst: "Corrected data. NO3 is accept- able." STATION 110 Cast 1 No comments on the Sample Log. 119 Oxygen: "Overtitrate." Oxygen as well as other data are acceptable. 107 ∆S at 2470db is -0.0049. Gradient area. Salinity is acceptable. 106 Salinity disagreed with CTD data. The first readings gave better results and are used in this salinity calculation. Salinity is acceptable. 104 Oxygen: "Overtitrate." Oxygen as well as other data are acceptable. 103 Salinity disagreed with CTD data. The first readings gave better results and are used in this salinity calculation. Salinity is acceptable. 102 ∆S at 3145db is -0.0041. CTD indicates a lower salin- ity at this level. Salinity is acceptable. 101 Footnote CTDO questionable 3188-3212db. STATION 111 Cast 1 No comments on the Sample Log. 119 Oxygen appears high, CTDO indicates higher oxygen is accept- able. PO4, SiO3 and NO3 low verifying this as a real fea- ture. 101-102 Footnote CTDO questionable 2608-2722db. STATION 112 Cast 1 No comments on the Sample Log. 119 Nutrients appear low, oxygen high. Salinity is acceptable. This feature is real. 115 Salinity appears high compared with CTD. CTD indicates a lot of mixing. Salinity is acceptable. STATION 113 Cast 1 No comments on the Sample Log. 109 Salinity: "Lip was cracked on the bottle." Replaced the bottle. Salinity is acceptable. STATION 114 125 Sample Log: "Ran out of water; no tritium, no salinity." 117 Oxygen high, nutrients low. Data are acceptable. 114 ∆S at 689db is -0.0090. Autosal diagnostics do not indicate a problem. PI: "High gradient." Data are accept- able. 101 Footnote CTDO questionable 2476-2508db. STATION 115 Cast 1 No comments on the Sample Log. 101 Footnote CTDO questionable 1968-2010db. STATION 116 Cast 1 No comments on the Sample Log. 122-123 Footnote CTDO bad 0-46db. 104 ∆S at 2529db is -0.0025. Autosal diagnostics do not indicate a problem. Large difference between down and up trace. Also a large difference at this bottle trip. Salin- ity is acceptable. 101 Salinity appears a little high compared with adjoining sta- tions and CTD. Footnote salinity questionable. STATION 117 Cast 1 No comments on the Sample Log. 113-114 SiO3 low, and so is NO3. Data are acceptable. 109 Triplicate O2 drawn. 102 Triplicate O2 drawn. STATION 118 Cast 1 No comments on the Sample Log. 101-102 Low SiO3, NO3 and PO4 also show this low feature and O2 a little higher than adjoining stations. STATION 119 Cast 1 No comments on the Sample Log. 131 Footnote CTDO questionable 0-6db. 119 Low NO3 and PO4, but SiO3 does not show this low feature. Nutrient Analyst: "No analytical problems. NO3 and PO4 are within WOCE specs. Data are acceptable." 111 ∆S at 2426db is -0.0025. Autosal diagnostics do not indicate a problem. Higher salinity value also seen in CTD down/up trace within a salinity minimum area. Salinity is acceptable. 101 Salinity a little high. The first readings gave better results and are used in this salinity calculation. Salinity is acceptable. Oxygen also appears slightly low, but nutri- ents are slightly compared with Station 118. Data are acceptable. Footnote CTDO questionable 4332-4352db. STATION 120 Cast 1 No comments on the Sample Log. 128 Triplicate O2 drawn. 126 Low nutrients, O2 slightly high. Data are acceptable. STATION 121 Cast 1 No comments on the Sample Log. 128-129 Footnote CTDO questionable 0-54db. 124 Nuts appear high. CO2 reports bottle problem. O2 low but CTDO confirms O2 is acceptable. Salinity agrees with CTD. Data are acceptable. 101-103 SiO3 appears low. PO4 is a little lower than adjoining sta- tions. Nutrient Analyst: "No analytical problem found. Salinity also appears to be a little lower on the station profile." Data are acceptable. STATION 122 130-131 Sample Log: "Closed just below the surface to avoid contami- nation from deck washing." There are no samples taken here. 124 Triplicate O2 drawn. 123 O2 low, nutrients high, salinity agrees with CTD. Data are acceptable. 118 Triplicate O2 drawn. 114 ∆S at 1312db is 0.0061. Autosal diagnostics do not indicate a problem. Does not agree with down or up CTD trace. Does not agree with adjoining stations, but there was not sampling at this pressure. Footnote salinity ques- tionable. 102 ∆S at 3539db is -0.0025. Autosal diagnostics do not indicate a problem. There is also a difference between the down and up CTD trace indicated a lot of variations in the water being sampled. Salinity is acceptable. 101 ∆S at 3639db is -0.0029. Autosal diagnostics do not indicate a problem. There is also a difference between the down and up CTD trace indicated a lot of variations in the water being sampled. Salinity is acceptable. STATION 123 Cast 1 No comments on the Sample Log. 130-131 Footnote CTDO questionable 0-54db. 113 Oxygen high compared with adjoining stations. Nutrients are low. Data are acceptable. Footnote CTDO questionable 1924-1980db. 103 Salinity high compared to CTD. The first readings gave bet- ter results and are used in this salinity calculation. Salinity is acceptable. 101 ∆S at 4313db is -0.0025. Autosal diagnostics do not indicate a problem. Salinity is lower than both the down and up CTD trace. It also appears low on the station pro- file. The adjoining stations are not as deep as this sta- tion. This is just slightly out of WOCE specs. Footnote salinity questionable. STATION 124 Cast 1 No comments on the Sample Log. 109-110 Nutrients low, oxygen high. Salinity agrees with CTD. Data are acceptable. 101 Footnote CTDO questionable 4028-4056db. STATION 125 124 Oxygen low, nutrients high. Salinity agrees with CTD. Data are acceptable. 123 Oxygen high, nutrients low. Salinity agrees with CTD. Data are acceptable. 121 Oxygen high, nutrients low. Salinity agrees with CTD. Data are acceptable. 109 Oxygen: "Overtitrated, no end point." Oxygen is acceptable. 105 Sample Log: "Oxygen had to be redrawn, bubbles after stop- pering." Oxygen is acceptable. STATION 126 Cast 1 No comments on the Sample Log. 130 Oxygen: "Overtitrate (No Endpoint)." Oxygen is acceptable. 127 Oxygen: "Overtitrate (No Endpoint)." Oxygen is acceptable. 126 Oxygen: "Overtitrate (No Endpoint)." Oxygen is acceptable. 125-130 Footnote CTDO questionable 0-264db. 120 ∆S at 630db is 0.01. Autosal diagnostics do not indi- cate a problem. Salinity minimum, large variation in CTD trace at bottle trip. Salinity is acceptable. Oxygen: "Overtitrate (No Endpoint)." Oxygen is acceptable. 113 Oxygen: "Overtitrate (No Endpoint)." Oxygen is acceptable. 108 Oxygen: "Overtitrate (No Endpoint)." Oxygen is acceptable. 106 Oxygen: "Overtitrate (No Endpoint)." Oxygen is acceptable. STATION 127 119 Sample Log: "Had to redraw O2." O2 agrees with CTDO. Oxy- gen is acceptable. 115 ∆S at 1406db is 0.008. Autosal diagnostics do not indicate a problem. Salinity agrees with CTD down trace; slight gradient. Salinity is acceptable. 109 ∆S at 2704db is 0.0051. Autosal diagnostics indicate 3 tries to get a good reading, indicating a problem with the samples. But none of the other readings make the salinity lower. Gradient area. Salinity is acceptable. 108 ∆S at 2957db is 0.0025. Autosal diagnostics do not indicate a problem. 103 Oxygen: "Overtitrate (No Endpoint)." Oxygen is acceptable. 102 Oxygen: "Overtitrate (No Endpoint)." Oxygen is acceptable. 101-104 SiO3 appears low compared to adjoining stations, doesn't show in PO4 or NO3, but O2 and salinity are higher than adjoining stations. Adjoining stations are not as deep as this station. Nutrient Analyst: "No analytical problems. Does agree with Station 126, also compares vs. oxygen. Data are acceptable." STATION 128 Cast 1 No comments on the Sample Log. 126-127 Footnote CTDO bad 0-36db. 110 ∆S at 1718db is 0.0029. salinity does appear slightly high compared with CTD. However, it does appear to agree with Station 127. Gradient area. Salinity is acceptable. 106 Triplicate O2 drawn. Oxygen: "Overtitrate (No Endpoint), this was on one of the duplicate samples." Original oxygen agree with CTDO and appears okay on station profile. STATION 129 Cast 1 No comments on the Sample Log. 128 Oxygen: "bad end point." O2 does appear slightly high. Footnote O2 questionable. 127 Oxygen: "bad end point." O2 appears to be acceptable, agrees with CTDO and station profile. 122 Oxygen: "Overtitrated (No EP)." O2 appears a little low, but in gradient area. Oxygen is acceptable. 120 Oxygen: "Overtitrated (No EP)." O2 appears a little high, but in gradient area. Oxygen is acceptable. ∆S at 660db is -0.0124. Variation in CTD trace. Salinity is acceptable. 119 Oxygen: "Overtitrated (No EP)." O2 appears okay on station profile and agrees with CTDO, in gradient area. Oxygen is acceptable. 116 ∆S at 1164db is 0.0327. Autosal diagnostics indicate 3 tries to get a good reading, indicating a problem with the samples. However, they were all fairly close and does not account for this large of a difference. It appears to be a drawing error. 114 Oxygen: "Overtitrated (No EP)." O2 appears okay on station profile and agrees with CTDO. Oxygen is acceptable. 101 Footnote CTDO questionable 4018-4048db. STATION 130 Cast 1 No comments on the Sample Log. 119 Oxygen: "Overtitrated (No EP)." Oxygen as well as other data are acceptable. 116 Oxygen: "Overtitrated (No EP)." Oxygen as well as other data are acceptable. STATION 131 Cast 1 No comments on the Sample Log. 128 ∆S at 31db is -0.0293. Autosal diagnostics do not indicate a problem. Variation in CTD trace. Salinity as well as other data are acceptable. 126 Large difference with CTD. Autosal diagnostics do not indi- cate a problem. Variation in CTD trace. Salinity as well as other data are acceptable. 122 Large difference with CTD. Autosal diagnostics do not indi- cate a problem. Variation in CTD trace. Salinity as well as other data are acceptable. STATION 132 Cast 1 No comments on the Sample Log. 102 Triplicate O2 drawn. 101-107 SiO3 may be high. Compared with adjoining stations and Sta- tion 034 and 031, it appears to be acceptable. 101-102 Footnote CTDO questionable 3496-3544db. STATION 133 Cast 1 No comments on the Sample Log. 121 Oxygen appears high, nutrients low. O2 agrees with CTDO. 101 Footnote CTDO questionable 3180-3294db. STATION 134 Cast 1 No comments on the Sample Log. 122 Oxygen: "Overtitration (No EP)." There is a feature in the CTD trace, which shows the oxygen low. Comparing to adjoin- ing stations it may be a little high. Oxygen is acceptable. 115 Oxygen high, does not fit station profile or CTDO. Other data are acceptable. Footnote O2 bad. 110 ∆S at 1612db is 0.0063. Autosal diagnostics do not indicate a problem. Gradient area. Salinity is acceptable. 108 ∆S at 1912db is 0.0043. Autosal diagnostics do not indicate a problem. Variation in the CTD at the bottle trip and between the down and up. STATION 135 Cast 1 No comments on the Sample Log. 123-124 Footnote CTDO bad 0-50db. 120 ∆S at 185db is 0.0262. Autosal diagnostics do not indicate a problem. Variation in CTD trace looking like a "spike", at the bottle trip. Salinity is acceptable. 118 Large difference between salinity and CTD. Autosal diagnos- tics do not indicate a problem. Variation in CTD trace looking like a "spike", at the bottle trip. Salinity is acceptable. 116 ∆S at 558db is 0.0129. Autosal diagnostics do not indicate a problem. Variation in CTD trace looking like a "spike", at the bottle trip. Salinity is acceptable. 101 Footnote CTDO questionable 3040-3072db. STATION 136 Cast 1 No comments on the Sample Log. 123 Large difference with CTD salinity. Autosal diagnostics do not indicate a problem. Variation in CTD at bottle trip showing as a "spike". 119 Large difference with CTD salinity. Autosal diagnostics do not indicate a problem. Compared with down and up salinity is acceptable. 116 ∆S at 567db is -0.0199. Autosal diagnostics do not indicate a problem. Gradient area. Salinity is acceptable. 114 ∆S at 739db is 0.0105. Autosal diagnostics do not indicate a problem. Variation in CTD at bottle trip showing as a "spike". STATION 137 Cast 1 No comments on the Sample Log. 117 Nutrients low and oxygen high. Data are acceptable. 101 Footnote CTDO questionable 2506-2560db. STATION 138 Cast 1 No comments on the Sample Log. 115 ∆S at 607db is -0.0158. Autosal diagnostics do not indicate a problem. Gradient area, also a variation in the CTD trace resulting in a "spike" at the bottle trip. Salin- ity is acceptable. 103 Triplicate O2 drawn. 101-102 Footnote CTDO questionable 2346-2444db. 101 Oxygen is a little low on the station profile. Nutrients do not confirm this as a real feature. But it is difficult to explain a low oxygen. CTDO confirms the lower oxygen "tail". STATION 139 Cast 1 No comments on the Sample Log. 117-118 Footnote CTDO questionable 0-78db. 101 Footnote CTDO bad 1772-1786db. STATION 140 Cast 1 No comments on the Sample Log. 117-118 Footnote CTDO questionable 0-34db. 109 ∆S at 656db is -0.014. No analytical problem noted. Gradient area, feature in the CTD trace. Data are accept- able. 101 Footnote CTDO bad 1726-1808db. STATION 141 Cast 1 No comments on the Sample Log. 115 CTD profile shows variation in the water which may cause a difference between the salinity and the CTD. Salinity is acceptable. 101 Footnote CTDO questionable 1942-1968db. STATION 142 Cast 1 No comments on the Sample Log. 121 ∆S at 30db is -0.0279. Autosal diagnostics do not indicate a problem. Variations in CTD profile indicating an explanation for a large difference with the salinity. Salinity is acceptable. 120 Duplicate O2 drawn. ∆S at 49db is -0.0255. Autosal diagnostics do not indicate a problem. Variations in CTD profile indicating an explanation for a large difference with the salinity. Salinity is acceptable. 115 Nutrients low and oxygen high. Data are acceptable. 108 ∆S at 1050db is 0.01. Autosal diagnostics do not indi- cate a problem. CTD profile indicates a "spike" at the bot- tle trip. Salinity is acceptable. STATION 143 Cast 1 No comments on the Sample Log. 120-121 Footnote CTDO questionable 0-40db. 114 Oxygen is high and nutrients are low. Data are acceptable. STATION 144 Cast 1 No comments on the Sample Log. 120-124 Footnote CTDO bad 0-192db. 110 ∆S at 1058db is -0.0073. Autosal diagnostics do not indicate a problem. Difference between down and up CTD pro- file. Salinity is acceptable. 105 ∆S at 1815db is -0.0027. Autosal diagnostics do not indicate a problem. Gradient area. Salinity is acceptable. STATION 145 Cast 1 No comments on the Sample Log. 105 Triplicate O2 drawn. 102 Triplicate O2 drawn. 101 ∆S at 2689db is 0.0029. Autosal diagnostics do not indicate a problem. Difference between the down and up CTD trace. Salinity is acceptable. Footnote CTDO questionable 2648-2688db. STATION 146 Cast 1 No comments on the Sample Log. 109 ∆S at 1767db is 0.0031. Autosal diagnostics do not indicate a problem. Gradient area. Data are acceptable. 103 Footnote CTDO questionable 2610-2740db. 101 Oxygen: "Overtitrate, (No End Point)." Oxygen is accept- able. Difference with the CTD salinity. The first readings gave better results and are used in this salinity calcula- tion. Salinity is acceptable. STATION 147 Cast 1 No comments on the Sample Log. 121-124 Footnote CTDO bad 0-146db. 116 Nutrients are high, oxygen is low. CTD agrees with salinity and oxygen. Feature is real. 110 ∆S at 1056db is 0.009. Autosal diagnostics do not indicate a problem. Salinity agrees with adjoining sta- tions. Salinity is acceptable. 106 ∆S at 1713db is 0.0026. Autosal diagnostics do not indicate a problem. Salinity agrees with adjoining sta- tions. Salinity is acceptable. 105 Oxygen: "Overtitrate (No End Point)." Oxygen is acceptable. 101 ∆S at 2648db is 0.0054. Autosal diagnostics do not indicate a problem. Salinity agrees with adjoining sta- tions. Variation in CTD trace as a "spike" at bottle trip. Salinity is acceptable. Footnote CTDO questionable 2602-2648db. STATION 148 Cast 1 No comments on the Sample Log. 118-120 Footnote CTDO questionable 0-84db. 112 Oxygen: "Overtitrate, (No End Point). Oxygen is acceptable. 104 Oxygen appears low. Gradient area, oxygen is acceptable. STATION 149 Cast 1 No comments on the Sample Log. 120-122 Footnote CTDO bad 0-100db. 115 Oxygen: "Overtitrate (No End Point)." Oxygen is acceptable. 110 ∆S at 758db is 0.0178. Autosal diagnostics do not indicate a problem. Gradient in a maximum salinity feature as shown by the CTD. Salinity is acceptable. 103 ∆S at 1921db is -0.0029. Autosal diagnostics do not indicate a problem. Feature in CTD up trace similar to a "spike" at bottle trip. Salinity is acceptable. STATION 150 Cast 1 No comments on the Sample Log. 116-119 Footnote CTDO questionable 0-154db. 115 High O2. Feature does not show in nutrients. Salinity is acceptable. CTDO shows that oxygen is higher at this level. Oxygen is acceptable. 110 ∆S at 668db is -0.0274. Gradient in a maximum salinity feature as shown by the CTD. Salinity is acceptable. 103 ∆S at 1617db is 0.0031. Variation in CTD trace appear- ing as a "spike" at the bottle trip. Salinity is accept- able. 101 ∆S at 1835db is 0.0027. Variation in CTD trace appear- ing as a "spike" at the bottle trip. Salinity is accept- able. Footnote CTDO questionable 1828-1836db. 101-102 Nutrients high, O2 low. Feature is real. STATION 151 Cast 1 No comments on the Sample Log. 115-117 Footnote CTDO questionable 0-112db. 102 Triplicate O2 drawn. STATION 152 Cast 1 No comments on the Sample Log. 115-117 Footnote CTDO bad 0-72db. 107 Nutrients high and oxygen and salinity low. Data are acceptable. 106 Oxygen: "Overtitrate, (No End Point)." Oxygen is accept- able. STATION 153 Cast 1 Console Ops: "Special cast for LADCP bottom tracking test, minimal sampling." Only salinity drawn. 101-103 No bottle oxygen data for fit, use corrections from nearby cast. Footnote CTDO questionable 0-1086db. 216 Sample Log: "Not enough water for salinity." 215-216 Footnote CTDO questionable 0-36db. 213 Oxygen: "Overtitrate, (No End Point)." Oxygen is accept- able. 211 O2 appears high on station profile, but CTDO also shows this high feature. Oxygen is acceptable. ___________________________________________________________________________________________________________ ___________________________________________________________________________________________________________ WHPO DATA CHECK a24_ct1.zip a24_hy1.csv About the '_check.txt', '_sal.ps' and '_oxy.ps' files: The WHP-Exchange format bottle and/or CTD data from this cruise have been examined by a computer application for contents and consistency. The parameters found for the files are listed, a check is made to see if all CTD files for this cruise contain the same CTD parameters, a check is made to see if there is a one-to-one correspondence between bottle station numbers and CTD station numbers, a check is made to see that pressures increase through each file for each station, and a check is made to locate multiple casts for the same station number in the bottle data. Results of those checks are reported in this '_check.txt' file. When both bottle and CTD data are available, the CTD salinity data (and, if available, CTD oxygen data) reported in the bottle data file are subtracted from the corresponding bottle data and the differences are plotted for the entire cruise. Those plots are the '_sal.ps' and '_oxy.ps' files*. Following parameters found for bottle file: EXPOCODE DEPTH SILCAT CFC-12_FLAG_W SECT_ID CTDPRS SILCAT_FLAG_W TCARBN STNNBR CTDTMP NITRAT TCARBN_FLAG_W CASTNO CTDSAL NITRAT_FLAG_W PCO2 SAMPNO CTDSAL_FLAG_W NITRIT PCO2_FLAG_W BTLNBR SALNTY NITRIT_FLAG_W ALKALI BTLNBR_FLAG_W SALNTY_FLAG_W PHSPHT ALKALI_FLAG_W DATE CTDOXY PHSPHT_FLAG_W PH TIME CTDOXY_FLAG_W CFC-11 PH_FLAG_W LATITUDE OXYGEN CFC-11_FLAG_W PCO2TMP LONGITUDE OXYGEN_FLAG_W CFC-12 CTDRAW THETA All ctd parameters match the parameters in the reference station. All stations correspond among all given files. No bottle pressure inversions found. Bottle file pressures are increasing. a24_hy1.csv -> contains stations with multiple casts: station -> 153: 2 casts. *_oxy.ps is not available, see pdf file for '_sal.ps' WHPO/CCHDO DATA PROCESSING NOTES DATE CONTACT DATA TYPE DATA STATUS SUMMARY -------- ----------- -------------- ---------------------------------------- 03/18/98 Talley Cruise Report Submitted: Data Update I have revised the A24 doc file (a24do.txt). I have added cruise summary information to the front, very slightly reorderd the information in the narrative section, including the tables, and removed the page separators. I have placed the edited file in the imani ftp site. Please replace the version in the website table with this one. 02/22/00 Diggs CFCs Submitted: by Weiss/Salameh To the best of my knowledge (and our database's) we did not receive any updated CFC values from you until today. We realize how important the CFC synthesis is, so I will put merging these data at the top of the list. 02/22/00 Diggs CFCs Submitted; sent to D.Newton to merge In the list of things to do, there are new CFCs from Weiss/Salameh for A24 ready to be merged. They are in the following directory (I converted them already to WOCE format for your program and ran the file through WOCECVT) 02/28/00 Huynh Cruise Report Website Updated: txt doc online pdf file is waiting for figures from Lynne Talley and the txt file is up. 02/29/00 Newton CFCs Update needed: replicate values "I'm merging the updated WOCE A24 CFC data you sent Steve Diggs on Feb 22. I've encountered a small problem that you'll need to resolve. At the very end of file "woce-a24.cfc" you sent is this fragment: 153 2 14 64 1.463 2.769 22 153 2 15 35 1.443 2.724 22 153 2 16 2 1.404 2.627 22 153 2 16 2 1.406 2.619 22 As you can see there are two station 153 cast 2 bottle 16 values. I can't merge them both. 03/06/00 Huynh Cruise Report Website Updated: pdf & txt docs online Both txt and pdf doc versions are up 03/13/00 Salameh CFCs Data Update: replicate value fixed Sorry it's taken me so long to get back to you on this! My software is supposed to take means of replicate samples before creating the file for WHPO, but obviously there is a bug when the replicate sample happens to be the last one in the list. I have now fixed the problem and attached a new version of the data file. DATE CONTACT DATA TYPE DATA STATUS SUMMARY -------- ----------- -------------- ---------------------------------------- 03/13/00 Swift CTD/BTL Data are Public Please make the CTD and S/O2/nut data from the Talley A24 line public (and unencrypted), as per the message just received from Lynne. Thanks. Jim - funny you should ask minutes after Worth's note about making A24 public. I told him that A24 should be public now, so please have Steve make the necessary changes. I would be interested in seeing what you find for the EGS. Lynne 03/14/00 Weiss CFCs Website Updated: Status changed to Public 03/14/00 Newton CFCs Website Updated: Data Online I received the correct a24 cfc file from Peter Salameh and have merged it. On whpo INCOMING please find: a24cfcmerg.tar.Z it contains the merged file, the corrected CFCs, and my notes. a24cfc_weiss_salameh_wocefmt.2000.02.24.txt on whpo in onetime/atlantic/a24/original/2000.02.23.A24.WEISS_SALAMEH.CFC is bogus (Quality codes not reordered with data) a24_cfc_salameh.2000.02.21.txt in that same directory contains an error at the last bottle (replicates not averaged) Those two files should be deleted/buried . -david Notes on merging CFC into A24 EXPOCODE 316N151/2 WHP-ID A24 merging went fine. no problems. D. Newton 13Mar2000 03/22/00 Chapman CTDO/NUTS/CFCs Data are Public ar24: no tracers; a24: BTL data pubic. I asked Mke Mccartney what, if any data were taken on AR24 other than CTDO data. He said that no tracer data were collected on either of these repeat cruises, and that nutrients were collected only on the first of them. Thus, it seems as though the only tracer data collected in this region were on the A24 cruise when Lynne Talley was chief scientist. Her latest message, and one from Ray Weiss, state that the CTDO, nuts and CFC data should all be public now. 03/24/00 Diggs CTD/BTL Website Updated: files online, public 03/24/00 Schlosser He/Tr Data are Public; NOT FINAL as mentioned in my recent message, we will release our data with a flag that indicates that they are not yet final. We started the process of transferring the data and we will continue with the transfer during the next weeks. I had listed the expected order of delivery in my last message. DATE CONTACT DATA TYPE DATA STATUS SUMMARY -------- ----------- -------------- ---------------------------------------- 07/10/00 Huynh Cruise Report Website Updated: pdf, txt versions updated, online 02/08/01 Kappa Cruise Report Update Needed Replace online ODF report w/ Orig. ODF report 04/06/01 Uribe CTD/BTL/SUM Website Updated: expocodes corrected Expocodes for sum and bottle were modified. 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. 05/04/01 Kozyr ALKALI/TCARBN Final Data Submitted; also CO2/pH/PCO2 I have put the final CO2-related data files for the N. Atlantic Ocean WOCE Sections A20, A22, and A24 to the WHPO ftp INCOMING area. There are 4 CO2 parameters: Total CO2, Total Alkalinity, pH, and pCO2 (with pCO2 temp) with quality flags. Note, that these data are different from those you have in your data base for these cruises on WHPO web site. Please confirm the data submissio 06/20/01 Uribe BTL Website Updated: Exchange file online Bottle file in exchange format has been linked to website. 06/21/01 Uribe CTD/BTL Website Updated: New Exchange files online The exchange bottle file name in directory and index file was modified to lower case. CTD exchange files were put online. 12/03/01 Muus BTL/CO2 Website Updated: New CSV & BTL files Merged Carbon data received from A. Kozyr, May 2001, into bottle file and placed on web together with new exchange file. REVPRS and REVTMP columns deleted. Notes on A24 Carbon merging Dec 3, 2001. D. Muus 1. New TCARBN, ALKALI, PH, PCO2, and PCO2TMP from: /usr/export/html-public/data/onetime/atlantic/a24/original /2001.05.04_A20_A22_A24_CARBON_KOZYR/a24carb_wocefmt.txt Merged into SEA file from web Nov 30, 2001 (20010406WHPOSIOKJU) No QUALT2 words in SEA file or new data file so added QUALT2 identical to QUALT1 after merging. 2. REVPRS and REVTMP columns removed. No reversing thermometers used. 3. Exchange file checked using Java Ocean Atlas. DATE CONTACT DATA TYPE DATA STATUS SUMMARY -------- ----------- -------------- ---------------------------------------- 12/17/01 Hajrasuliha CTD/BTL Internal DQE completed: summery of errors The following are results from the examminer.pl and plotter.pl code that were run on this cruise. Not all of the errors are reported but rather a summery of what was found. For more information you can go to the cruise directory, and look at the NEW file called CruiseLine_check.txt. Two plot files are also present. _oxy.ps and _sal.ps _oxy.ps and _sal.ps files are created for the cruise. No problems found in the BOTTLE and CTD file. 12/20/01 Uribe CTD Website Updated: Exchange file online CTD has been converted to exchange using the new code and put online. 04/10/02 Lebel CFCs Submitted Data ARE FINAL The data disposition is: Public The file format is: Plain Text (ASCII) The archive type is: NONE - Individual File The data type(s) is: Other: final CFC data The file contains these water sample identifiers: Cast Number (CASTNO) Station Number (STATNO) Bottle Number (BTLNBR) Sample Number (SAMPNO) LEBEL, DEBORAH would like the following action(s) taken on the data: Merge Data Place Data Online Update Parameters Any additional notes are: These are the final CFC data, including QUALT2 word. Scale is SIO98, units are pmol/kg. Data were recalibrated last fall, and these changes are incorporated as well. 08/20/02 Diggs TCARBN/CFCs Website Updated: data are final Merged TCARBN (Kozyr: 20020820), and FINAL cfc-11 and cfc-12 values from D. Lebel (20020410). Made new bottle Exchange files and NetCDF, as well as inventory files. 12/13/02 Kozyr CFCs Update Needed CFCs missing values I've noticed that CFCs missing values in the A24 bottle data file a24hy.txt are -9.074 (CFC11) and -9.048 (CFC12). Seems like it has happened when one added a constant correction for all cfc numbers. Same in the a24_hy.csv file. 02/10/03 Diggs He/Tr Submitted Excel and CSV files Excel files and CSVs submitted and placed in home directory. Excel files (along w/ CSVs) were submitted to ODF email address and decoded and placed in home directory for A24 data files. DATE CONTACT DATA TYPE DATA STATUS SUMMARY -------- ----------- -------------- ---------------------------------------- 02/12/03 Anderson He/Tr/CFCs Website Updated: Data Online Merge Notes: Alex Kozyr noted that the missing values for cfc11 was -9.074 and for cfc12 -9.048. These were the values in the file 20020410.123042_LEBEL_A24_a24.dat from Lebel found in original/20020410.123042_LEGEL_A24 that S. Diggs merged into the online file 20011130WHPOSIODM on Aug. 20, 2002. I changed the missing values to -9.000 for cfc11 and cfc12. Bottle: (cfc-11, cfc-12, tritum, helium, delhe3, triter, helier, delher, qualt1, qualt2) Merged the HELIUM, HELIER, DELHE3, DELHER, TRITIUM, and TRITER sent to S. Diggs from B. Newton found in file. A24_helium_tritium.csv found in original/20020522_A24_HE-TR_NEWTON into the online file 20011130WHPOSIODM (This is the file that S. Diggs merged the carbon and cfcs into, but he apparently didn't change the time stamp. Sarilee Anderson 09/22/03 Kozyr Cruise Report CO2 report online @ CDIAC The ORNL/CDIAC-143, NDP-082: "Carbon Dioxide, Hydrographic, and Chemical Data Obtained During the R/V Knorr Cruises in the North Atlantic Ocean on WOCE Sections AR24 (November 2 - December 5, 1996) and A24, A20, and A22 (May 30 - September 3, 1997)" is now available online through CDIAC web page: http://cdiac.ornl.gov/oceans/doc.html The hard copy is in production department and will be sent to you soon. Please let me know if you have any comments. Special thanks to Ken Johnson: even after retirement, he continues to supply CDIAC with all information needed for this and other NDPs. 10/18/06 Johnson Cruise Report Submitted Final cruise report The documentation files have been updated with post-cruise info and final comments. DATE CONTACT DATA TYPE DATA STATUS SUMMARY -------- ----------- -------------- ---------------------------------------- 10/18/06 Johnson CTD/BTL/SUM Submitted; Data are Final Final A24/ACCE data are now ready to go, with calibrations checked, CTDOXY data refit, and CTD data despiked as warranted. CTD data are coded for despiking and problems, and a few bottle quality codes were updated (codes for CTD data in the bottle files). Kristin gave us an updated bottle file with the final quality codes and CTD data, and an updated .sum file with theancillary codes added. The documentation files have been updated with post-cruise info and final comments. These were older cruise data without the database, so we do NOT have exchange formats available. However, Steve Diggs said he could handle that for us. Since all of the WOCE data have been declared public by the WHPO, the files are available for immediate access. CTDPRS CTDTMP CTDSAL CTDOXY THETA SALNTY OXYGEN SILCAT NITRAT NITRIT PHSPHT 11/03/06 Johnson Cruise Report Submitted updated cruise report I caught a buglet in the documentation - Appendix A, the T(t**1) column was wrong and wasn't separated from the first column in the plain-text version. It's now fixed; the difference in the value is fairly negligible, but when I noticed the bug while doing something else, I thought I should correct it. I re-did the main ftp releases, but also made one with JUST the documentation files. You can find the doc-files at: ftp://odf.ucsd.edu/pub/HydroData/woce/a24.acce/ The files called a24final-doc.{zip,tar.gz} are the new doc. No data files have been altered, and only Appendix A in the doc has been updated. 11/27/06 Kappa Cruise Report Website Updated: new cruise report New cruise report, pdf and ascii versions, include: * changes discussed in Mary Johnson's 11/3/06 email * CCHDO Data Processing Notes * Alex Kozyr's CO2 report * Hajrasuliha's CTD data check (see 12/17/01 note)