CRUISE REPORT: A16S (Updated OCT 2019) Highlights Cruise Summary Information WOCE Section Designation A16S Expedition designation (ExpoCodes) 33RO20131223 Chief Scientist Dr. Rik Wanninkhof / NOAA/AOML co-Chief Scientist Dr. Leticia Barbero / AOML/CIMAS Dates 2013 DEC 23 - 2014 FEB 05 Ship Ronald H. Brown Ports of call Recife, Brazil – Punta Arenas, Chile 6° 0' 6" S Geographic Boundaries 36°22'59" W 24°59'48" W 60° 0' 47" S Stations 113 Floats and drifters deployed 14 Argo floats deployed Moorings deployed or recovered 0 Contact Information: Dr. Rik Wanninkhof NOAA/Atlantic Oceanographic and Meteorological Laboratory R/E/AO/OCD • 4301 Rickenbacker Causeway • Miami, FL • 33149-1046 Tel: 305-361-4379 • Fax: 305-361-4582 • Email: wanninkhof@aoml.noaa.gov Final Report Assembly by Jerry Kappa, SIO/UCSD GO-SHIP CLIVAR A16S NOAAS Ronald H. Brown 23 December 2013 – 05 February 2014 Recife, Brazil – Punta Arenas, Chile Chief Scientist: Dr. Rik Wanninkhof National Oceanic and Atmospheric Administration, AOML Co-Chief Scientist: Dr. Leticia Barbero AOML/CIMAS Preliminary Cruise Report CTD Data Submitted by: Kristene E. McTaggart National Oceanic and Atmospheric Administration, PMEL Seattle, WA Preliminary Bottle Data Submitted by: Alejandro Quintero Shipboard Technical Support/Oceanographic Data Facility Scripps Institution of Oceanography/UC San Diego La Jolla, CA Contents Introduction Acknowledgements Background GO-SHIP CLIVAR A16S Participating Institutions Principal Programs of GO-SHIP CLIVAR A16S Scientific Personnel GO-SHIP CLIVAR A16S Measurement Program Summary 1. CTD DATA ACQUISITION AND ROSETTE OPERATION CTD Underwater Package CTD Data Acquisition Acquisition Problems CTD Data Processing Pressure Calibration Temperature Calibration Conductivity Calibration Oxygen Calibration Despiking Water Sampling Bottle Sampling Bottle Data Processing Analytical Problems 2. SALINITY 3. OXYGEN ANALYSIS 4. NUTRIENTS 5. CHLOROFLUOROCARBONS (CFCS) AND SULFUR HEXAFLUORIDE (SF6) 6. DISCRETE pCO2 7. DISSOLVED INORGANIC CARBON (DIC) 8. pH 9. TOTAL ALKALINITY 10. DISSOLVED ORGANIC CARBON (DOC) 11. CARBON ISOTOPES IN SEAWATER ((^14/13)C) 12. TRITIUM, HELIUM AND (^18)O 13. DENSITY 14. LADCP SADCP 15. CHIPOD 16. TRACE METAL PROGRAM Aerosol Samples Rain Samples Argo Float Deployments References APPENDIX Cast Bottom Data Bottle Data Quality Code Summary and Comments CCHDO Data Processing Notes Introduction The GO-SHIP CLIVAR/CO2 cruise in the South Atlantic on NOAA ship Ronald H. Brown was successfully completed over the period from 23 December 2013 to 05 February 2014. This cruise is part of a decadal series of repeat hydrography sections jointly funded by NOAA-CPO/COD and NSF-OCE as part of the GO-SHIP (Global Ocean Ship-Based Hydrographic Investigations Program) CLIVAR/CO2/hydrography/tracer program (http://ushydro.ucsd.edu). The goal of this effort is to occupy a set of hydrographic transects over the global ocean with full water column measurements to study physical and hydrographic trends and variability overtime. The A16S cruise began in Recife, Brazil and ended in Punta Arenas, Chile. Many academic institutions and two NOAA research laboratories participated in the cruise. The A16S section ran due south along 25°W from approximately 6°S to 35°S, and then transited in a Southwest direction to South Georgia Island at 54°S, 36°W. The last part of the section crossed the Scotia Sea with a terminus at 60°S, 31°W. This is a repeat of the section previously occupied by the U.S. in 1989 and 2005. A total of 113 full water column CTD/O2/LADCP/rosette casts were completed along the A16S section at 30 nautical mile (nm) (54 km) spacing, with closer spacing at the basin boundaries near South Georgia. Measurements taken from the instrument package include temperature, salinity, oxygen, currents (LADCP), micro-turbulence structure (Chipod), particles (transmissometer), and colored dissolved organic matter, CDOM (ﬂuorometry). Approximately 2700 Bullister bottle samples were collected on these casts and analyzed for a variety of parameters including salinity, dissolved oxygen, nutrients, chloroﬂuorocarbons (CFCs), SF6, dissolved inorganic carbon (DIC), alkalinity, pCO2, pH, carbon isotopes (14CDIC), dissolved organic carbon (DOC), 18O/16O, helium, tritium, density, and trace metals. Underway data collection included upper-ocean current measurements from the shipboard ADCP, surface oceanographic (proxi-chlorophyll by ﬂuorometry, temperature, salinity, CO2) and meteorological parameters from the ship’s scientiﬁc seawater supply, bathymetric data and atmospheric measurements of CO2, CFCs, and SF6. Data from this cruise are available from CCHDO at: http://cchdo.ucsd.edu/data_access/show_cruise?ExpoCode=33RO20131223 Acknowledgements The successful completion of the cruise relied on the dedicated assistance from many individuals on shore and on the NOAA ship Ronald H. Brown. Funded investigators in the project and members of the GO-SHIP CLIVAR/CO2 program were instrumental in the successful planning and executing of the cruise. All of the participants showed dedication, cooperation and camaraderie during their 45 days at sea. Ofﬁcers and crew of the Ronald H. Brown exhibited a high degree of professionalism and assistance in accomplishing the mission and made us feel at home during the voyage. Commanding ofﬁcer Joseph Pica oversaw a smoothly running ship and engaged with the scientiﬁc party. Operations ofﬁcer Paul Chamberlain was an excellent liaison before, during, and after the cruise to accommodate all scientiﬁc operations and scheduling. Survey Technicians Darcy Balcarce, Jonathan Shannahoff and Electronics Technician Clay Norﬂeet contributed to the success of this cruise through their able deck handling, stewardship of shipboard scientiﬁc gear and expert instrument and infrastructure troubleshooting experience. All ofﬁcers, deck crew, engineers, and galley staff contributed to the success of this long cruise that occurred over the holiday season. Their sacriﬁce, assistance and good cheer are gratefully acknowledged. The U.S. GO-SHIP Repeat Hydrography/CO2 Program is sponsored by the NOAA Climate Observation Division of the Climate Program Ofﬁce (COD/CPO) and the National Science Foundation. In particular, we wish to thank program managers David Legler and Joel Levy (NOAA/CPO), and Eric Itsweire and Don Rice (NSF/OCE), for their insights, moral and ﬁnancial support. Clearance was requested and granted from the sovereign nations of the United Kingdom and Argentina for research conducted in their declared territorial waters. Their permission to execute the research effort in the waters surrounding South Georgia Island/Isla Georgia del Sur was critical for the repeat occupation and is greatly appreciated. Background The CLIVAR Repeat Hydrography Program focuses on the need to monitor inventories of CO2, tracers, heat and freshwater and their transports in the ocean. Earlier programs under WOCE and JGOFS provided a baseline observational ﬁeld for these parameters. The new measurements reveal much about the changing patterns on decadal scales. The program serves as a backbone to assess changes in the ocean’s biogeochemical cycle in response to natural and/or man-induced activity. Global changes in the ocean’s transport of heat and freshwater, which can have a signiﬁcant impact on climate, can be followed through these long-term measurements. The CLIVAR/CO2 Repeat Hydrography Program provides a robust observational framework to monitor these long-term trends. These measurements are in support of: • Model calibration and testing • Carbon system studies • Heat and fresh water storage and ﬂux studies • Deep and shallow water mass and ventilation studies • Calibration of autonomous sensors This program follows the invasion of anthropogenic CO2 and transient tracers into intermediate and deep water on decadal timescales and determines the variability of the inorganic carbon system and its relationship to biological and physical processes. More details on the program can be found at the website: http://ushydro.ucsd.edu. Speciﬁc information about this cruise can be found at: http://www.aoml.noaa.gov/ocd/gcc/A16S_2014/ Thanks to science participant Rachel Shelley for her informal "blogs" that recount cruise/port highlights. A link to this blog can be found on the cruise website. GO-SHIP CLIVAR A16S Participating Institutions Abbre- Institution via- tion —————— ————————————————————————————————————————————————————————————————— AOML Atlantic Oceanographic and Meteorological Laboratory - NOAA RSMAS Rosenstiel School of Marine and Atmospheric Science/University of Miami PMEL Paciﬁc Marine Environmental Laboratory - NOAA FSU Florida State University SIO Scripps Institution of Oceanography/University of California at San Diego UH University of Hawaii at Manoa UCSB University of California Santa Barbara UT University of Texas at Austin WHOI Woods Hole Oceanographic Institution PU Princeton University OSU Oregon State University LDEO Lamont-Doherty Earth Observatory/Columbia University Principal Programs of GO-SHIP CLIVAR A16S Analysis Institution Principal Investigator email ——————————————————— ——————————— ——————————————— —————————————————————————— CTDO NOAA/PMEL Gregory Johnson Gregory.C.Johnson@noaa.gov NOAA/AOML Molly Baringer Molly.Baringer@noaa.gov Salinity NOAA/AOML Molly Baringer Molly.Baringer@noaa.gov UW & Discrete pCO2 NOAA/AOML Rik Wanninkhof Rik.Wanninkhof@noaa.gov Total CO2 (DIC) NOAA/PMEL Richard Feely Richard.A.Feely@noaa.gov NOAA/AOML Rik Wanninkhof Rik.Wanninkhof@noaa.gov Nutrients NOAA/AOML Jia-Zhong Zhang Jia-Zhong.Zhang@noaa.gov NOAA/PMEL Calvin Mordy Calvin.W.Mordy@noaa.gov Dissolved O2 NOAA/AOML Molly Baringer Molly.Baringer@noaa.gov RSMAS Chris Langdon clangdon@rsmas.miami.edu Total Alkalinity/pH RSMAS Frank Millero fmillero@rsmas.miami.edu Chlorofluorocarbons NOAA/PMEL John Bullister John.L.Bullister@noaa.gov (CFCs)/SF6 3He/Tritium LDEO Peter Schlosser peters@ldeo.columbia.edu WHOI William Jenkins wjenkins@whoi.edu CDOM UCSB/MSI Craig Carlson carlson@lifesci.ucsb.edu Chipod OSU Jonathan Nash nash@coas.oregonstate.edu ADCP/Lowered ADCP U Hawaii Eric Firing efiring@hawaii.edu Trace Metals FSU William Landing wlanding@fsu.edu UH Chris Measures measures@hawaii.edu 14C/DIC WHOI Ann McNichols amcnichol@whoi.edu PU Robert Key key@princeton.edu DOC RSMAS Dennis Hansell dhansell@rsmas.miami.edu Data Management SIO James Swift jswift@ucsd.edu SIO Susan Becker sbecker@ucsd.edu Scientific Personnel GO-SHIP CLIVAR A16S Duties Name Afﬁliation email —————————————————— ————————————————————————— —————————— ————————————————————————————— Chief Scientist Rik Wanninkhof AOML rik.wanninkhof@noaa.gov Co-Chief Scientist Leticia Barbero AOML/CIMAS leticia.barbero@noaa.gov Data Management Alex Quintero SIO alexq@ucsd.edu CTD Data Processor Kristene McTaggart PMEL kristene.e.mctaggart@noaa.gov CTD watch-stander Jonathan Christophersen FSU jac10r@my.fsu.edu CTD watch-stander Gabrielle Weiss U Hawaii gweiss@hawaii.edu LADCP Lora VanUffelen U Hawaii loravu@hawaii.edu LADCP/Salinity Jay Hooper V AOML/CIMAS james.hooper@noaa.gov Salinity Edward Hunt Contract edhuntjones@mindspring.com O2 Laura Stoltenberg RSMAS l.stolti@yahoo.com O2 Andrew Stefanick AOML Andrew.Stefanick@noaa.gov Nutrients Charles Fischer AOML Charles.Fischer@noaa.gov Nutrients Eric Wisegarver PMEL eric.wisegarver@noaa.gov DIC Robert Castle AOML robert.castle@noaa.gov DIC Julie Arrington PMEL julie.seahorse@gmail.com Alkalinity/pH Ryan Woosley RSMAS rwoosley@rsmas.miami.edu Alkalinity/pH Carmen Rodriguez RSMAS crodriguez@rsmas.miami.edu Alkalinity/pH Julie Paine RSMAS julie.seahorse@gmail.com Trace Metals William Landing FSU wlanding@fsu.edu Trace Metals Rachel Shelley FSU rshelley@fsu.edu Trace Metals Chris Measures U Hawaii measures@hawaii.edu Trace Metals Mariko Hatta U Hawaii mhatta@hawaii.edu CFCs/SF6 David Wisegarver PMEL eric.wisegarver@noaa.gov CFCs/SF6 Patrick Mears U Texas patrickamears@gmail.com Helium/Tritium Anthony Dachille LDEO dachille@ldeo.columbia.edu DI 14C/DOC Valentina Gonzalez-Caccia WHOI valecaccia@yahoo.com Chipod Byungho Lim OSU blim@coas.oregonstate.edu Measurement Program Summary NOAA Ship Ronald H. Brown departed Recife, Brazil, after a 2-day delay waiting for the arrival of two drums of conducting cable for the CTD winch, early morning on 23 December 2013 and arrived in Punta Arenas, Chile on 5 February 2014. A total of 113 stations were occupied during the A16S cruise which was run from north to south. The stations encompassed 113 CTD/O2/LADCP/rosette casts and 58 trace metal casts. Fourteen Argo ﬂoats were deployed during the cruise. CTD/O2 data, LADCP data, Chipod data, and 24 water samples were collected on the main CTD casts. Twelve samples were collected on most trace metal casts. With the use of the main rosette equipped with an altimeter, each cast came to within 8-20 meters of the bottom (see Appendix). The trace metal casts went to a depth of approximately 1000 meters. For all occupied stations, a 24-position, 11-liter Bullister bottle rosette frame (NOAA/AOML white frame) was used. A dedicated winch, 12-position rosette with 10-liter GO- FLO bottles, a white specially coated Rosette frame and special cable, to avoid trace metal contamination, supplied by UH/FSU was used every other station for trace metals. Salinity and nutrient samples were collected and analyzed on all the water samples collected from the CTD and trace metal casts. Detailed sample collection from the trace metal casts is outlined in the Trace Metals section describing the UH/FSU trace metal analytical program. The distribution of the Bullister bottle samples during the course of the cruise can be seen in Figures 1.1 and 1.2 below. 1. CTD DATA ACQUISITION AND ROSETTE OPERATION CTD Underwater Package Sea-Bird instrumentation was mounted in a white 24-position aluminum frame with 24, 11-liter PMEL Bullister bottles and PMEL 24-position carousel combination s/n 3210881-0053 (pylon, stations 1-44) or s/n 3217371-0163 (pylon, stations 45-113) and s/n 3232696-0471 (tripping mechanism, stations 1-30) or s/n 3217371-0163 (tripping mechanism, stations 31-113). Sea-Bird sensors on the package included AOML’s 9plus CTD s/n 09P54833-0957 and shared TCO (temperature, conductivity, oxygen) sensors: primary TCO s/n 03-02/F-1370, 04C-3860, 43-0664 with 05T-1227; and secondary TCO s/n 03-02-1710, 04C-1467, 43-1890 (stations 1-80) or 43-154 (stations 81-113) with 05T-0819. Equal distance between the temperature sensors was PMEL’s SBE 35RTinternally recording reference temperature sensor s/n 54996-0072. Also mounted on the underwater package was a Metrox load cell s/n 8756, Kongsberg altimeter s/n 1108078 (stations 1-8) or s/n 1108080 (stations 9-113) and battery pack, UH’s150 kHz downward looking LACDP and battery pack, TAMU’s Cstar transmissometer s/n CST-327DR, UCSB’s Wetlabs CDOM ﬂuorometer s/n FLCDRTD-3117(all stations except 11-12), AOML’s Wetlabs ﬂuorometer s/n FLRTD-2088 (stations 11-12), and 5 Chipod sensors and battery pack. There was no room to mount a pinger. The underwater package was electrically terminated to the new0.322" cable on the aft winch using hot glue in heat shrink. A grounding strap was necessary at the winch to prevent acquisition alarms and errors. A strand of armor was not used in the electrical termination as recommended by Sea-Bird. CTD Data Acquisition The CTD data acquisition system consisted of the ship’sSBE-11plus (V2) deck unit s/n 11P9852-0367 and a networked Dell Optiplex755 PC workstation running Windows XP Professional. SBE Seasave v.7.21d software (c.2011) was used for data acquisition and to close bottles on the rosette. Real-time digital data were backed up by the data manager, and raw data ﬁles were archived immediately after each cast on a thumb drive as well as on Survey and PMEL networked PCs. No real-time data were lost during this cruise. CTD deployments were initiated by Survey after the Bridge advised that the ship was on station. The computer console operator maintained a CTD Cast log recording position and depth information at the surface, depth, and end of each cast; a record of every attempt to close a bottle, and any pertinent comments. After the underwater package entered the water, the winch operator would lower it to 15 meters and hold. After a 60-second startup delay, the pumps turned on. The console operator watched the CTD data for reasonable values, waited three minutes at the soak depth for sensors to stabilize, instructed the winch operator to bring the package to the surface, paused for 20 seconds, and began the descent to a target depth approximately 10 meters above the sea ﬂoor. The descent rate was nominally 30 m/min to 50 m, 45 m/min to 200 m, and 60 m/min deeper than 200 m. These rates could vary depending on sea cable tension and the sea state. The console operator monitored the progress of the deployment and quality of the CTD data through interactive graphics and operational displays. The Chief or co-Chief created a sample log for the cast that would be used to record the water samples taken from each Bullister bottle. The altimeter channel, CTD depth, wire-out, and EM122 bathymetric depth were all monitored to determine the distance of the package from the bottom allowing a safe approach to within 10 meters. Bottles were closed on the upcast through the software, and were tripped 30 seconds after stopping at a bottle depth to allow the rosette wake to dissipate and the bottles to ﬂush. The winch operator was instructed to proceed to the next bottle stop 15 seconds after closing bottles to ensure that stable CTD and reference temperature data were associated with the trip. Near the surface, Survey directed the winch to stop the rosette just beneath the surface. After the surface bottle was closed, the package was recovered. Once on deck, the console operator terminated data acquisition, turned off the deck unit, and assisted with rosette sampling. At the end of each cast, primary and secondary CTDO sensors were ﬂushed with a solution of dilute Triton-X in de-ionized water using syringes ﬁtted with tubing. The syringes were left attached to the temperature ducts between casts, with the temperature and conductivity sensors immersed in the rinsing solution to guard against airborne contaminants. The transmissometer windows were cleaned and capped after each cast with the same solution to prevent salt buildup. The base of the ﬂuorometer was also cleaned but not capped after each cast. Acquisition Problems During the test cast, the primary conductivity sensor failed on the downcast and was replaced prior to the ﬁrst station with new04C sensor s/n 3860. During cast 7 and thereafter, the ﬂuorometer developed a positive offset and noisy excursions below about 3000 dbar. The connection at the ﬂuorometer as well as the y-cable between the optical sensors were tested and found not to be the problem. AOML’s FLRTD-2088 was used without issue on casts 11 and 12 to further conﬁrm the problem was with the UCSB sensor. Kongsberg altimeter s/n 078 was replaced with s/n 080 after the signal went full scale near the bottom of cast 8. Prior to cast 14, the Kongsberg altimeter battery s/n 01 was replaced with s/n 02 after corrosion and severe pitting was found at the connector. The battery charger was also investigated and the metal case was left open to facilitate air ventilation. The altimeter battery was charged every day rather than every other day because it seemed not to hold a charge as long as expected. The lithium batteries likely need to be replaced after several years of use now. The carousel trigger mechanism s/n 471 was replaced with s/n 163 prior to cast 31 after bottle 18 failed to close for the third time. The carousel pylon s/n 53 was replaced with s/n 163 prior to cast 45 after bottle 18 failed to close another four times. The transmissometer window caps were left on during cast 41. During cast 48, within the top 200 db of the upcast, the bottle ﬁring software did not increment properly. As a result, Niskins 21-24 didn’t close and the bottle data for Niskins 20, 21, and 23 were bad, and no reference temperature data were captured at those three depths. CTD data for Niskins 22 and 24 were good but there were no water samples taken. Shutting down the acquisition computer and rebooting ﬁxed the problem, and it was done every other day after that. Secondary oxygen sensor s/n 1890 was replaced with s/n 0154 prior to cast 81. The Secondary TCO sensors were slimed during cast 80 at 1600 dbar on the downcast, and secondary oxygen didn’t recover so it was replaced with AOML s/n 154 prior to cast 81. After vigorous ﬂushing with dilute Triton- X solution, temperature and conductivity differences remained the same. The new oxygen differences were even better than before. At the bottom of cast 87/2, modem errors prevented bottles from being ﬁred through the software or through the deck unit. Carousel s/n 163 was found to be at fault and was replaced with s/n 471. The station was reoccupied successfully as cast 87/3. During cast 113/1, modulo errors indicative of data dropouts began on the downcast and increased signiﬁcantly at depth. Communication was lost to the carousel so the cast was aborted. After exhaustive troubleshooting, including anew electrical termination, a second cast 113/3 was successfully collected, along with water samples. This cast still contained several modulo errors, which was believed to be caused by the wire since there was only a few meters cut off of it during termination. The top ~20 meters are usually discarded during retermination, getting rid of the section that is repeatedly strained over the block during deployments and recoveries. CTD Data Processing The reduction of proﬁle data began with a standard suite of processing modules using Sea-Bird Data Processing Version 7.21d software in the following order: • DATCNV converts raw data into engineering units and creates a .ROS bottle ﬁle. Both down and up casts were processed for scan, elapsed time(s), pressure, t0, t1, c0, c1, oxvo1, oxvo2, ox1 and ox2. Optical sensor data were converted to voltages and also carried through the processing stream. MARKSCAN was used to skip over scans acquired on deck and while priming the system under water. • ALIGNCTD aligns temperature, conductivity, and oxygen measurements in time relative to pressure to ensure that derived parameters are made using measurements from the same parcel of water. Primary and secondary conductivity were automatically advanced in the V2 deck unit by 0.073 seconds. No further alignment was warranted. It was not necessary to align temperature or oxygen. • BOTTLESUM averages burst data overan8-second interval (± 4 seconds of the conﬁrm bit) and derives both primary and secondary salinity, potential temperature (θ), and potential density anomaly (σθ). Primary and secondary oxygen (in µmol/kg) were derived in DATCNV and averaged in BOTTLESUM, as recommended recently by Sea-Bird. • FILTER applies a lowpass ﬁlter to pressure with a time constant of 0.15 seconds. In order to produce zero phase (no time shift) the ﬁlter is ﬁrst run forward through the ﬁle and then run backwards through the ﬁle. • CELLTM uses a recursive ﬁlter to remove conductivity cell thermal mass effects from measured conductivity. In areas with steep temperature gradients the thermal mass correction is on the order of 0.005 PSS-78. In other areas the correction is negligible. Nominal values of 0.03 and 7.0 s were used for the thermal anomaly amplitude (α)and the thermal anomaly time constant (ß^(-1)), respectively, as suggested by Sea-Bird. • LOOPEDIT removes scans associated with pressure slowdowns and reversals. If the CTD velocity is less than 0.25 m/s or the pressure is not greater than the previous maximum scan, the scan is omitted. • DERIVE uses 1-dbar averaged pressure, temperature, and conductivity to compute primary and secondary salinity, as well as more accurate oxygen values. • BINAV G averages the data into 1-dbar bins. Each bin is centered on an integer pressure value, e.g. the 1-dbar bin averages scans where pressure is between 0.5 dbar and 1.5 dbar. There is no surface bin. The number of points averaged in each bin is included in the data ﬁle. • STRIP removes oxygen that was derived in DATCNV. • TRANS converts the binary data ﬁle to ASCII format. Package slowdowns and reversals owing to ship roll can move mixed water in tow to in front of the CTD sensors and create artiﬁcial density inversions and other artifacts. In addition to Seasoft module LOOPEDIT, MATLAB program deloop.m computes values of density locally referenced between every 1 dbar of pressure to compute the square of the buoyancy frequency, N2, and linearly interpolates temperature, conductivity, and oxygen voltage over those records where N2 is less than or equal to -1x10(^-5)m/s(^2). Some proﬁles failed the criteria in the top 5-13 dbars. These data were retained by program deloop_post.m and will be ﬂagged as questionable in the ﬁnal WOCE formatted ﬁles. Program calctd.m reads the delooped data ﬁles and applies preliminary calibrations to temperature, conductivity, and oxygen; and computes calibrated salinity. Pressure Calibration Pre-cruise pressure calibrations did not account for the 2.4 dbar mean offset that existed with CTD s/n 0957. This offset was not applied during data acquisition but was subtracted prior to preliminary salinity and oxygen calibrations and to the preliminary data set at the end of the cruise. On-deck pressure readings prior to each cast were examined and remained within 0.5 dbar of their offsets. Differences between ﬁrst and last submerged pressures for each cast were also examined and the residual pressure offsets were also less than 0.5 dbar. Post-cruise, the ship’s barometric pressure record was used to correct the CTD pressure sensor by -2.4505 dbar. This uniform correction was based on comparing in-air pressure values from the CTD to the ship’s barometer and setting the pressure to 0 dbar at standard atmospheric pressure (1013.25 millibars), which is the TEOS-10 deﬁnition. An average offset was calculated for the entire cruise. Pressure calibrations were applied to proﬁle data using program calctd.m and to burst data using calclo.m. Temperature Calibration A viscous heating correction of -0.0006°C was applied (as recommended by Sea-Bird) prior to preliminary temperature, conductivity, and oxygen calibrations; and to the preliminary data set at the end of the cruise. Post-cruise, SBE 35 reference temperature sensor data were used to correct SBE 3 temperature sensor data. For each SBE 3 sensor, residuals between its data and that from the SBE 35 were minimized to determine a slope, offset, and pressure correction term to be applied to temperatures below a determined pressure. For secondary temperature sensor s/n 1710, these values were 8.0555e-04, -3.4122e-06, -2.9144e-07, and 2140 dbar, respectively. Temperature corrections were applied to proﬁle data using program calctd.m and to burst data using calclo.m. Conductivity Calibration Seasoft module BOTTLESUM creates a sample ﬁle for each cast. These ﬁles were appended using program sbecal.f. Program addsal.f matched sample salinities to CTD salinities by station/sample number. For secondary conductivity sensor s/n 1467, a quadratic station-dependent slope, a single conductivity bias, and a single pressure correction (pressure times measured conductivity) were determined using program calcop2.m to produce the best ﬁt to sample data for stations 1-113: • number of points used 2204 • total number of points 2636 • % of points used in ﬁt 83.61 • ﬁt standard deviation 0.001128 • ﬁt bias 0.0033106492 • ﬁt co pressure correction -3.5805367e-007 • min ﬁt slope 0.99990882 • max ﬁt slope 0.99998348 Conductivity calibrations were applied to proﬁle data using program calctd.m and to burst data using calclo.m. CTD-bottle conductivity differences plotted against station number (Figure 1.1) and pressure (Figure 1.2) allow a visual assessment of the success of the ﬁts. Figure 1.1: A16S CTD-bottle conductivity differences versus station. Figure 1.2: A16S CTD-bottle conductivity differences versus pressure. Oxygen Calibration A hybrid of the Owens-Millard (1985) and Murphy-Larson (revised 2010) oxygen sensor modeling equations was used to calibrate the SBE-43 oxygen sensor data from this cruise. The equation has the form dV Os(^T×T(cor)P×P(cor)) Ox = Soc × [V + V + τ(^DI×P+D2×T)——— ] × ———————————————————————— off dt 273.15 + T Where Ox is the CTD oxygen (µmol/kg), Soc is the oxygen signal slope, V is the measured oxygen voltage (in volts), dV/dt is the temporal gradient of the oxygen voltage (in volts/s estimated by running linear ﬁts made over 5 seconds), P is the CTD pressure (in dbar), T is the CTD temperature (in °C), and Os is the oxygen saturation computed from the CTD data following Garcia & Gordon (1992). Oxygen sensor hysteresis was improved by matching upcast bottle oxygen data to downcast CTD data by potential density anomalies referenced to the closest 1000-dbar interval using program match_sgn.m. We used the values provided by SBE for each sensor for the constants D1(1.9263e(^-4)) and D2 (-4.6480e(^-2)) to model the pressure and temperature dependence of the response time for the sensor. For each group of stations ﬁt we determined values of Soc (sometimes station dependent), V(off), τ, T(cor), and P(cor) by minimizing the residuals between the bottle oxygen and CTD oxygen. W (listed in the tables below) represents ﬁtting switches. If the switches are set to 0,0 the ﬁt is a regular L2 (least squares) norm for the entire group. If the switches are set to 1,0 the ﬁt is a regular L2 norm for the entire group but with a slope that is a linear function of station number. If the switches are set to 2,0 the program ﬁrst ﬁts the entire group, then goes back and ﬁts a slope and bias to individual stations, keeping the other parameters at the group values. If the switches are set to 0,1 the ﬁt is a regular L2 norm for the entire group but it is weighted by the nominal oxygen bottle spacing, thus ﬁtting the deep portion of the water column better. Program addsal.f matched bottle sample oxygen values to CTD oxygen values by station/sample number. Program run_oxygen_cal_ml.m was used to determine calibration coefﬁcients for two station groupings (owing to a fouling event) for primary oxygen sensor s/n 664 determined by visual inspection: Stns Start Voff Tau Tcor Pcor Points Used StdDev W Soc —————— —————— ——————— —————— ——————— —————— ——————————— —————— —— 1-79 0.4960 -0.5128 7.8554 -0.0011 0.0404 24 ea 83.3% 1.2185 20 80-113 0.5172 -0.5110 8.2289 -0.0026 0.0390 24 ea 91.7% 1.0956 20 Oxygen calibration coefﬁcients were applied to proﬁle data using program calctd.m, and to burst data using calclo.m. Calibrated (CTD - bottle) oxygen differences plotted against station number (Figure 1.3) and pressure (Figure 1.4) allow a visual assessment of the success of the ﬁts Despiking Proﬁle 10 was edited after DATCNV to remove three bad 24-Hz records around 57 dbar down and 175 dbar up. Proﬁle 80 went through some biomass around 1600 dbar down rendering the secondary conductivity and oxygen data unusable. Figure 1.3: A16S CTD-bottle oxygen differences versus station. Figure 1.4: A16S CTD-bottle oxygen differences versus pressure. Figure 1.1: A16S Sample distribution, stations 1-60. Figure 1.2: A16S Sample distribution, stations 61-113. Water Sampling The NOAA Ship Ronald H. Brown has two Markey DESH-5 winches. The Forward winch was used for all stations on A16S. All rosette casts were lowered to within 8-20 meters of the bottom, using both the altimeter to determine distance. Details of these bottom approaches can be found in the Appendix. We utilised a sample plan to stagger sample depths for all stations throughout A16S. Staggering sample depths was to avoid spatial aliasing within this sample data set. The 24-place SBE32 carousel had few bottle lanyard or mis-tripped bottle problems. Rosette maintenance was performed on a regular basis. O-rings were changed and lanyards repaired as necessary. Bottle maintenance was performed each day to insure proper closure and sealing. Valves were inspected for leaks and repaired or replaced as needed. Periodic leaks were noted on sample logs. Log notes were cross referenced with sample data values and quality coded. Log notes, mis-trips, bottle lanyard issues and associated quality codes can be found in Appendix. Bottle Sampling At the end of each rosette deployment water samples were drawn from the bottles in the following order: • Chloroﬂuorocarbons (CFCs) • Helium 3He • Dissolved Oxygen O2 • Discrete pCO2 • Dissolved Inorganic Carbon (DIC) • pH(sw25) • Total Alkalinity (TAlk) • 14CDIC • Dissolved Organic Carbon (DOC) • Oxygen Isotopes 18O/16O • Tritium • Nutrients • Density • Salinity The correspondence between individual sample containers and the rosette bottle position (1-24) 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 the proper drawing order. Normal sampling practice included opening the drain valve and then 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 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 for analysis. On-board analyses were performed on computer- assisted analytical equipment networked to the data processing computer for centralized data management. Bottle Data Processing Shipboard CTDO data were re-processed automatically at the end of each deployment using SIO/ODF CTD processing software v.5.2.0. The raw CTDO data and bottle trips acquired by SBE SeaSave on the Windows XP workstation were copied onto the Linux database and web server system. Pre-cruise calibration data were applied to CTD Pressure, Temperature and Conductivity sensor data, then the data were processed to a 0.5-second time series. A1-decibar down-cast pressure series was created from the time series; CTDO data from downcasts were matched along isopycnals to upcast trips and extracted, then ﬁt to bottle O2 data at trips. The pressure series data were used by the web service for interactive plots, sections and on-board CTDO data distribution; the 0.5 second time series data were also available for distribution through the web service. CTDO data at bottle trips were extracted and added to the bottle database to use for CTD Pressure, Temperature and Salinity data in the preliminary bottle ﬁles. Downcast CTDO data, matched to upcast bottle trips along isopycnals, were used for preliminary bottle ﬁle CTDO data. When ﬁnal CTDO data are submitted, the NOAA/PMEL ﬁnal PTSO data will replace the preliminary SIO/ODF CTD data in the bottle ﬁles. Water samples collected and properties analyzed shipboard were managed centrally in a relational database (PostgreSQL-8.1.23-6.el5_8) run on a CentOS-5.9 Linux system. A web service (OpenACS-5.3.2-3 and AOLServer- 4.5.1-1) front-end provided ship-wide access to CTD and water sample data. Web-based facilities included on-demand arbitrary property-property plots and vertical sections as well as data uploads and downloads. The Sample Log information (and any diagnostic comments) were entered into the database once sampling was completed. Quality ﬂags associated with sampled properties were set to indicate that the property had been sampled, and sample container identiﬁcations were noted where applicable (e.g., oxygen ﬂask number). Analytical results were provided on a regular basis by the various analytical groups and incorporated into the database. These results included a quality code associated with each measured value and followed the coding scheme developed for the World Ocean Circulation Experiment (WOCE) Hydrographic Programme (WHP) [Joyc94]. Various consistency checks and detailed examination of the data continued throughout the cruise. A summary of Bottle Data Quality Codes and sampling comments are included in the Appendix. Analytical Problems Few bottle problems occurred during A16S. Those that occurred are noted in the quality table in the Appendix. More speciﬁc details on analysis problems can be found in the various water property sections below. 2. SALINITY Figure 2.1: A16S shallow salinities for stations 1-113. Figure 2.2: A16S all salinities for stations 1-113. Equipment and Techniques A single Guildline Autosal, model 8400B salinometer (S/N 60843, nicknamed Joysey), located in salinity analysis room, was used for all salinity measurements. The autosal was recently calibrated on 7/20/2013 before the previous expedition, A16N. The salinometer readings were logged on a computer using Ocean Scientiﬁc International’s logging hardware and software. The Autosal’s water bath temperature was set to 24°C, which the Autosal is designed to automatically maintain. The laboratory’s temperature was also set and maintained to just below 24°C, to help further stabilize reading values and improve accuracy. Salinity analyses were performed after samples had equilibrated to laboratory temperature, usually at least 12 hours after collection. The salinometer was standardized for each group of samples analyzed (usually 2 casts and up to 52 samples) using two bottles of standard seawater: one at the beginning and end of each set of measurements. The salinometer output was logged to a computer ﬁle. The software prompted the analyst to ﬂush the instrument’s cell and change samples when appropriate. Prior to each run a sub-standard ﬂush, approximately 200 ml, of the conductivity cell was conducted to ﬂush out the DI water used in between runs. Foreach calibration standard, the salinometer cell was initially ﬂushed 6 times before a set of conductivity ratio reading was taken. For each sample, the salinometer cell was initially ﬂushed at least 3 times before a set of conductivity ratio readings were taken. IAPSO Standard Seawater Batch P-154 was used to standardize all casts. Sampling and Data Processing The salinity samples were collected in 200 ml Kimax high-alumina borosilicate bottles that had been rinsed at least three times with sample water prior to ﬁlling. The bottles were sealed with custom-made plastic insert thimbles and Nalgene screwcaps. This assembly provides very low container dissolution and sample evaporation. Prior to sample collection, inserts were inspected for proper ﬁt and loose inserts replaced to insure an airtight seal. Laboratory temperature was also monitored electronically throughout the cruise. PSS-78 salinity [UNES81] was calculated for each sample from the measured conductivity ratios. The offset between the initial standard seawater value and its reference value was applied to each sample. Then the difference (if any) between the initial and ﬁnal vials of standard seawater was applied to each sample as a linear function of elapsed run time. The corrected salinity data was then incorporated into the cruise database. When duplicate measurements were deemed to have been collected and run properly, they were averaged and submitted with a quality ﬂag of 6. On A16S, approximately 3450 salinity measurements were taken, including 219 duplicates, and approximately 112 vials of standard seawater (SSW) were used. Up to two duplicate sample, one for shallow casts, was drawn from each cast to determine total analytical precision. The running standard calibration values and duplicates are below. Through the course of the 45 day cruise, the autosal standards changed by 0.00014 in conductivity ratio (about 0.005 in salinity). The duplicates taken during the cruise showed a median precision of 0.0001 ± 0.0007 psu. Figure 2.1: A16S SSW values for stations 1-113. The good and bad starts represent the QC’d calibration standards at the beginning and end of each run used to calculate and apply the drift correction. 3. OXYGEN ANALYSIS Figure 3.1: A16S stations 1-113 Equipment and Techniques Dissolved oxygen analyses were performed with an automated titrator using amperometric end-point detection [Lang10]. Sample titration, data logging, and graphical display were performed with a PC running a LabView program written by Ulises Rivero of AOML. Lab temperature was maintained at 19.2-22.7°C. The temperature-corrected molarity of the thiosulfate titrant was determined as given by [DOE94]. Thiosulfate was dispensed by a 2 ml Gilmont syringe driven with a stepper motor controlled by the titrator. The whole-bottle titration technique of Carpenter [Carp65], with modiﬁcations by Culberson et al. [Culb91], was used. Three to four replicate 10 ml iodate standards were run every 3-4 days (SD<1 uL). Standards prepared with KIO3 solution prepared at AOML before the cruise were compared with standards prepared using KIO3 certiﬁed reference material (OSIL iodate standard). The KIO3 solutions from Guildeline were certiﬁed to be 1.667 millimolar (0.0100 N). A total of three standards were prepared using AOML (0.0100 N) KIO3 solutions and three using the OSIL certiﬁed iodate solution (bottles 26017 and 26012), with a mean and S.D. of 707.77±0.47 uL and 706.21±0.11 uL, respectively. The reagent blank determined as the difference between V1 and V2, the volumes of thiosulfate required to titrate 1-ml aliquots of the iodate standard, was determined at the beginning, middle and end of the cruise. A new step in the technique was to leave the probes soaking in 10% HNO3 between stations. This seemed to keep the response of the detector constant overtime (minimal changes in titration slope). Sampling and Data Processing Dissolved oxygen samples were drawn from Bullister bottles into calibrated 125-150 ml iodine titration ﬂasks using silicon tubing to avoid contamination of DOC and CDOM samples. Samples were drawn by counting while the ﬂask was allowed to ﬁll at full ﬂow from the Bullister. This count was then doubled and repeated thereby allowing the ﬂask to be overﬂowed by two ﬂask volumes. At this point the silicone tubing was pinched to reduce the ﬂow to a trickle. This was continued until a stable draw temperature was obtained on the Oakton meter. These temperatures were used to calculate µmol/kg concentrations, and provide a diagnostic check of Bullister bottle integrity. 1 ml of MnCl2 and 1 ml of NaOH/NaI were added immediately after drawing the sample using a Re- pipetor. The ﬂasks were then stoppered and shaken well. DIW was added to the neck of each ﬂask to create a water seal. 24 samples plus two duplicates were drawn at each station. The total number of samples collected from the rosette was 2866. The samples were stored in the lab in plastic totes at room temperature for 1 hour before analysis. The data were incorporated into the cruise database shortly after analysis. Thiosulfate normality was calculated for each standardization and corrected to the laboratory temperature. This temperature ranged between 19.2-22.7°C. Reagent blanks were run at the beginning (2.6±0.7 µL), middle (2.5±0.4 µL) and end of the cruise (3.9±0.8 µL). Volumetric Calibration The dispenser used for the standard solution (SOCOREX Calibrex520) and the burette were calibrated gravimetrically just before the cruise. Oxygen ﬂask volumes were determined gravimetrically with degassed deionized water at AOML. The correction for buoyancy was applied. Flask volumes were corrected to the draw temperature. Duplicate Samples Duplicate samples were drawn at two depths on every cast, with the exception of a very shallow cast where a duplicate was drawn at one depth only. The Bullisters selected for the duplicates and hence the oxygen ﬂasks were changed for each cast. A total of 225 sets of duplicates were run. The average standard deviation of all sets was 0.19 µmol/kg. Figure 3.2: Standard deviation of duplicate oxygen analyses performed during A16S. Median was 0.13 µmol/kg, IQR was 0.06-0.28 µmol/kg, n=223. Problems One ﬂask was replaced with a different ﬂask from a separate set due to poor ﬁtting of the stopper. At each ﬁlling of the NaI/NaOH reagent, the dispenser was rinsed out with DIW to prevent sticking. None of these problems ever rose to the point that the errors exceed 1 µmol/kg. Assigned quality codes along with comments can be found in the Appendix. 4. NUTRIENTS Figure 4.1: A16S silicate stations 1-113 Figure 4.2: A16S nitrate stations 1-113 Figure 4.3: A16S nitrite for stations 1-113 Figure 4.4: A16S phosphate stations 1-113 Equipment and Techniques Dissolved nutrients (phosphate, silicate, nitrate and nitrite) were measured by using an automated continuous ﬂow analytical system with segmented ﬂow and colormetric detection. The four channel auto-analyzer was customized with various components from other systems. The major components of the nutrient system consisted of an Alpkem auto- sampler, (model 301), two peristaltic pumps, four Lab Alliance monochrometer detectors (model 500) and custom software for digitally logging and processing the chromatograms. In addition, glass coils were used for the mixing of the nutrients. Detailed methodologies are described by [Gord94] Silicic acid was analyzed using a modiﬁcation of [Arms67]. An acidic solution of ammonium molybdate was added to a seawater sample to produce silicomolybic acid. Oxalic acid was then added to inhibit a secondary reaction with phosphate. Finally, a reaction with ascorbic acid formed the blue compound silicomolybdous acid. The color formation was detected at 814 nm. The use of oxalic acid and ascorbic acid (instead of tartaric acid and stannous chloride by [Gord94] were employed to reduce the toxicity of our waste steam. Nitrate and Nitrite analyses were also a modiﬁcation of [Arms67]. Nitrate was reduced to nitrite via a copperized cadmium column to form a red azo dye by complexing nitrite with sulfanilamide and N-1- naphthylethylenediamine (NED). Color formation was detected at 540 nm. The same technique was used to measure nitrite, (excluding the reduction step). Phosphate analysis was based on a technique by [Bern67]. An acidic solution of ammonium molybdate was added to the sample to produce phosphomolybdate acid. This was reduced to the blue compound phosphomolybdous acid following the addition of hydrazine sulfate. The color formation was detected at 819 nm. Sampling and Standards Nutrient samples were drawn in 30ml HDPE Nalgene sample bottles that had been stored in 10% HCl. The bottles are rinsed 3-4 times with sample prior to ﬁlling. A replicate was normally drawn from the deep Niskin bottle at each station for analysis to reduce carry over. Samples were then brought to room temperature prior to analysis. Fresh mixed working standards were prepared before each analysis. In addition to the samples, each analysis consisted of 4replicate standards, 3 deionized water (DIW) blanks and 3 Matrix blanks placed at the beginning and then repeated at the end (with the addition of a fourth Matrix Blank) of each run. Also, one mixed working standard from the previous analytical run was used at the beginning of the new run to determine differences between the two standards. Samples are analyzed from deep water to the surface. Low Nutrient Seawater (LNSW) was used as a wash, base line carrier and medium for the working standards. The working standard was made by the addition of 0.2 ml of primary nitrite standard and 15.0 ml of a secondary mixed standard (containing silicic acid, nitrate, and phosphate) into a 500ml calibrated volumetric ﬂask of LNSW. Working standards were prepared daily. Dry standards of a high purity were pre-weighed at PMEL. Nitrite standards were dissolved at sea. The secondary mixed standard was prepared by the addition of 30ml of a nitrate - phosphate primary standard to the silicic acid standard. Nutrient concentrations were reported in micromoles per liter. Lab temperatures were recorded for each analytical run. All the pump tubing was replaced at least three times during the A16S cruise. Approximately 3252 samples were analyzed. 5. CHLOROFLUOROCARBONS (CFCS) AND SULFUR HEXAFLUORIDE (SF6) Figure 5.1: A16S stations 1-113 Figure 5.2: A16S stations 1-113 Figure 5.3: A16S stations 1-113 A PMEL analytical system [Bull08] was used for CFC-11, CFC-12, sulfur hexaﬂuoride (SF6) and nitrous oxide (N2O) analyses on the 2013 CLIVAR A16S expedition. Approximately 1850 samples of dissolved CFC-11, CFC-12, and SF6 (’CFC/SF6’) were analysed. In general, the analytical system performed well for CFC-12, SF6 and nitrous oxide during the cruise. There were some analytical problems with CFC-11. Typical dissolved SF6 concentrations in modern surface water are approximately 1-2 fmolkg(^-1) seawater (1 fmol= femtomole = 10(^-15) moles), approximately 1000 times lower than dissolved CFC-11 and CFC-12 concentrations. The limits of detection for SF6 were approximately 0.03 fmol kg(^-1). SF6 measurements in seawater remain extremely challenging. Improvements in the analytical sensitivity to this compound at low concentrations are essential to make these measurements more routine on future CLIVAR cruises. Water samples were collected in bottles designed with a modiﬁed end-cap to minimize the contact of the water sample with the end-cap O-rings after closing. Stainless steel springs covered with a nylon powder coat were substituted for the internal elastic tubing provided with standard Niskin bottles. When taken, water samples collected for dissolved CFC-11, CFC-12 and SF6 analysis were the ﬁrst samples drawn from the bottles. Care was taken to coordinate the sampling of CFC/SF6 with other samples to minimize the time between the initial opening of each bottle and the completion of sample drawing. Samples easily impacted by gas exchange (dissolved oxygen, 3He, DIC and pH) were collected within several minutes of the initial opening of each bottle. To minimize contact with air, the CFC/SF6 samples were drawn directly through the stopcocks of the bottles into 250 ml precision glass syringes equipped with three-way plastic stopcocks. The syringes were immersed in a holding tank of clean surface seawater held at ~10°C until 20 minutes before being analyzed. At that time, the syringe was place in a bath of surface seawater heated to 30°C. For atmospheric sampling, a ~75 m length of 3/8" OD Dekaron tubing was run from the CFC van located on the fantail to the bow of the ship. A ﬂow of air was drawn through this line into the main laboratory using an Air Cadet pump. The air was compressed in the pump, with the downstream pressure held at ~1.5 atm. using a back pressure regulator. A tee allowed a ﬂowof~100 ml/min of the compressed air to be directed to the gas sample valves of the CFC/SF6 analytical systems, while the bulk ﬂow of the air (>7 l/min) was vented through the back-pressure regulator. Air samples were analyzed only when the relative wind direction was within 60 degrees of the bow of the ship to reduce the possibility of shipboard contamination. Analysis of bow air was performed at ~18 locations along the cruise track. At each location, at least ﬁve air measurements were made to determine the precision of the measurements. Analysis Concentrations of CFC/SF6 in air samples, seawater, and gas standards were measured by shipboard electron capture gas chromatography (EC-GC) using techniques modiﬁed from those described by Bullister and Weiss [Bull88] and Bullister and Wisegarver [Bull08], as outlined below. For seawater analyses, water was transferred from a glass syringe to a glass- sparging chamber (volume ˜200 ml). The dissolved gases in the seawater sample were extracted by passing a supply of CFC/SF6 free purge gas through the sparging chamber for a period of 6 minutes at ~200 ml/min. Water vapor was removed from the purge gas during passage through a Naﬁon drier. Carbon dioxide was removed with an 18 cm long, 3/8" diameter glass tube packed with Ascarite and a small amount of magnesium perchlorate desiccant. The sample gases were concentrated on a cold-trap consisting of a 1/16" OD stainless steel tube with a 2.5 cm section packed tightly with Porapak Q (60-80 mesh), a 15 cm section packed with Carboxen 1000 and a 2.5 cm section packed with MS5A. A Neslab Cryocool CC-100 was used to cool the trap to ~-70°C. After 6 minutes of purging, the trap was isolated, and it was heated electrically to ~175°C. The sample gases held in the trap were then injected onto a precolumn (~61 cm of 1/8" O.D. stainless steel tubing packed with 80-100 mesh Porasil B, held at 80°C) for the initial separation of CFC-12, CFC-11, SF6 and CCL4 from later eluting peaks. After the SF6 and CFC-12 had passed from the pre-column and into the second precolumn (25 cm of 1/8" O.D. stainless steel tubing packed with MS5A, 80°C) and into the analytical column #1 (174 cm of 1/8" OD stainless steel tubing packed with MS5A + 60 cm Porasil C held at 80°C), the outﬂow from the ﬁrst precolumn was diverted to the second analytical column (180 cm 1/8" OD stainless steel tubing packed with Porasil B, 80-100 mesh, held at 80°C). The gases remaining after CCl4 had passed through the ﬁrst pre-column, were backﬂushed from the pre column and vented. After CFC-12 had passed through the second pre-column, a ﬂow of Argon-Methane (95:5) was used to divert the N2Otoathird analytical column (30 cm of MS5A, 150°C). Column #3 and the second pre-column were held in a Shimadzu GC8 gas chromatograph with an electron capture detector (ECD) held at 330°C. Columns #1, #2, and the ﬁrst precolumn were in another Shimadzu GC8 gas chromatograph with ECD. The outﬂow from column #2 was directed to a Shimadzu Mini-2 gas chromatograph (no column) with the ECD held at 250°C. The analytical system was calibrated frequently using a standard gas of known CFC/SF6 composition. Gas sample loops of known volume were thoroughly ﬂushed with standard gas and injected into the system. The temperature and pressure were recorded so that the amount of gas injected could be calculated. The procedures used to transfer the standard gas to the trap, precolumn, main chromatographic column, and ECD were similar to those used for analyzing water samples. Four sizes of gas sample loops were used. Multiple injections of these loop volumes could be made to allow the system to be calibrated over a relatively wide range of concentrations. Air samples and system blanks (injections of loops of CFC/SF6 free gas) were injected and analyzed in a similar manner. The typical analysis time for seawater, air, standard or blank samples was ˜11 minutes. Concentrations of the CFC-11 and CFC-12 in air, seawater samples, and gas standards are reported relative to the SIO98 calibration scale [Prin00], [Bull10]. Concentrations of SF6 in air, seawater samples, and gas standards are reported relative to the SIO-2005 calibration scale [Bull10]. Concentrations in air and standard gas are reported in units of mole fraction CFC in dry gas, and are typically in the parts per trillion (ppt) range. Dissolved CFC concentrations are given in units of picomoles per kilogram seawater (pmol/kg) and SF6 concentrations in fmol/kg. CFC/SF6 concentrations in air and seawater samples were determined by ﬁtting their chromatographic peak areas to multi-point calibration curves, generated by injecting multiple sample loops of gas from a working standard (PMEL cylinder WRS72611) into the analytical instrument. The response of the detector to the range of moles of CFC/SF6 passing through the detector remained relatively constant during the cruise. Full-range calibration curves were run at intervals of 4-5 days during the cruise. Single injections of a ﬁxed volume of standard gas at one atmosphere were run much more frequently (at intervals of ~90 minutes) to monitor short-term changes in detector sensitivity. The purging efﬁciency was estimated by re-purging a high-concentration water sample and measuring this residual signal. At a ﬂow rate of 200 cc/min for 6 minutes, the purging efﬁciency for both SF6 and CFC gases was > 99%. The efﬁciency for N2O was about 97%. On this expedition, based on the analysis of more than 190 pairs of duplicate samples, we estimate precisions (1 standard deviation) of about 1% or 0.002 pmol/kg (whichever is greater) for dissolved CFC-12 and CFC-11 measurements. The estimated precision for SF6 was 2% or 0.02 fmol kg(^-1), (whichever is greater). Overall accuracy of the measurements (a function of the absolute accuracy of the calibration gases, volumetric calibrations of the sample gas loops and purge chamber, errors in ﬁts to the calibration curves and other factors) is estimated to be about 2% or 0.004 pmol/kg for CFC11 and CFC-12 and 4% or 0.04 fmol/kg for SF6). A small number of water samples had anomalously high CFC-12 and/or SF6 concentrations relative to adjacent samples. These samples occurred sporadically during the cruise and were not clearly associated with other features in the water column (e.g., anomalous dissolved oxygen, salinity, or temperature features). This suggests that these samples were probably contaminated with CFCs/SF6 during the sampling or analysis processes. Measured concentrations for these anomalous samples are included in the data ﬁle, but are given a quality ﬂag value of either 3 (questionable measurement) or 4 (bad measurement). Less than 2% of samples were ﬂagged as bad or questionable during this voyage. A quality ﬂag of 5 was assigned to samples which were drawn from the rosette but never analyzed due to a variety of reasons (e.g., leaking stopcock, plunger jammed in syringe barrel, etc.). During the cruise an analytical problem developed with the analysis of CFC-11. After numerous attempts to solve the problem, it was determined that the calibration loop used for monitoring the stability of the detector, was producing large and variable responses. A second large loop was created and its volume crudely determined using CFC-12 and nitrous oxide. It is believed this determination of the volume is within about 2% of the true volume, and will require a robust calibration upon its return in the laboratory. However, using this loop allowed the measurements of CFC-11 to continue. The worst of the problems occurred between stations 30 and 60 and these data were ﬂagged as questionable. A signiﬁcant number of samples in the deep (>3000 m) Brazil Basin between about 20°S and 33°S had anomalously high SF6 concentrations relative to the CFC-11 and CFC-12 concentrations. These high SF6 concentrations occurred in a coherent pattern in the water column over more than 20 stations and are thought to be due to earlier deliberate deep SF6 tracer release experiments in this region [Rye12]. 6. DISCRETE pCO2 Figure 6.1: A16S stations 1-113 Sampling Samples were drawn from 11-L Bullister bottles into 500 ml glass bottles using Tygon tubing with a Silicone adapter that ﬁt over the spigot to avoid contamination of DOM samples. Bottles were rinsed twice with about 200 ml of seawater. Then they were ﬁlled from the bottom, overﬂowing half a volume while taking care not to entrain any bubbles. About 5 ml of water were withdrawn to allow for expansion of the water as it warms and to provide space for the stopper and tubing of the analytical system. Saturated mercuric chloride solution (0.2 ml) was added as a preservative. The sample bottles were sealed with glass stoppers lightly covered with grease (Down Corning silicone high vacuum grease) and were stored at room temperature for a maximum of twelve hours prior to analysis. The analyses for pCO2 were done with the discrete samples at 20°C. A primary water bath was kept within 0.03°C of the analytical temperature; a secondary bath was kept within 0.3°C of the analytical temperature. The majority of the samples were analyzed in batches of twelve bottles with 17 minute run time, which with standards took approximately 4 hours. When twelve bottles were moved into the primary water bath for analyses, the next twelve bottles were moved into the secondary water bath. Sample bottles spent at least two hours in the secondary water bath prior to being moved to the analytical water bath. A spot check indicated that bottom water samples (approx. 2°C) reached a temperature of 18.6-18.8°C after 2.5 hours in the pre-bath. The sampling focus was on drawing full casts every 2 degrees in latitude. Duplicate samples from the same Niskin were drawn to check the precision of the sampling and analysis. Some discrete samples were collected from the underway (UW) ﬂowing sea water line aboard the ship. The UW samples will be compared to the results from the autonomous pCO2 instrument. Most discrete UW samples were collected as a station was being completed. Over 700 samples were drawn at 113 stations. About 28 duplicate samples were collected from the UW seawater line. More than 140 sets of duplicate bottles were drawn at various depths. The average relative deviation / Max - Av \ | = ————————— | of these duplicate pairs was 0.3% while the median \ Av × 100 / relative error was 0.1%. Analyzer Description The principles of the discrete pCO2 system are described in [Wann93] and [Chip93]. The major difference in the current system is the method of equilibrating the water sample by passing it once through the equilibriation module into a drain, with the constantly circulating gas phase. This system uses miniature membrane contactors (Micromodules from Membrana, Inc.), which contain bundles of hydrophobic micro-porous tubes in polycarbonate shells (2.5 x 2.5 x 0.5 cm). The sample water is pumped for 17 minutes over the outside of the tubing bundles in two contactors in series at approximately 20 ml/min, with a total of 350 ml of the 550 ml of the bottle used. The gas is recirculated in a vented loop, which includes the tubing bundles and a non-dispersive infrared analyzer (LI- COR™ model 840) at approximately 24 ml/min. There was a slight draw into the vent of 0-1 ml/min based on the ﬂuctuations of an Aalborg electronic ﬂowmeter on the vent line. The ﬂow rates of the water (20 ml/min) and gas (24 ml/min) for the A16S cruise are chosen with consideration of competing concerns. This optimization differs for different cruises. Faster water and gas ﬂows yield faster equilibration. A slower water ﬂow would allow collection of smaller sample volume; plus a slower gas ﬂow would minimize the pressure increase in the contactor. Additionally, the ﬂowrates are chosen so that the two ﬂuids generate equal pressures at the micro-pores in the tubes to avoid leakage into or out of the tubes. A signiﬁcant advantage of this instrumental design is the complete immersion of the miniature contactors in the constant temperature bath. Also in the water bath are coils of stainless steel tubing before the contactors that ensure the water and gas enter the contactors at the known equilibration temperature. The instrumental system employs a large insulated cooler (Igloo Inc.) that accommodates twelve sample bottles, the miniature contactors, a water stirrer, a copper coil connected to a refrigerated circulating water bath, an immersion heater, a12-position sample distribution valve, two thermistors, and two miniature pumps. The immersion heater works in opposition to the cooler water passing through the copper coil. One thermistor is immersed in the water bath, while the second thermistor is in a sample ﬂow cell after the second contactor. The difference between the two thermistor readings was consistently less than 0.05°C. In a separate enclosure are the 8-port gas distribution valve, the infrared analyzer, a barometer, and other electronic components. The gas distribution valve is connected to the air-circulation pump and to six standard gas cylinders. The instrumental system was designed and built by Tim Newberger and was supported by C. Sweeney and T. Takahashi. Their skill, assistance, and generosity were essential to the successful use of this instrumental system during this cruise. Standardization To ensure analytical accuracy, a set of six gas standards (ranging from 288 to 1534 ppm) was run through the analyzer before and after every sample batch. The standards were obtained from Scott-Marin and referenced against primary standards purchased from C.D. Keeling in 1991, which are on the WMO-78 scale. Standard Gas Cylinders Cylinder ppm CO2 ———————— ——————— JB03282 288.46 JB03268 384.14 JB03309 567.40 CA05980 792.51 CA05984 1036.95 CA05940 1533.7 Data Processing A custom program developed using LabView™ controls the system and graphically displays the CO2 concentration as well as the temperature and pressure during the equilibration step of the process. The CO2 in the gas phase changes greatly during the ﬁrst minute of a new sample and then goes through several more oscillations. The oscillations dampen quickly as the concentration asymptotically approaches equilibrium. The ﬂows are stopped after 17 minutes, and the program records an average of ten readings from the infrared analyzer along with other sensor readings. The data ﬁles from the discrete pCO2 program are reformatted so that a Matlab program designed for processing data from the continuous pCO2 systems can be used to calculate the fugacity of the discrete samples at 20°C. The details of the data reduction are described in [Pier09]. Problems There were several issues with the system that had remained on the ship after A16N and did not get its usual pre-cruise check and refurbishment. During the ﬁrst run at the test station water got into the Naﬁon drier and IR possibly due to a blocked distribution valve. The Naﬁon drier was replaced. The IR did not respond except to the highest standard. The IR (Li-840) ﬂow cell was removed following downloaded instructions and it was discovered that the bottom half of the gold mirrored cell was lightly coated with salt. It was cleaned with acetone and DI water and dried. The zero and span software was downloaded but because of interface issues only the CO2 channel was spanned and not the H2O channel which was unresponsive and showed a reading of about 8 mmol/mol throughout the cruise, irrespective if sample or standard was run. On several occasions the head of the 8-position gas distribution valve came loose and the gas ﬂow was interrupted. Initially it was thought that the valve was clogged and cleaning was attempted. The distribution valve was cleaned once and then replaced. To get enough torque on the hexscrew on the collar of the head securing it to the valve body, a small hole was drilled in the enclosure to be able to use a long allen wrench. The water pump had issues starting to pump water from sample bottles and priming was required to start the ﬂow. The pump was replaced mid-cruise and this solved the problem. Samples did not reach full equilibrium in the ﬁrst stations, regardless of increasing the equilibration time. As the cruise progressed, the equilibration achieved decreased from 99% to 96%. The membrane modules were cleaned with acid to improve performance and when that didn’t work, they were replaced. After replacement of the modules, equilibration (> 99.7 %) was achieved before the end of the equilibration time. In the last stations, a decrease of up to 6 ppm in the measurements was sometimes observed in the last minutes of the equilibration period. For some samples the sinusoidal response observed for the ﬁrst 6 minutes reappeared suddenly around 10 minutes. During the cruise, the laptop controlling the analytical system suffered occasional crashes (blue screen of death). The error message indicated the problem was with a memory overload or interaction with the keyspan in the system. Rebooting the computer every 24 samples seemed to decrease the frequency of the crashes. The response to all standards decreased appreciably (by about 80 ppm for the 1533 ppm standard) in the last week of the cruise but relative response remained unaffected. Tests Several tests were performed during the cruise in part to facilitate post-cruise data reduction. A test was run to evaluate the difference in CO2 measurements when the six standard gases were wetted by bubbling through a small volume of acidiﬁed DI water versus running them dry. No signiﬁcant differences were observed. To check for possible gas loss during equilibration through the Naﬁon drier and/or the vent, a duplicate sample was run with the regular N2 gas through the naﬁon drier. The air circulation loop vent line was placed in the N2 ﬂow, such that N2 would enter the vent. Then for the next duplicate the N2 was replaced by the 1533 ppm std. No difference was seen indicating the integrity of the air circulation loop. During the cruise we tested the preservation of the water samples with and without preservative (mercuric chloride) and with and without grease on the stopper. Samples were stored up to 48 hours and analyzed later. No signiﬁcant difference was observed between the greased/poisoned and ungreased/non-poisoned samples. Post cruise data reduction The data supplied are preliminary and represent the pCO2(20) values as calculated by the data acquisition program, developed by Tim Newberger using the preceding standards and water bath temperature readings by the thermistors that appear very precise but biased high by 0.3°C compared to a Fluke/Hart thermometer. The water channel was not functioning. For ﬁnal data reduction the thermistors need to be calibrated in the lab, the response of the detector needs to be compared with current setting and after spanning and zeroing both CO2 and H2O channels. The response of equilibration needs to be determined from the RAW ﬁles that log data for each run at 1-second intervals and data has to be adjusted. These RAW ﬁles will also be used to pick the plateau in concentrations for the samples where concentrations changed in the last 5 minutes as the correct value. Undwerway pCO2 Analysis During the A16S cruise, there was an automated underway pCO2 system from AOML situated in the hydrolab, as it has been since 1997. The current design of the instrumental system is based on [Wann93], and Feely et al. [Feel98], while the details of the instrument and of the data processing are described in Pierrot, et.al. [Pier09]. The repeating cycle of the system includes 4 gas standards, 5 ambient air samples, and 66 headspace samples from its equilibrator within 3.3 hours. The concentrations of the standards range from 285 to 546 ppm CO2 in compressed natural air. They were purchased from NOAA/ESRL in Boulder and are directly traceable to the WMO scale. The system includes an equilibrator where approximately 0.6 liters of constantly refreshed surface seawater from the bow intake is equilibrated with 0.8 liters of gaseous headspace. The water ﬂowrate through the equilibrator was 1.5 -2.0 liters/min, which yielded a vigorous spray pattern during this cruise. The equilibrator headspace is circulated through a non-dispersive infrared analyzer (IR) (LI-COR™ model 6262) and then returned to the equilibrator. When ambient air or standard gas is analyzed, the gas leaving the analyzer is vented to the lab. A KNF pump constantly draws 6- 8 liter/min of marine air through 100 m of 0.95 cm (= 3/8") OD Dekoron™ tubing from an intake on the bow mast. The intake has a rain guard and a ﬁlter of glass wool to prevent water and larger particles from reaching the pump. The headspace and marine air gases are dried before ﬂushing the IR analyzer. A custom program developed using LabView™ controls the system and graphically displays the air and water results. The program records the output of the infrared analyzer, the GPS position, water and gas ﬂows, water and air temperatures, internal and external pressures, and a variety of other sensors. The program records all of these data for each analysis. Problems The system ran very well during the cruise and only two problems were encountered. During the start of the cruise the circulation gas was high and variable at about 120 ml/min. This did not seem to affect the CO2 values. Flow was decreased to 80 ml/min and ﬂows were steadier. On Jan. 22nd, the uncontaminated seawater line pump was turned off for about 12 hours after the strainer became clogged twice with salps. 7. DISSOLVED INORGANIC CARBON (DIC) Figure 7.1: A16S stations 1-113 Sampling Samples for TCO2 measurements were drawn according to procedures outlined in the Handbook of Methods for CO2 Analysis [DOE94] from Bullister bottles into cleaned 294-ml glass bottles. Bottles were rinsed and ﬁlled from the bottom, leaving 6 ml of headspace; care was taken not to entrain any bubbles. After 0.2 ml of saturated HgCl2 solution was added as a preservative, the sample bottles were sealed with glass stoppers lightly covered with Apiezon-L grease and were stored at room temperature for a maximum of 12 hours prior to analysis. TCO2 samples were collected from a variety of depths with one to three replicate samples. Typically the replicate seawater samples were taken from the surface, around 1000 m, and bottom Bullister bottles and run at different times during the cell. No systematic difference between the replicates was observed. Analysis The TCO2 analytical equipment was set up in a seagoing laboratory van. The analysis was done by coulometry with two analytical systems (AOML3 and AOML4) used simultaneously on the cruise. Each system consisted of a coulometer (UIC, Inc.) coupled with a Dissolved Inorganic Carbon Extractor (DICE) inlet system. DICE was developed by Esa Peltola and Denis Pierrot of NOAA/AOML and Dana Greeley of NOAA/PMEL to modernize a carbon extractor called SOMMA [John85] [John87] [John92] [John93] [John99]. In the coulometric analysis of TCO2,all carbonate species are converted to CO2 (gas) by addition of excess hydrogen ion (acid) to the seawater sample, and the evolved CO2 gas is swept into the titration cell of the coulometer with pure air or compressed nitrogen, where it reacts quantitatively with a proprietary reagent based on ethanolamine to generate hydrogen ions. In this process, the solution changes from blue to colorless, triggering a current through the cell and causing coulometrical generation of OH(^-) ions at the anode. The OH(^-) ions react with the H(^+), and the solution turns blue again. A beam of light is shone through the solution, and a photometric detector at the opposite side of the cell senses the change in transmission. Once the percent transmission reaches its original value, the coulometric titration is stopped, and the amount of CO2 that enters the cell is determined by integrating the total charge during the titration. The coulometers were calibrated by injecting aliquots of pure CO2 (99.99%) by means of an 8-port valve outﬁtted with two sample loops with known gas volumes bracketing the amount of CO2 extracted from the water samples for the two AOML systems. The stability of each coulometer cell solution was conﬁrmed three different ways: two sets of gas loops were measured at the beginning; also the Certiﬁed Reference Material (CRM), Batch 129, supplied by Dr. A. Dickson of SIO, was measured at the beginning; and the duplicate samples at the beginning, middle, and end of each cell solution. The coulometer cell solution was replaced after 25-30 mg of carbon was titrated, typically after 9-12 hours of continuous use. The pipette volume was determined by taking aliquots at known temperature of distilled water from the volumes. The weights with the appropriate densities were used to determine the volume of the pipettes. Calculation of the amount of CO2 injected was according to the CO2 handbook (DOE 1994). The concentration of CO2 ([CO2]) in the samples was determined according to: (Counts - Blank × Run Time) × K [CO2] = Cal. Factor time —————————————————————————————————— Pipette Volume × Sample Density where Cal. Factor is the calibration factor, Counts is the instrument reading at the end of the analysis, Blank is the counts/minute determined from blank runs performed at least once for each cell solution, Run Time is the length of coulometric titration (in minutes), and K is the conversion factor from counts to µmol. All TCO2 values were recalculated to a molar weight (µmol/kg) using density obtained from the CTD’s salinity. The TCO2 values were corrected for dilution by 0.2 ml of saturated HgCl2 used for sample preservation. The total water volume of the sample bottles was 288 ml (calibrated by Esa Peltola, AOML). The correction factor used for dilution was 1.0007. A correction was also applied for the offset from the CRM. This correction was applied for each cell using the CRM value obtained in the beginning of the cell. The average correction was -3.22 µmol/kg for AOML 3 and 1.57 for AOML 4. The average difference of the duplicates was 1.58 µmol/kg for AOML 3 and 1.57 for AOML 4. The results underwent initial quality control on the ship using TCO2-pressure proﬁles and TCO2-NO3 and TCO2-pH plots. Analytical Problems In general, both systems worked well. One solenoid valve failed and was replaced. Two cell caps went bad and a new one was constructed. On station 34, the calibration factor was unusually high after running 3 gas loops. The CRM value was very good with the high calibration factor, but later comparisons with NO3 and pH showed that all analyses for this station are likely bad. This anomalous calibration factor did not recur during the cruise. The total dissolved inorganic carbon data reported to the database directly from the ship are to be considered preliminary until a more thorough quality assurance can be completed shore side. 8. pH Figure 8.1: pH (sea water at 25 C) on A16S stations 1-113 Sampling Samples were collected in 50ml borosilicate glass syringes rinsing 2 times and thermostated to 25°C before analysis. Two duplicates were collected from each station. Samples were collected on the same Bullister bottles as total alkalinity and dissolved inorganic carbon in order to completely characterize the carbon system. One sample per station was collected and analyzed with double the amount of indicator in order to correct for pH changes as a result of adding the indicator, this correction has not been applied to the preliminary data. All data should be considered preliminary. Analysis pH (umol/kg seawater) on the seawater scale was measured using a Agilent 8453 spectrophotometer according to the methods outlined by [Clay93] An RTE10 water bath maintained spectrophotometric cell temperature at 25.0°C. A 10cm ﬂow through cell was ﬁlled automatically using a Kloehn 6v syringe pump. The sulfonephthalein indicator m-cresol purple (mCP) was also injected automatically by the kloehn 6v syringe pump into the spectrophotometric cells, and the absorbance of light was measured at three different wavelengths (434 nm, 578 nm, 730 nm). The ratios of absorbances at the different wavelengths were input and used to calculate pH on the total and seawater scales, incorporating temperature and salinity into the equations. The equations of [Dick87], Dickson and Riley [Dick79], and Dickson [Dick90] were used to convert pH from total to seawater scales. Salinity data were obtained from the conductivity sensor on the CTD. These data were later corroborated by shipboard measurements. Temperature of the samples was measured immediately after spectrophotometric measurements using a Guildline 9540 digital platinum resistance thermometer. Reagents The mCP indicator dye was a concentrated solution of approx. 2.0 mM. Unpurifed indicator was used purchased from Alpha-Aeser. Standardization The precision of the data can be accessed from measurements of duplicate samples, certiﬁed reference material (CRM) Batch 129 (Dr. Andrew Dickson, UCSD) and TRIS buffers. The measurement of CRM and TRIS was alternated at each station. The mean and standard deviation for the CRMs was 7.9125± 0.0033 (n=58) and 8.0879±0.0035 (n=40) for TRIS buffer. TRIS bottles 6 and 7 were high by approximately 0.01 relative to all measurements on both A16N and A16S and have thus been excluded. Data Processing Addition of the indicator affects the pH of the sample, and the degree to which pH is affected is a function of the pH difference between the seawater and indicator. Therefore, a correction is applied for each batch of dye. One sample from each station was measured twice, once normally and a second time with double the amount of indicator. The change in the ratio is then plotted versus the change in the isobestic point to develop an empirical relationship for the effect of the indicator on the pH. A preliminary correction based on the measurements of A16N has been applied to this data. The mean and standard deviation of the duplicates was 0.0004 ± 0.0017 (N = 198). The preliminary quality control is shown in the Appendix Table. Problems The only major problem that occurred was on station 108 when the water bath failed and was unable to cool. The variability in the temperature of the water bath showed increased variability the few days before it failed, but was still within the acceptable range. The water bath was quickly replaced and no samples were lost. 9. TOTAL ALKALINITY Figure 9.1: A16S stations 1-113 Sampling At each station total alkalinity (TA) samples were drawn from Bullister bottles into 500 ml borosilicate ﬂasks using silicone tubing that ﬁt over the stopcock. Bottles were rinsed a minimum of three times, then ﬁlled from the bottom and allowed to overﬂow half of the bottle volume. The sampler was careful not to entrain any bubbles during the ﬁlling procedure. Approximately 15 ml of water was withdrawn from the ﬂask by halting the sample ﬂow and removing the sampling tube, thus creating a reproducible headspace for thermal expansion during thermal equilibration. The sample bottles were sealed at a ground glass joint with a glass stopper. The samples were then thermostated at 25°C before analysis. Three duplicates were collected at each station. Samples were collected from the same Bullister bottles as pH or dissolved inorganic carbon (DIC) in order to completely characterize the carbon system. Analyzer Description The sample TA was then evaluated from the proton balance at the alkalinity equivalence point, 4.5 at 25°C and zero ionic strength. This method utilized a multi-point hydrochloric acid titration of seawater [Dick81]. The instrument program used a Levenberg-Marquardt nonlinear least-squares algorithm to calculate the TA, DIC, and pH from the potentiometric titration data. The program was patterned after those developed by [Dick81], [Joha82], and [DOE94]. The least-squares algorithm of the potentiometric titrations not only gave values of TA but also those of DIC, initial pH as calculated from the initial EMF, the standard potential of the electrode system (E0), and the ﬁrst dissociation constant of CO2 at the given temperature and ionic strength (pK1). Two titration systems, A and B were used for TA analysis. Each of them consisted of a Metrohm 765 Dosimat titrator, an Orion 720A or 720A+, pH meter and a custom designed plexiglass water-jacketed titration cell [Mill93]. The titration cell allowed for the titration to be conducted in a closed system by incorporating a 5 ml ground glass syringe to allow for volume expansion during the acid addition. The seawater samples were temperature equilibrated to a constant temperature of 25± 0.1°C with a water bath (Neslab, RTE-10). The electrodes used to measure the EMF of the sample during a titration were a ROSS glass pH electrode (Orion, model 810100) and a double junction Ag, AgCl reference electrode (Orion, model 900200). The water-jacketed cell was similar to the cells used by [Brad88] except a larger volume (~200 ml) was employed to increase the precision. Each cell had a ﬁll and drain valve which increased the reproducibility of the volume of sample contained in the cell. A typical titration recorded the stable solution EMF (deviation less than 0.09 mV) and added enough acid to change the voltage a pre-assigned increment (13 mV). A full titration (25 points) took about 20 minutes. A 6 port valve (VICI, Valco EMTCA-CE) allowed 6 samples to be loaded into the instrument and successively measured. Reagents A single 50-l batch of -0.25 m HCl acid was prepared in 0.45 m NaCl by dilution of concentrated HCl, AR Select, Mallinckrodt, to yield a total ionic strength similar to seawater of salinity 35.0 (I = 0.7 M). The acid was standardized by a coulometric technique [Mari68] [Tayl59], and veriﬁed with alkalinity titrations on seawater of known alkalinity. The calibrated molarity of the acid used was 0.24361 ±0.0001 N HCl. The acid was stored in 500-ml glass bottles sealed with Apiezon L grease for use at sea. Standardization The reproducibility and precision of measurements were checked using low nutrient surface seawater, used as a substandard, and Certiﬁed Reference Material (CRM) from Dr. Andrew Dickson, Marine Physical Laboratory, La Jolla, California. The CRM was utilized to account for instrument drift over the duration of the cruise and to maintain measurement precision. One CRM was measured on each instrument every other station as well as the low nutrient surface. Duplicate analysis provided additional quality assurance. Three duplicates were taken, in which 2 samples were taken from the same Bullister bottle, at each station. The duplicates were then analyzed on system A, system B, or split between systems A and B. This provided a measure of the precision on the same system and between systems. Laboratory calibrations of the Dosimat burette system with water indicated the systems delivered 3.000 ml of acid (the approximate value for a titration of 200 ml of seawater) to a precision of ±0.0004 ml, resulting in an error of ±0.3 µmol/kg in TA. Data Processing Measurements on CRM batches 129 were made. The difference between the measured and certiﬁed values on system A is 1.87 ± 2.85 (N=55) and on B is 2.73 ± 3.45 (N=55). Part way through the cruise a noticeable decrease in precision of the CRMs occurred. It was determined to be caused by using old CRMs from DIC, the use of which was immediately stopped. These old CRMs have not yet been excluded from the data analysis; this is the reason for the high standard deviation of the CRMs and will be improved when they are excluded during ﬁnal data analysis. Six different batches of low nutrient surface water were used. All had standard deviations between 0.5 and 2.5µmol/kg. A total of 306 sets of duplicates were analyzed. The preliminary mean and standard deviations for both run on system A is 0.04 ± 1.84 (N = 103), for both run on system B is -0.13 ± 1.75 (N = 93), and for one on each system (A-B) is 2.04 ± 278 (N = 98). Problems The only major problem occurred on station 105 when the computer for system B irreparably crashed. It was quickly replaced and only resulted in the loss of one sample. 10. DISSOLVED ORGANIC CARBON (DOC) DOC and Total Dissolved Nitrogen (TDN) samples were taken from every Bullister bottle at every other station (odd stations). 1368 samples were taken from 57 stations in total. Samples from depths of 250m and shallower were ﬁltered through GF/F ﬁlters using in-line ﬁltration. Samples from deeper depths were not ﬁltered. High-density polyethylene 60 ml sample bottles were pre-cleaned with 10% HCl and rinsed with Mili-Q water. Filters were combusted a 450°C overnight. Filter holders and silicone tube were cleaned with 10% HCl and rinsed with Mili-Q water before sampling. Bottles were rinsed three times with the seawater before collecting 50-60 ml of sample at each Bullister bottle. Samples were kept frozen in coolers inside the ship’s freezer. Frozen samples will ship back to Miami in four coolers for laboratory analysis. Gloves were used during all process of collection and storage. 11. CARBON ISOTOPES IN SEAWATER ((^14/13)C) A total of 576 samples were collected from 25 stations. In addition, surface samples were also collected from 14 stations. Seven stations were partially sampled (16 samples) while the rest were full cast (24 samples). Duplicates were collected at almost all stations. Samples were collected in 500 ml airtight glass bottles. Using silicone tubing, the ﬂasks were rinsed 2 times with the seawater from the correspondent Niskin bottle. While keeping the tubing at the bottom of the ﬂask, the ﬂask was ﬁlled and ﬂushed by allowing it to overﬂow one and a half times its full volume. Once the sample was taken, a small amount (about 30 cc) of water was removed to create a headspace and 200 l of 50% saturated mercuric chloride solution was added in the sampling bay. In order to avoid contamination, gloves were used during all collection, handling, and storage processes. Sample handling was done on a clean table covered with new aluminum foil for each batch. After all samples were collected from a station the glass stoppers were dried and greased with Apiezon-M grease to ensure an air tight seal. The stoppers were secured with a rubber band which wrapped over the entire bottle. The samples were stored in AMS crates or boxes inside the ship’s main laboratory during the cruise. The samples will be shipped to WHOI for analysis. The radiocarbon/DIC content of seawater (DI14C) is measured by extracting the inorganic carbon as CO2 gas, converting the gas to graphite, then counting the number of 14C atoms in the sample directly using an accelerator mass spectrometer (AMS). Radiocarbon values will be reported as 14C using established procedures modiﬁed for AMS applications. The 13C/12C of the CO2 extracted from seawater is measured relative to the 13C/12C a CO2 gas standard calibrated to the PDB standard using an isotope radio mass spectrometer (IRMS) at NOSAMS. Problems 16 boxes of pre-cleaned bottles got wet with rainwater in Recife, Brazil prior to leaving. Samples were collected in 10 of these boxes making sure that bottles were clean and dry and not affected by the rain water at all. 12. TRITIUM, HELIUM AND (^18)O Helium samples were taken from designated Niskins in 90 cc 316 type stainless steel gas tight vessels with valves. The samples were then extracted into aluminum silicate glass storage vessels within 24 hours using the at sea gas extraction system. The helium samples are to be shipped to the Lamont-Doherty Earth Observatory of Columbia University Nobel Gas Lab for mass spectrometric measurements. A corresponding one- liter water sample was collected from the same Niskin as the helium sample in a preprocessed glass bottle for degassing back at the shore based laboratory and subsequent tritium determination by 3He in-growth method. 18O samples were collected and shipped to LDEO for analysis. During A16S, 18 stations were sampled, collecting 346 samples for tritium, 414 samples for helium and 254 samples for 18O analysis. No duplicate samples were taken. 13. DENSITY Sampling Over the course of A16S, 5 stations were sampled (stations 19, 43, 67, 85 and 111), for a total of 111 density samples. Each Niskin was sampled using a 150 ml HDPE bottle. The bottles were rinsed 3 times, allowed to ﬁll until overﬂowing, capped, and sealed with Paraﬁlm. This procedure leaves as little head space as possible to minimize evaporation until analysis. Analyzer Description The sealed samples will be shipped to the Millero Lab at RSMAS in Miami where the salinity will be re-measured on a salinometer (Guildline Portosal), and the density will be measured using an Anton-Paar DMA 5000 densitometer. 14. LADCP System Conﬁguration A single downward-facing WH150-kHz LADCP (serial number 16283) was secured with brackets to a metal plate mounted on 24-bottle CTD rosette frame. The ADCP was positioned to avoid interference with the rosette frame. The instrument was connected to a NOAA 48-Volt rechargeable lead- acid battery pack mounted in the center of the rosette via a NOAA custom star cable assembly typically used for conﬁgurations consisting of both upward and downward looking ADCPs. Since only one ADCP was used in this conﬁguration, the unused cable connectors were covered with dummy caps. On deck, the rosette was moved into and out of a sheltered sampling hanger atop a platform mounted on two tracks. The power supply and data transfer was handled independently from any CTD connections. While on deck, a communications and power cable was connected to a cable in the sampling hangar that ran into the hydro lab on the NOAA Ship Ronald H. Brown. This cable connected to a NOAA battery charger located in the Hydro lab for power and an acquisition computer via USB connection for data download. The LADCP and CTD acquisition computer clocks both used NTP to stay in sync with the ship clock and to assure that the absolute time recorded by the CTD and LADCP were the same. Figure 14.1: Cross-sectional diagram (looking down) of CTD rosette showing relative position and orientation of ADCP. LADCP Operation Operational LADCP scripts, written in python by Eric Firing and the group at the University of Hawaii, were used for instrument control and data transmission. The command ﬁle used in communication with the LADCP is shown below: •CR1 # factory defaults •PS0 # Print system serial number and other info. •WM15 # sets LADCP mode; WB -> 1, WP -> 001, TP -> 000100, TE -> 0000010 0 •TC2 # 2ensembles per burst •TB 00:00:02.80 •TE 00:00:01.20 •TP 00:00.00 •WN40 # 40 cells, so blank + 320 m with 8-m cells •WS0800 # 8-m cells •WT1600 # 16-m pulse •WF1600 # Blank, 16-m •WV330 # 330 is max effective ambiguity velocity for WB1 •EZ0011101 # Soundspeed from EC (default, 1500) •EX00100 # No transformation (middle 1 means tilts would be used otherwise) •CF11101 # automatic binary, no serial •LZ30,230 # for LADCP mode BT; slightly increased 220->230 from Dan Torres •CL0 # don’t sleep between pings (CL0 required for software break) This command ﬁle was sent to the instrument prior to each cast. Communication between the computer and the instrument was then terminated, the battery charger was turned off, the power cable was disconnected, and all connections were sealed with dummy plugs and secured. After the CTD was brought back on deck after a cast, the data and the power supply cable was rinsed with fresh water and reconnected to the computer and battery charger. The data acquisition was terminated, the battery was charged, and the data were downloaded using the LADCP software. The battery charger remained on from the time of data download until the time the instrument was prepared for the next cast. Log ﬁles were kept for each cast to ensure that all the steps were completed and a data acquisition log was maintained during the cruise to summarize the data collected and document any special situations in the data collection or processing. Data Processing Within 10 hours after each cast, the data were preliminarily processed using Lamont-Doherty Earth Observatory (LDEO) LADCP software for data processing in Matlab [Thur08]. Ancillary data were downloaded including the CTD proﬁle and timeseries, and the shipboard ADCP data. These data were used in conjunction with the LADCP data to produce both shear and inverse solutions for the absolute velocities. The preliminary processing produced velocity proﬁles, rosette frame angular movements, and Matlab ﬁles. Section plots of U and V were produced and were made available on the cruise website on the local network. The data acquisition log summarizes errors in the data processing. A common error was "Increased error because of shear-inverse difference." This was common in the early casts during the cruise and was presumably due to a lack of scatterers in the water column at these lower latitudes. Occasionally there were errors indicating a U and/or V bottom track bias. In all but one instance, this was resolved by setting p.btrack_mode=0 in the matlab script set_cast_params. Problems Prior to starting casts, LADCP battery problems were indicated by faint pinging that terminated prematurely during deck tests. The battery was swapped out for another NOAA battery, and the star cable was also replaced with a brand new cable. All problems were resolved with deck testing prior to the test cast, which preceded the ﬁrst station. Data collection was largely routine and problem free until cast 93. When this cast came up, the data processing indicated that one of the beams had failed. There was a severe drop in voltage and corresponding increase in current evident near the bottom of the cast. In the sampling hangar, the top of the ADCP was removed and the inside of the instrument was inspected. There was no indication of leaking or corrosion and all connections were secure. The O-rings were replaced and the instrument re- sealed. The instrument remained on the rosette for the duration of the cruise and continued to collect data from the 3 remaining beams. Summary and Preliminary Results Data were successfully collected on all 113 stations sampled during the cruise. Issues with the CTD led to repeat casts on two stations (87 and 113) and LADCP data were collected on both the problematic and repeat casts in each case. Latitude-depth sections of measured zonal (U) and meridional (V) velocities are shown in Figure 14.2 and 14.3. Stations 1-60 followed the 25 West line of longitude (Figure 14.2), and Stations 60-113 were between 25 and 36.5 South (Figure 14.3). Currents were much stronger in the southern part of the transect. Note the difference in scale between Figures 14.2 and 14.3. Much of the northern portion of the transect (Figure 14.2) is in the subtropical gyre and was characterized by weaker currents and fewer scatterers in the water column. Strong currents extending from the surface to the full ocean depth are observable at around 47 degrees South. This may correspond with the southern boundary of the South Atlantic Current. The Antarctic Circumpolar Current is observable heading East at the end of the transect, below South Georgia Island. Figure 14.2: Zonal (U, upper) and meridional (V, lower) velocities measured from Stations 1-60. Figure 14.3: Zonal (U, upper) and meridional (V, lower) velocities measured from Stations 60-113. SADCP Sampling The Ronald H. Brown has a permanently mounted 75 kHz acoustic Doppler current proﬁler (Teledyne RDI) for measuring ocean velocity in the upper water column. The ADCP is a Phased Array instrument, capable of pinging in broadband mode (for higher resolution), narrowband mode (lower resolution, deeper penetration), or interleaved mode (alternating). On this cruise, data were collected with 8m broadband pings and 16m narrowband pings. The depth range achieved depends on weather (bubbles), installation (e.g. ship noise), scattering levels, and other factors. Data were recorded during the entire cruise. Processing Specialized software developed at the University of Hawaii has been installed on the Brown for the purpose of ADCP acquisition, preliminary processing, and ﬁgure generation during each cruise. The acquisition system ("UHDAS", University of Hawaii Data Acquisition System) acquires data from the ADCPs, gyro heading (for reliability), Mahrs and POSMV headings (for increased accuracy), and GPS positions from various sensors. Single-ping ADCP data are automatically edited and combined with ancillary feeds, averaged, and disseminated via the ship’s web, as regularly-updated ﬁgures on a web page and as Matlab and netCDF ﬁles. Summary Shipboard ADCP data were collected for the duration of A16S. The ADCP system and data were monitored remotely. There were no changes or errors noted, beyond a continuing 15 percent failure level of the POSMV. Although the Mahrs and the POSMV are supposed to be accurate, neither is perfect and post-processing of the ADCP data will be necessary to obtain best accuracy for data while the ship is steaming. When the ship speed is near zero, heading errors do not cause signiﬁcant errors in ocean velocity. Therefore the automated at-sea product should be good enough for preliminary use while the ship is on station. All in all, the instrument, ancillary devices, and acquisition system performed reasonably well. 15. CHIPOD System Conﬁguration and Sampling Three Chipods were mounted on the CTD rosette frame to measure temperature (T), its time derivative (Tt), and acceleration at 50, 100, and 50 Hz, respectively. One Chipod-CTD has two T/Tt sensors, looking upward, and three-dimensional accelerator. Two RBR-Chipods, one looking upward and the other looking downward, are a combination of RBR Duo, which measures T and pressure at 1 Hz, and Chipod with one T/Tt sensor and one horizontal accelerator. Figure 15.1 shows details of the conﬁguration of the Chipods and sensors. Three upward looking T/Tt sensors were positioned above the Niskin bottles by 8.25 inches and above the bottom of the CTD rosette frame by 82.25 inches using a unistrut in order to avoid false turbulence, which might be generated by the movement of the rosette frame during the upcast. The upward looking Chipod-RBR was assembled lower than the neighboring upward looking T/Tt sensors to avoid possible disturbances by its position due to the rotation of the CTD frame, and collected data from cast 12 onward. The downward looking T/Tt sensor was placed on the LADCP battery pack above the bottom of the CTD frame by 2 inches toward the center of the CTD rosette to avoid picking up false signals due to turbulence from the LADCP modules and/or CTD system during the downcast. Figure 15.1: Chipod conﬁguration on the rosette. The red, cyan, and yellow circles show the positions of T/Tt sensors, Chipod- CTD, and upward looking RBR-Chipod, respectively. The downward looking RBR-Chipod is not seen in this photo. Data Processing To derive proﬁles of turbulent kinetic energy dissipation (ε)and thermal variance dissipation (X), Chipod T/Tt records ﬁrst need to be aligned to pressure. Since Chipod does not have a pressure sensor, double- integration of vertical acceleration, thus displacement of the unit, has to be ﬁt to pressure from CTD to align T/Tt to pressure. Then, ε and X as a function of pressure can be estimated by ﬁtting the vertical temperature gradient (Tz)spectrum, which can be computed from Tt and Chipod descent rate, to the theoretical temperature gradient spectrum, which requires buoyancy frequency and Tz, by using an iterative procedure suggested by [Moum09]. Problems In the ﬁrst thee casts, 0.3 sec interval noise was found in the signal from the secondary Chipod-CTD Tt sensor, which disappeared after the sensor cable was replaced. From station 90 onward, T/Tt sensor malfunction occurred when the package was submerged in cold water (< -0.15°C), and the T/Tt signals drifted with signiﬁcant noise. Summary Figure 15.2 shows a comparison of upward looking Chipod-CTD (red) and downward looking RBR-Chipod data. In the top panel, all T signals represent the temperature variation during the entire cast. The RBR- Chipod Tt signal (black line in the bottom panel) shows a distinct transition between the downcast and the upcast, which occurred at ~11:27 AM. Compared to the downcast Tt signal, the upcast signal shows more noise, which seems linked to a signiﬁcant disturbance by the ascending CTD structure, i.e., 24 Bullister bottles, CTD and LADCP instruments, and the frame. The upward looking Tt signals (blue and red lines) do not show such distinct changes at the transition that may be related to the rotation of the CTD frame during the cast. The LADCP heading record shows the CTD rosette rotating much faster during the upcast compared to the downcast at most stations. Such spinning of the CTD frame implies the revolution of Tt sensors around the winch cable. Thus, false turbulence might be generated by the sensor protector and/or any structure nearby while the CTD frame is rotating due to the position of the sensors (see Figure 15.1), and measured by the sensors, yielding noise in the signal. However, the downward looking sensor, which is placed in the center of the CTD frame, may not be affected signiﬁcantly by the spinning of the CTD frame. Moreover, the rotation rate of the CTD frame during the downcast is less than that during the upcast. Figure 15.2: An example proﬁle of Chipod-CTD and RBR-Chipod data. The blue and red lines indicate the ﬁrst and secondary upward looking Chipod-CTD T/Tt, and the black line shows the downward looking RBR-Chipod T/Tt at station 5 16. TRACE METAL PROGRAM Figure 16.2: A16S Sample distribution for stations 61-113 Water Column Sampling 627 water-column trace metal samples were collected at 53 stations and a test station using a dedicated trace-element rosette with 12 Teﬂon- coated, 12 L General Oceanics GO-FLO bottles [Meas08] modiﬁed with the addition of curved Teﬂon tubing from the sample valve reaching the bottom of the bottle (for quantitative suspended matter sampling). Bottles were conditioned for 24 hours with sub-surface (approx. 1000 m) seawater collected during the test cast. Sub-sampling was conducted in a clean van. Bottles were ﬁrst sub-sampled for unﬁltered seawater samples (nutrients and salinity) then pressurized with ﬁltered, compressed air. Filtered trace metal sub-samples were collected by ﬁltration through acid-washed 0.4 µm polycarbonate track-etched 47 mm ﬁlters in polypropylene ﬁlter holders. Filtered subsamples collected in acid-washed 125 ml LDPE bottles were acidiﬁed to 0.024M HCl and analyzed shipboard for dissolved Al and Fe using ﬂow injection analyses [Resi94] [Meas95]. Replicate samples were collected at all depths for post-cruise analysis at FSU. Total suspended matter samples on 0.4 µm, 47 mm PCTE ﬁlters were rinsed immediately after collection with 15-20 ml DI water (adjusted to pH 8 with dilute ammonia) and stored for post-cruise analysis at FSU. Several planned stations (73, 75, 77, 91 & 93) were not sampled as a result of high winds and large swells that made launching from the stern A frame imprudent. Generally most samples were collected as planned, but on a few occasions bottles were found not to have tripped correctly as a result of a lanyard catching on various parts of the system. Initial problems with the signals from the SBE T probe were diagnosed as a problem of the probe itself, which was replaced with a spare at Stn 007. This probe had not been calibrated since its original use in 2004 and gave relatively high readings using the old calibration factors. It will be recalibrated after the cruise. The SBE O2 sensor started giving problems at station 021 and attempts to ﬁx this by changing cables etc. did not solve the problem. As there was no spare it was left on the rosette but the data are not correct. Preliminary values for dissolved Al concentrations are shown in Figure 16.3 High surface values reﬂecting the inﬂuence of the Saharan plume and gyre transport systems are evident in the surface waters to approximately 18°S. Continuing south, values decrease throughout the upper 1,000m. A small maximum between 200 and 400m between 32 and 41°S appears to be related to mode water formation. To the south of this latitude surface waters are extremely low reﬂecting the lack of aerosol inputs to the surface waters of this region. Both surface and sub-surface Al values increase again to the south of South Georgia Island in the tectonically active East Scotia Basin. Figure 16.3: A16S Stations 1-113. Preliminary shipboard FIA dissolved Al in the top 1000 m. Aerosol Samples Aerosol samples (representing 25 separate deployment intervals) were collected using a Tisch-5170VBL High Volume sampler onto 12 Whatman-41 (W41) mixed cellulose ester ﬁlters over 24-48 hour sampling periods. The sampler was automatically activated only when the wind was within 60° of either side of the bow (away from ship exhaust). Throughout the cruise, 1 or 3 replicates were processed for instantaneously soluble elements [Buck06] and frozen for subsequent analysis at FSU. The remaining subsamples were stored frozen to be digested and analyzed for major and trace elements including Al, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb and others (FSU). While no samples were analyzed at sea, the ﬁlters were visually inspected for some indication of the composition of the aerosols collected. Filters from Stations 1-18 were colored grey, indicating a primarily anthropogenic composition, possibly biomass burning. The ﬁlters for the remainder of the cruise were only lightly loaded. Rain Samples Rainwater was collected using a trace element-clean funnel and bottle system in a tall bucket in an NCON automated wet deposition collector, where falling rain triggers a sensor to open the lid automatically. A minimum of 40 ml of rainwater is necessary to adequately sample a rain event for unﬁltered and ﬁltered trace elements, as well as major anions. Nine rain samples were collected of varying volumes (5-390 ml). There were no rain events north of 21.5°S. In addition, two snow samples were collected (57 and 60°S), with sufﬁcient volume to allow both ﬁltered and unﬁltered sub-samples and an aliquot for major anion determination to be taken. Trace elements and major anions will be determined in the home laboratory. Argo Float Deployments Fourteen Argo proﬁling CTD ﬂoats were deployed during this cruise at the request of WHOI and PMEL groups. These ﬂoats are part of the Argo array, a global network of over 3000 proﬁling ﬂoats. The ﬂoats are designed to sink to a depth of 1000m. They then drift freely at depth for ten days, before sinking to 2000m and then immediately rising to the surface, collecting CTD data as they rise. Conductivity (salinity), temperature, and pressure are measured and recorded at various levels (about 73 levels for Navis and every 2 decibars for the SOLOs) during each ﬂoat ascent. At the surface, before the next dive begins, the acquired data is transmitted to shore via satellite, along with a location estimate taken while the ﬂoat sits at the surface. The typical lifetime of the ﬂoats in the water is about four years. All Argo ﬂoat data is made publicly available on the web in real-time at http://www.usgodae.org/argo/argo.html. All SOLO ﬂoats were checked on the ship and started at least 8 hours before deployment, by passing a magnet over the ’reset’ area on the ﬂoat. The Navis ﬂoats were preprogrammed and did not require this before deployment. Each ﬂoat’s startup time was logged. When in position, each Navis ﬂoat was launched by carefully lowering it into the water using a hand-held line strung through the deployment collar. Each SOLO ﬂoat was deployed in the protective box the ﬂoat shipped with. Deployments were done after the completion of the CTD station nearest to the requested deployment location, immediately after the ship had turned, and begun its course to the next station and had reached a speed of approximately one knot. All fourteen ﬂoats were deployed successfully. An e-mail report was sent to WHOI or PEML, depending on who provided the ﬂoat, to report the ﬂoat ID number, ﬂoat start time, exact ﬂoat deployment time, location, wind speed, wind direction, sea state and deployer’s name(s). The following table shows the location of each Argo Float deployment made on GO-SHIP CLIVAR/CO2. Number Latitude Longitude Time(GMT) Serial Number —————— ——————————— ——————————— ————————— ——————————————————— 1 lat: -06.00 lon: -25.00 07:19 WHOI_S2A-7190 2 lat: -08.00 lon: -25.00 14:38 WHOI_S2A-7191 3 lat: -10.00 lon: -25.00 19:55 WHOI_S2A-7192 4 lat: -12.00 lon: -25.00 00:13 WHOI_S2A-7198 5 lat: -14.00 lon: -25.00 08:09 WHOI_S2A-7182 6 lat: -17.00 lon: -25.00 04:15 WHOI_SOLO-1-1157 7 lat: -20.00 lon: -25.00 01:35 WHOI_SOLO-1-IR-1107 8 lat: -24.00 lon: -25.00 13:20 WHOI_SOLO-1-1159 9 lat: -38.00 lon: -26.55 19:00 PMEL_NAVIS-280 10 lat: -40.00 lon: -27.80 01:33 WHOI_SOLO-1-1163 11 lat: -42.00 lon: -29.03 07:14 PMEL_NAVIS-281 12 lat: -44.00 lon: -30.27 01:53 PMEL_NAVIS-163 13 lat: -46.00 lon: -31.52 08:57 WHOI_SOLO-1-1168 14 lat: -48.00 lon: -32.75 16:53 PMEL_NAVIS-285 References Arms67. 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APPENDIX Cast Bottom Data Foreach station/cast the following table shows the following information for the bottom of each cast, respectively: • Station/Cast Number • GMT Date and Time • Latitude and Longitude • Bathymetric Depth (meters) • Distance Above Bottom (via Altimeter reading, meters) • CTD Pressure of deepest bottle tripped (decibars) A ’-999’ for any of these values indicates either an instrument error or data was not given. A16S Cast bottom data SSS/CC Date & Time Latitude & Longitude Bathy DAB CTDPres Depth —————— ——————————————————— —————————————————————————— ————— ————— ——————— 1/2 2013-12-26 04:58:50 6 0.0984 S, 24 59.9886 W 5809 9.4 5905.6 2/1 2013-12-26 12:15:32 6 29.8620 S, 24 59.9934 W 5628 9.6 5715.5 3/2 2013-12-26 21:01:15 6 59.9298 S, 25 0.2556 W 5578 15 5661.5 4/1 2013-12-27 04:02:41 7 29.9802 S, 25 0.0006 W 5795 9 5885.9 5/2 2013-12-27 11:23:58 7 59.9364 S, 24 59.9550 W 5709 -999 5805.4 6/1 2013-12-27 19:19:59 8 29.9904 S, 24 59.9970 W 5739 10 5829.6 7/2 2013-12-28 03:13:05 8 59.9514 S, 25 0.0042 W 5691 10.3 5720.5 8/1 2013-12-28 10:00:19 9 30.0366 S, 24 59.8086 W 5783 9.3 5661 9/2 2013-12-28 17:46:44 10 0.0216 S, 25 0.0078 W 5406 -999 5517.7 10/1 2013-12-29 00:22:35 10 29.9880 S, 24 59.9898 W 5427 10.5 5495.8 11/1 2013-12-29 07:09:43 10 59.9406 S, 24 59.9934 W 5417 -999 5507.1 12/1 2013-12-29 14:25:33 11 29.9892 S, 24 59.9892 W 4331 10.5 4397.2 13/2 2013-12-29 21:59:57 11 59.9052 S, 24 59.9916 W 5808 -999 5914.3 14/2 2013-12-30 05:37:46 12 30.0318 S, 25 0.0078 W 5587 8.9 5686.7 15/1 2013-12-30 12:32:21 12 59.9544 S, 24 59.9802 W 5778 -999 5870.6 16/1 2013-12-30 20:50:18 13 30.0006 S, 25 0.0198 W 5158 10.4 5250.1 17/2 2013-12-31 05:48:23 14 0.0090 S, 25 0.0090 W 5922 -999 6019.5 18/1 2013-12-31 12:53:30 14 30.0270 S, 25 0.0492 W 5405 10 5487.7 19/2 2013-12-31 20:43:47 15 0.0024 S, 25 0.0066 W 5247 10 5322.9 20/1 2014-01-01 03:27:02 15 29.9646 S, 24 59.9940 W 4995 10.5 5072 21/1 2014-01-01 10:29:02 16 0.0288 S, 25 0.0900 W 5657 11.1 5746.5 22/1 2014-01-01 18:18:12 16 30.0204 S, 25 0.0042 W 5118 10.7 5193.8 23/2 2014-01-02 02:11:55 16 59.9988 S, 25 0.0024 W 5279 9.9 5342.9 24/1 2014-01-02 09:08:07 17 30.1356 S, 25 0.0006 W 5172 10.1 5246.3 25/2 2014-01-02 16:59:18 18 0.0198 S, 25 0.0042 W 5564 10.8 5649.6 26/1 2014-01-03 00:00:17 18 30.0138 S, 25 0.0048 W 5471 10.1 5613.8 27/1 2014-01-03 07:06:04 18 59.8368 S, 25 0.1008 W 5816 9.8 5929 28/1 2014-01-03 14:58:28 19 30.0300 S, 25 0.0036 W 5460 10.5 5550.7 29/2 2014-01-03 23:13:30 19 59.9676 S, 24 59.8722 W 6028 10.3 6133.8 30/1 2014-01-04 06:17:40 20 30.0072 S, 25 0.0042 W 5433 10 5521.8 31/1 2014-01-04 13:03:41 21 0.1134 S, 25 0.2466 W 5231 10 5301.6 32/1 2014-01-04 21:06:23 21 30.0306 S, 25 0.0084 W 5330 11.5 5416.1 33/2 2014-01-05 05:23:16 21 59.9874 S, 25 0.0078 W 5133 10.2 5217.1 34/1 2014-01-05 12:27:52 22 29.9958 S, 24 59.9934 W 5533 10.5 5616 35/2 2014-01-05 20:18:03 22 59.9598 S, 24 59.9802 W 5114 -999 5178.8 36/1 2014-01-06 03:10:19 23 30.0096 S, 25 0.0126 W 5435 11.9 5503.2 SSS/CC Date & Time Latitude & Longitude Bathy DAB CTDPres Depth —————— ——————————————————— —————————————————————————— ————— ————— ——————— 37/1 2014-01-06 10:17:16 23 59.9946 S, 25 0.0114 W 5619 10.9 5706.5 38/1 2014-01-06 17:55:02 24 30.0018 S, 25 0.0012 W 5217 10 5367.8 39/2 2014-01-07 01:42:07 25 0.0318 S, 25 0.0216 W 5430 9 5551.3 40/1 2014-01-07 08:19:06 25 29.7648 S, 25 0.2832 W 4981 9.8 5058.6 41/2 2014-01-07 15:48:08 26 0.0054 S, 25 0.0078 W 4897 -999 4966.9 42/1 2014-01-07 22:13:32 26 30.0666 S, 25 0.0834 W 4765 9.5 4837.4 43/2 2014-01-08 05:50:35 26 59.9868 S, 25 0.0090 W 4721 10.4 4784.9 44/1 2014-01-08 12:05:41 27 30.0426 S, 25 0.2964 W 4848 9.2 4911 45/2 2014-01-08 19:37:29 28 0.0030 S, 25 0.0126 W 5323 -999 5403.5 46/1 2014-01-09 02:14:57 28 30.0300 S, 25 0.1230 W 5307 10.3 5392.2 47/1 2014-01-09 08:47:36 28 59.9610 S, 25 0.1062 W 5031 -999 5107.5 48/1 2014-01-09 16:33:32 29 30.0180 S, 25 0.0006 W 5348 8.4 5431.1 49/2 2014-01-10 00:19:16 30 0.0144 S, 24 59.8512 W 5593 -999 5688.5 50/1 2014-01-10 06:56:31 30 30.0216 S, 24 59.9772 W 4675 10.3 4741.1 51/1 2014-01-10 13:06:29 31 0.1992 S, 25 0.0342 W 4537 10.2 4602.2 52/1 2014-01-10 20:31:04 31 30.0216 S, 25 0.0204 W 4494 10.3 4561.4 53/2 2014-01-11 03:49:37 32 0.0288 S, 25 0.0066 W 4321 9.6 4382.9 54/1 2014-01-11 10:05:38 32 30.0210 S, 24 59.9718 W 4158 12.1 4218 55/2 2014-01-11 17:22:01 33 0.0060 S, 25 0.0018 W 4586 -999 4643.6 56/1 2014-01-11 23:48:09 33 29.8098 S, 24 59.9100 W 4388 8.6 4446.9 57/2 2014-01-12 07:12:56 34 0.0138 S, 25 0.0282 W 4079 10.2 4140.2 58/1 2014-01-12 13:19:39 34 29.9802 S, 24 59.9598 W 3973 9.2 4022 59/2 2014-01-12 20:31:05 34 59.8614 S, 24 59.9916 W 4115 -999 4171 60/1 2014-01-13 03:11:22 35 29.9928 S, 25 0.0030 W 4113 11.8 4162.3 61/1 2014-01-13 10:04:30 36 0.0006 S, 25 18.0090 W 4039 10.3 4098.6 62/1 2014-01-13 17:57:07 36 29.9940 S, 25 36.0090 W 4093 9.9 4140.3 63/2 2014-01-14 01:59:39 36 59.9628 S, 25 53.9634 W 4126 10.5 4182.9 64/1 2014-01-14 09:19:19 37 29.9634 S, 26 12.0150 W 4195 9.3 4251.2 65/2 2014-01-14 17:15:01 38 0.0000 S, 26 26.3244 W 4068 -999 4117.3 66/1 2014-01-15 01:25:04 38 29.9178 S, 26 52.0212 W 4173 10.6 4233.9 67/1 2014-01-15 08:52:40 38 59.6754 S, 27 9.6684 W 4138 -999 4197.7 68/1 2014-01-15 16:19:26 39 30.0066 S, 27 29.0928 W 4502 9.2 4568.9 69/2 2014-01-15 23:46:46 39 59.9148 S, 27 48.0090 W 4301 8.1 4360.6 70/1 2014-01-16 06:22:31 40 29.9760 S, 28 6.0354 W 4360 10 4429 71/2 2014-01-16 14:00:22 41 0.7140 S, 28 24.2910 W 4328 10.5 4396.2 72/1 2014-01-16 21:00:14 41 30.0186 S, 28 42.9426 W 4355 10.6 4427 73/1 2014-01-17 05:15:59 41 59.9922 S, 29 1.9680 W 4437 12.6 4507 74/1 2014-01-17 14:24:56 42 30.0288 S, 29 20.8440 W 4506 9.7 4580.3 75/1 2014-01-18 08:40:21 43 0.2556 S, 29 38.6556 W 4479 14.1 4542.5 76/1 2014-01-18 16:51:51 43 29.9814 S, 29 57.7998 W 4689 -999 4763.1 77/1 2014-01-19 00:04:17 44 0.0888 S, 30 15.8160 W 4620 9.8 4692 78/1 2014-01-19 07:01:36 44 30.0048 S, 30 34.9896 W 5106 9.9 5202.5 79/1 2014-01-19 13:53:46 45 0.0012 S, 30 54.2496 W 4817 12 4899.9 80/1 2014-01-19 22:03:57 45 29.4738 S, 31 11.1168 W 5094 10.8 5181.4 81/2 2014-01-20 06:51:58 45 59.9454 S, 31 30.7794 W 5262 8.8 5346 82/1 2014-01-20 14:26:11 46 29.9196 S, 31 48.4728 W 5240 -999 5343.7 83/1 2014-01-20 21:53:32 46 59.9550 S, 32 7.4442 W 5179 16.3 5276.8 84/1 2014-01-21 06:47:25 47 30.5040 S, 32 27.4422 W 5352 25.5 5438.9 85/1 2014-01-21 13:44:46 48 0.4248 S, 32 46.6032 W 5325 27.1 5418.2 86/1 2014-01-21 21:50:55 48 30.1992 S, 33 4.0284 W 4961 17 5048.7 87/3 2014-01-22 13:37:33 49 0.3876 S, 33 22.1406 W 4940 85.3 5014.2 88/1 2014-01-22 20:54:52 49 30.2460 S, 33 40.3404 W 5176 -999 5273 SSS/CC Date & Time Latitude & Longitude Bathy DAB CTDPres Depth —————— ——————————————————— —————————————————————————— ————— ————— ——————— 89/2 2014-01-23 05:18:37 50 0.0462 S, 34 0.0090 W 5043 9.9 5132.5 90/1 2014-01-23 12:24:07 50 30.0756 S, 34 17.8866 W 4892 10.8 4969.8 91/1 2014-01-23 19:55:51 51 0.0264 S, 34 36.8706 W 5000 9.8 5089.7 92/1 2014-01-24 13:09:57 51 29.9664 S, 34 55.8840 W 4816 9.8 4897.6 93/1 2014-01-24 20:24:02 52 0.0018 S, 35 13.9800 W 4453 16.4 4528.6 94/1 2014-01-25 03:20:40 52 29.9886 S, 35 33.0000 W 3868 18 3928.3 95/1 2014-01-25 09:35:15 53 0.0564 S, 35 50.8296 W 3526 8.7 3575.8 96/1 2014-01-25 15:24:46 53 15.4182 S, 36 1.6608 W 3295 -999 3339.7 97/1 2014-01-25 19:26:51 53 25.9002 S, 36 6.9132 W 2716 14.4 2746.1 98/1 2014-01-25 23:44:27 53 35.6526 S, 36 12.6408 W 1779 -999 1796.6 99/2 2014-01-26 03:12:01 53 44.4006 S, 36 14.5884 W 923 10.5 923.8 100/2 2014-01-26 05:49:12 53 51.0132 S, 36 22.9896 W 219 10.2 209.8 101/1 2014-01-26 17:37:54 55 13.8114 S, 34 44.2662 W 177 15.4 170.4 102/1 2014-01-26 19:34:02 55 16.0608 S, 34 37.7562 W 941 11.7 945 103/2 2014-01-26 22:50:10 55 19.7742 S, 34 31.7706 W 1836 9 1849.4 104/1 2014-01-27 03:11:56 55 35.9640 S, 34 10.9590 W 2210 15.3 2234.7 105/1 2014-01-27 08:22:58 55 59.9526 S, 33 37.9692 W 2552 -999 2577.4 106/1 2014-01-27 15:48:24 56 30.0036 S, 32 56.8896 W 3719 10.2 3778.3 107/1 2014-01-27 22:32:00 56 59.9250 S, 32 17.2584 W 3703 15.9 3753.9 108/1 2014-01-28 06:35:50 57 29.9832 S, 31 35.9508 W 3399 10.7 3439 109/1 2014-01-28 13:13:06 58 1.6848 S, 30 54.7092 W 3554 -999 3607.3 110/1 2014-01-28 20:05:32 58 30.0612 S, 30 55.7736 W 2926 15.9 2949.3 111/2 2014-01-29 02:44:31 58 59.9448 S, 30 55.4226 W 3093 11 3141.3 A16S Trace Metals Cast bottom data SSS/CC Date & Time Latitude & Longitude Bathy CTDPres Depth —————— ——————————————————— —————————————————————————— ————— ——————— 1/1 2013-12-26 02:29:07 6 0.0690 S, 25 0.1380 W 5799 1022.6 3/1 2013-12-26 18:12:12 7 0.0108 S, 25 0.1446 W 5580 986 5/3 2013-12-27 14:00:38 7 59.9718 S, 24 59.9328 W 5708 1001.3 7/1 2013-12-28 00:47:40 9 0.0060 S, 25 0.1788 W 5619 1019.9 9/1 2013-12-28 15:29:05 9 59.9952 S, 25 0.1188 W 5426 999.3 11/2 2013-12-29 09:41:36 11 0.0510 S, 24 59.9412 W 5417 980.3 13/1 2013-12-29 19:37:47 11 59.9886 S, 25 0.0510 W 5808 1020.2 15/2 2013-12-30 15:06:39 12 59.9892 S, 24 59.8344 W 5779 977.6 17/1 2013-12-31 02:22:45 14 0.0486 S, 25 0.0390 W 5927 1000.2 19/1 2013-12-31 18:29:26 15 0.0210 S, 25 0.0768 W 5272 979.8 21/2 2014-01-01 12:59:43 16 0.0648 S, 24 59.9946 W 5667 1020.4 23/1 2014-01-01 23:51:50 17 0.0270 S, 25 0.0336 W 5245 990.3 25/1 2014-01-02 14:42:19 18 0.1080 S, 25 0.0228 W 5558 999.7 27/2 2014-01-03 09:37:10 18 59.8398 S, 25 0.0072 W 5799 981.3 29/1 2014-01-03 20:42:29 20 0.0804 S, 24 59.9682 W 6035 1021.8 31/2 2014-01-04 15:26:31 21 0.0672 S, 25 0.1434 W 5217 582 33/1 2014-01-05 03:04:48 21 59.9970 S, 25 0.0054 W 5093 1002.2 35/1 2014-01-05 18:02:49 22 59.8734 S, 25 0.2676 W 5099 979.9 37/2 2014-01-06 12:43:48 23 59.9820 S, 24 59.8920 W 5626 1022 39/1 2014-01-06 23:21:43 24 59.9946 S, 25 0.0708 W 5468 989.9 41/1 2014-01-07 13:36:42 26 0.0054 S, 25 0.2442 W 4894 1000.6 43/1 2014-01-08 03:36:13 26 59.9658 S, 25 0.2460 W 4767 979.6 45/1 2014-01-08 17:16:37 27 59.9148 S, 25 0.2160 W 5316 1025.1 47/2 2014-01-09 11:05:26 28 59.9262 S, 25 0.0522 W 5027 986.1 49/1 2014-01-09 22:00:03 30 0.2010 S, 25 0.0366 W 5606 998.1 53/1 2014-01-11 01:50:51 31 59.7330 S, 25 0.0840 W 4326 1021.5 55/1 2014-01-11 15:16:57 32 59.8302 S, 24 59.8932 W 4622 978.2 57/1 2014-01-12 05:15:33 34 0.0810 S, 24 59.9250 W 4027 1002.7 59/1 2014-01-12 18:36:47 35 0.1392 S, 24 59.9250 W 4112 979.8 61/2 2014-01-13 12:08:34 36 0.1674 S, 25 18.0360 W 4037 1021.5 63/1 2014-01-14 00:02:22 36 59.7768 S, 25 53.7684 W 4119 991.6 65/1 2014-01-14 15:13:57 37 59.5920 S, 26 26.1432 W 4069 1001 67/2 2014-01-15 11:01:24 38 59.8662 S, 27 9.7398 W 4136 980.7 69/1 2014-01-15 21:51:23 39 59.8692 S, 27 47.9166 W 4299 1022.4 71/1 2014-01-16 11:49:57 41 0.3744 S, 28 24.7746 W 4340 912.2 79/2 2014-01-19 16:22:57 44 59.9262 S, 30 53.8440 W 4843 1172.1 81/1 2014-01-20 04:31:36 45 59.5356 S, 31 30.6702 W 5254 978.1 83/2 2014-01-21 00:25:53 47 0.4320 S, 32 5.7234 W 5167 994.4 85/2 2014-01-21 16:17:32 48 0.4320 S, 32 48.3606 W 5346 990.5 87/1 2014-01-22 03:38:27 48 59.9646 S, 33 22.5834 W 4751 1002.7 89/1 2014-01-23 02:56:19 50 0.3960 S, 33 59.3682 W 5045 964.5 95/2 2014-01-25 11:34:24 52 59.9700 S, 35 50.8830 W 3526 1022.1 97/2 2014-01-25 21:10:46 53 26.0052 S, 36 7.2600 W 2622 991.7 99/1 2014-01-26 02:12:12 53 44.4018 S, 36 14.3940 W 935 895.2 100/1 2014-01-26 05:16:04 53 50.9706 S, 36 22.3068 W 225 181.6 101/2 2014-01-26 18:09:22 55 13.8822 S, 34 44.3514 W 177 146.5 103/1 2014-01-26 21:34:48 55 19.7382 S, 34 31.6104 W 1847 1002.8 105/2 2014-01-27 10:06:02 55 59.9844 S, 33 38.1882 W 2548 993.4 107/2 2014-01-28 00:44:58 56 59.6286 S, 32 17.3688 W 3687 1021.1 109/2 2014-01-28 15:19:43 58 1.7472 S, 30 54.6936 W 3553 992.7 111/1 2014-01-29 01:00:07 59 0.0240 S, 30 55.1250 W 3095 1009.4 Bottle Data Quality Code Summary and Comments This section contains WOCE quality codes [Joyc94] used during this cruise, and remarks regarding bottle data. A16S Water Sample Quality Code Summary Property 1 2 3 4 5 6 7 8 9 Total ——————————— ———— ———— ——— —— —— ——— — — — ————— Bottle 0 3210 36 24 8 0 0 0 6 3284 Al 15 582 4 13 0 4 0 0 0 618 CFC-11 0 1285 374 5 38 0 0 0 2 1704 CFC-12 0 1659 3 2 38 0 0 0 2 1704 SF6 0 1655 7 2 38 0 0 0 2 1704 cf 13C/ 14C 1703 0 0 0 0 0 0 0 0 1703 density 113 0 0 0 0 0 0 0 0 113 Fe 15 579 10 10 0 4 0 0 0 618 3He 414 0 0 0 0 0 0 0 0 414 Ammonium 3261 0 0 0 0 0 0 0 0 3261 18O 254 0 0 0 0 0 0 0 0 254 O2 0 2634 0 5 3 0 0 0 0 2642 ph 0 2008 10 62 14 200 0 0 2 2296 pCO2 0 687 2 3 4 1 0 0 0 697 DIC 0 1941 4 9 3 317 0 0 1 2275 tAlk 0 1923 20 33 12 306 0 0 2 2296 13C/ 14C 524 0 0 0 0 0 0 0 0 524 Tritium 346 0 0 0 0 0 0 0 0 346 Nitrate 0 2588 0 1 2 661 0 0 9 3261 Nitrite 0 2567 0 1 2 682 0 0 9 3261 Phosphate 0 2588 1 1 2 660 0 0 9 3261 Silicic Acid 0 2602 0 1 2 647 0 0 9 3261 sAlt 0 3030 0 0 0 201 0 0 4 3235 Quality evaluation of data included comparison of bottle salinity and bottle oxygen data with CTDO data using plots of differences; and review of various property plots and vertical sections of the station proﬁles and adjoining stations. Comments from the Sample Logs and the results of investigations into bottle problems and anomalous sample values are included in this report. Sample number in this table is the cast number times 100 plus the bottle position number. Table 16.3: A16S Bottle Quality Codes and Comments Station Sample Quality /Cast Number Property Code Comment ——————— ——————— ———————————— ——————— ———————————————————————————————————————————————— 001/02 201 Bottle 3 Bottle leaking. 001/02 206 Bottle 3 Bottle leaking. 001/02 206 Dissolved O2 4 Bottle value low for CTD up and down proﬁle. 001/02 207 Bottle 3 Bottle leaking. Loose o-ring. 002/01 101 Bottle 3 Bottle leaking. 002/01 104 Total Alkalinity 9 Sample not drawn. 002/01 104 pH 9 Sample not drawn. 002/01 122 Bottle 3 Bottle leaking due to open vent. 003/02 201 Bottle 3 Bottle leaking. 004/01 109 Bottle 3 Spigot leaking. 004/01 124 Dissolved O2 5 Sample lost. 005/02 201-224 Bottle 4 All Bottles offset by one position. 005/02 214 Bottle 4 Both Nutrients and Oxygen values are off. Likely mistrip. 005/02 214 Dissolved O2 4 Bottle value high for CTD up and down proﬁle. 006/01 106 Bottle 3 Lanyard caught in top cap. Leaking (air in sample). 007/02 215 Bottle 3 Vent valve was open. 008/01 108 Salinity 9 Sample not taken. 009/02 109 Bottle 4 Bottle did not close. No samples. 009/02 109 Bottle 4 Bottle did not close. No samples. 009/02 109 Salinity 4 Bottle did not close. No samples. 010/01 117 Bottle 3 Vent valve was open. 011/01 101 Bottle 3 Vent valve was open. 015/01 121-124 Bottle 2 Incinerator burning. Possible carbon contamination. 021/01 101-106 Bottle 2 No gloves worn during sampling. 021/01 108 Bottle 3 Vent valve was open. 021/01 108 Dissolved O2 4 Bottle value low for CTD up and down proﬁle. 021/01 115 Bottle 3 Major Bottle leak. 021/01 116 Bottle 3 Major Bottle leak. 022/01 118 Bottle 5 Niskin didn’t close. 025/02 213 Bottle 3 Slight leak. Bottle dripping. 027/01 101 Bottle 3 Vent valve was open. 028/01 102 Total CO2 2 DIC Bottle 303 is greaseless, without HgCl 2. 028/01 104 Total CO2 2 DIC Bottle 304 is greaseless, without HgCl 2. 029/02 206 Bottle 3 Spigot leaking. 029/02 206 Dissolved O2 4 Bad oxygen value. Likely due to leak. 029/02 206 Total Alkalinity 9 No sample taken due to the leak. 029/02 206 Total CO2 9 No sample taken due to the leak. 029/02 206 pH 9 No sample taken due to the leak. 029/02 206 pcDissolved O2 9 No sample taken due to the leak. 029/02 212 Salinity 9 No water left for sample. 029/02 217 Salinity 9 No water left for sample. 029/02 218 Bottle 5 Bottle did not close. 030/01 118 Bottle 5 Bottle did not close. Carousel head changed after sampling. 030/01 124 Bottle 3 Bad Leak. 035/02 206 Bottle 3 Lanyard caught in top cap. 035/02 208 Bottle 3 Lanyard caught in top cap. 036/01 101 Bottle 3 Bottle leaking. 037/01 106 Bottle 3 Lanyard from Niskin 5 caught in top cap. 037/01 106 Dissolved O2 4 Oxygen low. Likely due to leak. 041/02 218 Bottle 5 Niskin didn’t close. 042/01 118 Bottle 5 Niskin didn’t close. 043/02 218 Bottle 5 Niskin didn’t close. 044/01 118 Bottle 5 Niskin didn’t close. 048/01 120-124 Bottle 5 Niskin didn’t close. Computer error. 051/01 106 Bottle 3 Bad leak. 051/01 115 Bottle 2 Hands without gloves sampled. 051/01 123 Bottle 2 Blackish residue on niskin nipple. 061/01 101 Bottle 2 No gloves worn by 1 person. 061/01 102 Bottle 2 No gloves worn by 1 person. 061/01 122 Bottle 3 Lanyard caught in Bottle cap. Leaking bottle. 069/02 215 Bottle 3 Lanyard caught in top cap. Possible leak. 070/01 118 Bottle 3 Leaking. 072/01 122 Bottle 3 Lanyard caught in cap. Leaking. 072/01 122 Dissolved O2 5 Sample lost. 075/01 122 Bottle 3 Lanyard caught in bottle top cap. Leaking. 076/01 122 Bottle 3 Lanyard caught in bottle top cap. Leaking. 083/01 116 Dissolved O2 5 Sample lost. 091/01 122 Bottle 3 Lanyard caught in Bottle cap. Leaking. 093/01 118 Bottle 3 Leaking. 094/01 101 Bottle 5 Niskin didn’t close but pin tripped. 095/01 118 Bottle 3 Major leak. 099/02 101 Bottle 5 Niskin didn’t close but pin tripped. 103/02 218 Bottle 3 Leaking. 107/01 121 Bottle 3 Bottle hit during recovery. Leaking. 109/01 122 Bottle 3 Lanyard caught in Bottle cap. Leaking. 111/02 218 Bottle 3 Leaking. 112/01 118 Bottle 3 Leaking. 112/01 122 Bottle 3 Leaking with vent closed. 113/03 313 Bottle 2 Cigarette smoke. 113/03 314 Bottle 2 Cigarette smoke. References Joyc94. Joyce, T., ed. and Corry, C., ed., “Requirements for WOCE Hydrographic Programme Data Reporting,” Report WHPO 90-1, WOCE Report No. 67/91., pp. 52-55, WOCE Hydrographic Programme Ofﬁce, Woods Hole, MA, USA (May 1994, Rev. 2). CCHDO Data Processing Notes • File Online Carolina Berys 33RO20131223.exc.csv (download) #0269b Date: 2019-05-21 Current Status: unprocessed • File Submission Robert Key 33RO20131223.exc.csv (download) #0269b Date: 2018-12-18 Current Status: unprocessed Notes File includes final C13 and C14 data. Previous submissions were missing two stations. Header edited accordingly. • File Online Carolina Berys 33RO20131223.exc.csv (download) #2deb1 Date: 2018-08-06 Current Status: unprocessed • File Submission Robert Key 33RO20131223.exc.csv (download) #2deb1 Date: 2018-07-19 Current Status: unprocessed Notes Updated file with C14 and C13 added. There will eventually be carbon isotope data for 2 more stations (57 and 73). Please do take this opportunity to clean up the header, particularly removal of the e-mail addresses! thx • File Merge CCHSIO 33RO20131223_ct1.zip (download) #5bc5f Date: 2017-11-14 Current Status: merged • File Merge CCHSIO 33RO20131223_nc_ctd.zip (download) #6eba1 Date: 2017-11-14 Current Status: merged • File Merge CCHSIO 2013A16S.TXT (download) #eb03a Date: 2017-11-14 Current Status: merged • Merged CTDBEAMCP into CTD files CCHSIO Date: 2017-11-14 Data Type: CTD Action: Website Update Note: A16S 2013 33RO20131223 processing - CTD merge CTDBEAMCP into existing Exchange file 2017-11-14 CCHDO Submission filename submitted by date id ------------ ------------ ---------- ----- 2013A16S.TXT Wilf Gardner 2017-06-01 12768 Changes ------- 33RO20131223_ct1.zip - merged CTDBEAMCP data from Wilf Gardner - removed TRANSM, no longer needed since CTDBEAMCP is available - changed FLUORM to CTDFLUOR - Separated the CTDFLUOR column into two columns: STNNBR 11,12 are from a chloryphyll fluorometer (CTDFLUOR), the remaining stations are from a CDOM (CTDCDOMFRAW) fluorometer - Changed units of CTDFLUOR from VDC to 0-5VDC - Changed units of CTDCDOMFRAW from VDC to 0-5VDC, although max is 5.3V - Station 41 did not have CTDBEAMCP data to merge, so used fill values. - added header and unit comments - added cruise comments Conversion ---------- file converted from software ----------------------- -------------------- ----------------- 33RO20131223_nc_ctd.zip 33RO20131223_ct1.zip 0.8.2-48-g594e1cb Updated Files Manifest ---------------------- file stamp --------------------- ---------------- 33RO20131223_ct1.zip 20171114CCHSIO 33RO20131223_nc_ctd.zip 20171114CCHSIO :Removed parameters: TRANSM, TRANSM_FLAG_W :Merged parameters: CTDBEAMCP, CTDBEAMCP_FLAG_W :Separated parameters: FLUORM into CTDFLUOR and CTDCDOMFRAW opened in JOA with no apparent problems: 33RO20131223_ct1.zip 33RO20131223_nc_ctd.zip opened in ODV with no apparent problems: 33RO20131223_ct1.zip • File Online Carolina Berys 2013A16S.TXT (download) #eb03a Date: 2017-06-01 Current Status: merged • File Submission see 2013A16S.TXT (download) #eb03a Date: 2017-06-01 Current Status: merged Notes Wilf Gardner's CTDBEAMCP final data to be merged • Exchange and netCDF files online Rox Date: 2015-03-30 Data Type: O2_TCO2_PCO2 Action: Website Update Note: ====================================================================== ======================================================= 33RO20131223 processing - BTL/merge - BTLNBR_FLAG_W, CTDPRS, TCARBN, TCARBN_FLAG_W, PCO2, PCO2_FLAG_W, PCO2TMP, OXYGEN_FLAG_W ====================================================================== ======================================================= 2015-03-30 R Lee .. contents:: :depth: 2 Submission ========== ========================================= ============== ========================== =============== ==== filename submitted by date data type id ========================================= ============== ========================== =============== ==== A16S2013_NiskinQCdataCCHDO.xls Carolina Berys 2015-02-09 19:03:20.415735 data_suggestion 6390 A16S_33RO20131223_TCO2_PCO2_final_hy1.csv Carolina Berys 2015-02-09 19:03:48.652953 data_suggestion 6392 a16s_2013_final_discrete_o2.csv Carolina Berys 2015-03-09 16:55:53.217389 data_suggestion 6439 ========================================= ============== ========================== =============== ==== Parameters ---------- A16S2013_NiskinQCdataCCHDO.xls ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ - CTDPRS A16S_33RO20131223_TCO2_PCO2_final_hy1.csv ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ - CTDPRS - TCARBN [1]_ - PCO2 [1]_ - PCO2TMP a16s_2013_final_discrete_o2.csv ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ - CTDOXY [1]_ - OXYGEN [1]_ .. [1] parameter has quality flag column .. [2] parameter only has fill values/no reported measured data .. [3] not in WOCE bottle file .. [4] merged, see merge_ Process ======= Changes ------- a16s_2013_final_discrete_o2.csv ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ - PH_TMP unit changed from 'DEG_C' to 'DEG C' Merge ------- A16S2013_NiskinQCdataCCHDO.xls ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ - Merged A16S2013_NiskinQCdataCCHDO.xls into 33RO20131223_hy1.csv using hydro 0.8.2-40-g569f4c2. - Updated parameters: BTLNBR_FLAG_W, CTDPRS A16S_33RO20131223_TCO2_PCO2_final_hy1.csv ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ - Merged A16S_33RO20131223_TCO2_PCO2_final_hy1.csv into 33RO20131223_hy1.csv using hydro 0.8.2-40-g569f4c2. - Updated parameters: TCARBN, TCARBN_FLAG_W, PCO2, PCO2_FLAG_W, PCO2TMP a16s_2013_final_discrete_o2.csv ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ - Merged a16s_2013_final_discrete_o2.csv into 33RO20131223_hy1.csv using hydro 0.8.2-40-g569f4c2. - Updated parameters: OXYGEN_FLAG_W .. _merge: Conversion ---------- ======================= ==================== ======================= file converted from software ======================= ==================== ======================= 33RO20131223_nc_hyd.zip 33RO20131223_hy1.csv hydro 0.8.2-40-g569f4c2 ======================= ==================== ======================= All converted files opened in JOA with no apparent problems. Updated Files Manifest ====================== ======================= ================= file stamp ======================= ================= 33RO20131223_hy1.csv 20150327CCHSIORJL 33RO20131223_nc_hyd.zip 20150327CCHSIORJL ======================= ================= • File Submission Chris Langdon a16s_2013_final_discrete_o2.csv (download) #10b34 Date: 2015-03-09 Current Status: merged Notes Expocode: 33RO20131223 Ship: Ron H Brown Woce Line: A16S Note: None • As Received Carolina Berys Date: 2015-03-09 Data Type: Action: Data available Note: The following data are now available As Received, unprocessed by the CCHDO. http://cchdo.ucsd.edu/cruise/33RO20131223 a16s_2013_final_discrete_o2.csv • As Received Carolina Berys Date: 2015-02-09 Data Type: Action: Data available Note: The following data are now available As Received, unprocessed by the CCHDO. http://cchdo.ucsd.edu/cruise/33RO20131223 A16S2013_NiskinQCdataCCHDO.xls • As Received Carolina Berys Date: 2015-02-09 Data Type: Action: Data available Note: The following data are now available As Received, unprocessed by the CCHDO. http://cchdo.ucsd.edu/cruise/33RO20131223 A16S_33RO20131223_TCO2_PCO2_final_hy1.csv • File Submission Alex Kozyr A16S_33RO20131223_TCO2_PCO2_final_hy1.csv (download) #96336 Date: 2015-02-03 Current Status: merged Notes Expocode: 33RO20131223 Ship: Ronald H. Brown Woce Line: A16S Note: The final and public TCARBN and PCO2 data were submitted to CDIAC by Rik Wanninkhof on 20150202. • File Submission Leticia Barbero A16S2013_NiskinQCdataCCHDO.xls (download) #67f47 Date: 2015-02-02 Current Status: merged Notes Expocode: 33RO20131223 Ship: Ron Brown Woce Line: A16S 2013 Note: Please use this file, which includes updated QC flags and corrected Niskin depths instead of the file I sent earlier today. Sorry for the mess! • ALKALI and PH_SWS update online in all formats Carolina Berys Date: 2015-01-28 Data Type: ALKALI-PH Action: Website Update Note: =========================================================== A16S 2013 33RO20131223 processing - BTL/merge - ALKALI, PH =========================================================== 2015-01-28 C Berys .. contents:: :depth: 2 Submission ========== ========================================== ============== ========================== =============== ==== filename submitted by date data type id ========================================== ============== ========================== =============== ==== A16S_2013_ALKALI_PH_SWS_FINAL_20150127.csv Carolina Berys 2015-01-27 12:55:04.142401 data_suggestion 6380 ========================================== ============== ========================== =============== ==== Parameters ---------- A16S_2013_ALKALI_PH_SWS_FINAL_20150127.csv ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ - ALKALI [1]_ [4]_ - PH_SWS [1]_ [4]_ - CTDPRS - PH_TMP .. [1] parameter has quality flag column .. [2] parameter only has fill values/no reported measured data .. [3] not in WOCE bottle file .. [4] merged, see merge_ Process ======= .. _merge: Merge ----- A16S_2013_ALKALI_PH_SWS_FINAL_20150127.csv ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ Merged A16S_2013_ALKALI_PH_SWS_FINAL_20150127.csv into 33RO20131223_hy1.csv using hydro 0.8.2-40-g569f4c2. :Updated parameters: PH_SWS, PH_SWS_FLAG_W, PH_TMP, ALKALI, ALKALI_FLAG_W All comment lines from original file copied back in following merge. 33RO20131223_hy1.csv opened in JOA with no apparent problems. Conversion ---------- ======================= ==================== ======================= file converted from software ======================= ==================== ======================= 33RO20131223_nc_hyd.zip 33RO20131223_hy1.csv hydro 0.8.2-40-g569f4c2 33RO20131223hy.txt 33RO20131223_hy1.csv hydro 0.8.2-40-g569f4c2 ======================= ==================== ======================= All converted files opened in JOA with no apparent problems. Updated Files Manifest ====================== ======================= ================= file stamp ======================= ================= 33RO20131223_hy1.csv 20150127CCHSIOCBG 33RO20131223_nc_hyd.zip 20150127CCHSIOCBG 33RO20131223hy.txt ======================= ================= • File Submission Alex Kozyr A16S_2013_ALKALI_PH_SWS_FINAL_20150127.csv (download) #c7b99 Date: 2015-01-27 Current Status: merged Notes Expocode: 33RO20131223 Ship: Ronald H. Brown Woce Line: A16S Note: The ALKALI and pH flags were changed since last submission per PI request. Please, replace these data in the .hy file at CCHDO. • As Received Carolina Berys Date: 2015-01-27 Data Type: Action: Data available Note: The following data are now available As Received, unprocessed by the CCHDO. http://cchdo.ucsd.edu/cruise/33RO20131223 A16S_2013_ALKALI_PH_SWS_FINAL_20150127.csv ALKALI/PH • Updated ALKALI, PH, DOC, TDN, NUTS, CFCs, bottle data online in all formats Carolina Berys Date: 2014-12-18 Data Type: ALKALI-PH_DOC-TDN_NUTS_CFCs Action: Website Update Note: ====================================================================== ========== A16S 2013 33RO20131223 processing - BTL/merge - ALKALI, PH, DOC, TDN, NUTS, CFCs ====================================================================== ========== 2014-12-16 C Berys .. contents:: :depth: 2 Submission ========== ========================================== ================ ========================== =============== ==== filename submitted by date data type id ========================================== ================ ========================== =============== ==== A16S_2013_ALKALI_PH_SWS_FINAL_20140722.csv Alex Kozyr 2014-11-10 00:00:00 data_suggestion 5654 A16S_33RO20131223_DOC_TDN_final_v2.csv Alex Kozyr 2014-11-11 00:00:00 data_suggestion 5656 A16S_2013_NUTS_umol-kg_141112.txt Eric Wisegarver 2014-11-12 00:00:00 data_suggestion 5658 a16s_2013_cfc_cchdo_8_dec_2014.txt David Wisegarver 2014-12-08 16:54:43.955708 bottle_exchange 6331 ========================================== ================ ========================== =============== ==== Parameters ---------- A16S_2013_ALKALI_PH_SWS_FINAL_20140722.csv ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ - CTDPRS - ALKALI [1]_ [4]_ - PH_SWS [1]_ [4]_ - PH_TMP [4]_ A16S_33RO20131223_DOC_TDN_final_v2.csv ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ - CTDPRS - DOC [1]_ [4]_ - TDN [1]_ [3]_ [4]_ A16S_2013_NUTS_umol-kg_141112.txt ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ - SILCAT [1]_ [4]_ - NITRAT [1]_ [4]_ - NITRIT [1]_ [4]_ - PHSPHT [1]_ [4]_ a16s_2013_cfc_cchdo_8_dec_2014.txt ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ - CTDPRS - CFC-11 [1]_ [4]_ - CFC-12 [1]_ [4]_ - SF6 [1]_ [4]_ - N2O [1]_ [3]_ [4]_ - CCL4 [1]_ [2]_ [4]_ .. [1] parameter has quality flag column .. [2] parameter only has fill values/no reported measured data .. [3] not in WOCE bottle file .. [4] merged, see merge_ Process ======= .. _merge: Merge ----- A16S_2013_ALKALI_PH_SWS_FINAL_20140722.csv ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ Merged A16S_2013_ALKALI_PH_SWS_FINAL_20140722.csv into 33RO20131223_hy1.csv using hydro 0.8.2-40-g569f4c2. :Updated parameters: PH_SWS, PH_SWS_FLAG_W, PH_TMP, ALKALI, ALKALI_FLAG_W A16S_33RO20131223_DOC_TDN_final_v2.csv ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ Merged A16S_33RO20131223_DOC_TDN_final_v2.csv into 33RO20131223_hy1.csv using hydro 0.8.2-40-g569f4c2. :New parameters: DOC, DOC_FLAG_W, TDN, TDN_FLAG_W A16S_2013_NUTS_umol-kg_141112.txt ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ Merged A16S_2013_NUTS_umol-kg_141112.txt into 33RO20131223_hy1.csv using hydro 0.8.2-40-g569f4c2. :Updated parameters: PHSPHT, SILCAT, NITRAT, NITRIT, PHSPHT_FLAG_W, SILCAT_FLAG_W, NITRAT_FLAG_W, NITRIT_FLAG_W a16s_2013_cfc_cchdo_8_dec_2014.txt ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ Merged a16s_2013_cfc_cchdo_8_dec_2014.txt into 33RO20131223_hy1.csv using hydro 0.8.2-40-g569f4c2. :Updated parameters: CFC-11, CFC-11_FLAG_W, CFC-12, CFC-12_FLAG_W, SF6, SF6_FLAG_W, N2O, N2O_FLAG_W All comment lines from original file copied back in following merge. 33RO20131223_hy1.csv opened in JOA with no apparent problems. Conversion ---------- ======================= ==================== ======================= file converted from software ======================= ==================== ======================= 33RO20131223_nc_hyd.zip 33RO20131223_hy1.csv hydro 0.8.2-40-g569f4c2 33RO20131223hy.txt 33RO20131223_hy1.csv hydro 0.8.2-40-g569f4c2 ======================= ==================== ======================= All converted files opened in JOA with no apparent problems. Updated Files Manifest ====================== ======================= ================= file stamp ======================= ================= 33RO20131223_hy1.csv 20141218CCHSIOCBG 33RO20131223_nc_hyd.zip 20141218CCHSIOCBG 33RO20131223hy.txt ======================= ================= • File Submission David Wisegarver a16s_2013_cfc_cchdo_8_dec_2014.txt (download) #1c4b2 Date: 2014-12-08 Current Status: merged Notes Expocode: 33RO20131223 Ship: Ronald H Brown Woce Line: None Note: None • Updated CFC data submitted Carolina Berys Date: 2014-12-08 Data Type: CFC Action: submission Note: Updated CFC file received with correction to sample 101 station 94. Available as received. • As Received Carolina Berys Date: 2014-12-08 Data Type: Action: Data available Note: The following data are now available As Received, unprocessed by the CCHDO. http://cchdo.ucsd.edu/cruise/33RO20131223 a16s_2013_cfc_cchdo_8_dec_2014.txt CFC • Available under 'Files as received' CCHDO Staff Date: 2014-11-14 Data Type: CFC Action: Website Update Note: The following files are now available online under 'Files as received', unprocessed by the CCHDO. a16s_2013_cfc_cchdo_13_nov_2014.txt • to go online David Wisegarver Date: 2014-11-13 Data Type: CFCs Action: Submitted • File Submission Eric Wisegarver A16S_2013_NUTS_umol-kg_141112.txt (download) #090f2 Date: 2014-11-12 Current Status: merged Notes Expocode: 33RO20131223 Ship: Ronald H. Brown Woce Line: A16S Note: None • Available under 'Files as received' CCHDO Staff Date: 2014-11-12 Data Type: NUTS Action: Website Update Note: The following files are now available online under 'Files as received', unprocessed by the CCHDO. A16S_2013_NUTS_umol-kg_141112.txt • Available under 'Files as received' CCHDO Staff Date: 2014-11-12 Data Type: DOC/TDN Action: Website Update Note: The following files are now available online under 'Files as received', unprocessed by the CCHDO. A16S_33RO20131223_DOC_TDN_final_v2.csv • Available under 'Files as received' CCHDO Staff Date: 2014-11-12 Data Type: ALKALI/PH Action: Website Update Note: The following files are now available online under 'Files as received', unprocessed by the CCHDO. A16S_2013_ALKALI_PH_SWS_FINAL_20140722.csv • Place Online, Merge Data, Updated Parameters Eric Wisegarver Date: 2014-11-12 Data Type: NUTs Action: Submitted • File Submission Alex Kozyr A16S_33RO20131223_DOC_TDN_final_v2.csv (download) #75933 Date: 2014-11-11 Current Status: merged Notes Expocode: 33RO20131223 Ship: RONALD H. BROWN Woce Line: A16S_2013 Note: This is a resubmission of final and public DOC/TDN data with some data and flag corrections. Please, replace the file submitted on 20141110 with this one. • flag corrections Alex Kozyr Date: 2014-11-11 Data Type: DOC/TDN Action: Re-submitted Note: This is a resubmission of final and public DOC/TDN data with some data and flag corrections. Please, replace the file submitted on 20141110 with this one. • File Submission Alex Kozyr A16S_2013_ALKALI_PH_SWS_FINAL_20140722.csv (download) #32f65 Date: 2014-11-10 Current Status: merged Notes Expocode: 33RO20131223 Ship: RONALD H. BROWN Woce Line: A16S_2013 Note: The ALKALI and PH_SWS data were submitted by Frank Millero to CDIAC on 20140722. • Final data, to go online Alex Kozyr Date: 2014-11-10 Data Type: DOC/TDN Action: Submitted Note: The final and public DOC/TDN data were sent to CDIAC by Dennis Hansell on 20141110. • Available under 'Files as received' CCHDO Staff Date: 2014-11-10 Data Type: DOC/TDN Action: Website Update Note: The following files are now available online under 'Files as received', unprocessed by the CCHDO. A16S_33RO20131223_DOC_TDN_final.csv • File Merge Carolina Berys a16s_hy1.csv (download) #7c4c0 Date: 2014-10-14 Current Status: merged Notes BTL • Fixed station 5 flags, bottle data online in all formats Carolina Berys Date: 2014-10-14 Data Type: BTL-fix Action: Website Update Note: ======================= 33RO20131223 processing ======================= 2014-10-14 C Berys .. contents:: :depth: 2 Process ======= - replaced files Directories =========== :working directory: /data/co2clivar/atlantic/a16/a16s_33RO20131223/original/2014.10.14_BTL -fix_CBG :cruise directory: /data/co2clivar/atlantic/a16/a16s_33RO20131223 Updated Files Manifest ====================== ======================= ================= file stamp ======================= ================= 33RO20131223_nc_hyd.zip 20141014CCHSIOCBG 33RO20131223_hy1.csv 20141014CCHSIOCBG ======================= ================= • Fixed station 5 flags, bottle data online in all formats Carolina Berys Date: 2014-10-14 Data Type: BTL Action: Website Update Note: ====================================================================== =================== A16S 2013 33RO20131223 processing - BTL/merge - BTLNBR, SALNTY, CTDOXY flags at station 5 ====================================================================== =================== 2014-10-14 C Berys .. contents:: :depth: 2 Submission ========== ============ ============= ========== ========= ==== filename submitted by date data type id ============ ============= ========== ========= ==== a16s_hy1.csv Alex Quintero 2014-06-20 BTL 1183 ============ ============= ========== ========= ==== Parameters ---------- a16s_hy1.csv ~~~~~~~~~~~~ - BTLNBR [1]_ [4]_ - CTDPRS - CTDTMP - CTDSAL [1]_ - SALNTY [1]_ [4]_ - CTDOXY [1]_ [4]_ - OXYGEN [1]_ - SILCAT [1]_ - NITRAT [1]_ - NITRIT [1]_ - PHSPHT [1]_ - CFC-11 [1]_ - CFC-12 [1]_ - SF6 [1]_ - TCARBN [1]_ - ALKALI [1]_ - PCO2TMP - PH_TOT [1]_ - PH_TMP - TRITUM [1]_ [2]_ - HELIUM [1]_ [2]_ - REFTMP [3]_ - REFTMP_FLAG [3]_ - SALTREF [1]_ [3]_ - N2O [1]_ [3]_ - PCO2 [1]_ - DOC [1]_ [2]_ - 14C_DIC [1]_ [2]_ [3]_ - OXY_18 [1]_ [2]_ [3]_ - SIGMA-THETA [3]_ - SIGMA-1 [3]_ - SIGMA-2 [3]_ - SIGMA-3 [3]_ - SIGMA-4 [3]_ .. [1] parameter has quality flag column .. [2] parameter only has fill values/no reported measured data .. [3] not in WOCE bottle file .. [4] merged, see merge_ Process ======= Changes ------- 33RO20131223_hy1.csv ~~~~~~~~~~~~~~~~~~~~ - edits to header and added citation information .. _merge: Merge ----- a16s_hy1.csv ~~~~~~~~~~~~ Merged a16n_hy1.csv into 33RO201312239_hy1.csv using hydro 0.8.2-40- g569f4c2. :Updated parameters: BTLNBR_FLAG_W, SALNTY_FLAG_W, CTDOXY_FLAG_W All comment lines from original file copied back in following merge. 33RO20131223_hy1.csv opened in JOA with no apparent problems. Conversion ---------- ======================= ==================== ======================= file converted from software ======================= ==================== ======================= 33RO20131223_nc_hyd.zip 33RO20131223_hy1.zip hydro 0.8.2-40-g569f4c2 33RO20131223hy.txt 33RO20131223_hy1.csv hydro 0.8.2-40-g569f4c2 ======================= ==================== ======================= All converted files opened in JOA with no apparent problems. Directories =========== :working directory: /data/co2clivar/atlantic/a16/a16s_33RO20131223/original/2014.10.14_BTL _CBG :cruise directory: /data/co2clivar/atlantic/a16/a16s_33RO20131223 Updated Files Manifest ====================== ======================= ================= file stamp ======================= ================= 33RO20131223_nc_hyd.zip 20141014CCHSIOCBG 33RO20131223hy.txt 33RO20131223_hy1.csv 20141014CCHSIOCBG ======================= ================= • Available under 'Files as received' CCHDO Staff Date: 2014-06-23 Data Type: BTL Action: Website Update Note: The following files are now available online under 'Files as received', unprocessed by the CCHDO. a16s_hy1.csv • File Submission Alex Quintero a16s_hy1.csv (download) #7c4c0 Date: 2014-06-20 Current Status: merged Notes Fixed station 5 flags. • File Submission Alex Quintero a16s_hy1.csv (download) #7c4c0 Date: 2014-06-20 Current Status: merged Notes Expocode: 33RO20131223 Ship: Ronald H. Brown Woce Line: None Note: Fixed station 5 flags. • Fixed station 5 flags. Alex Quintero Date: 2014-06-20 Data Type: BTL Action: Submitted • Exchange and netCDF files online Rox Lee Date: 2014-06-17 Data Type: BTL Action: Website Update Note: ================================== 33RO20131223 processing - Citation ================================== 2014-06-17 R Lee .. contents:: :depth: 2 Process ======= Changes ------- - Added citation instructions for data use Conversion ---------- ======================= ==================== ======================== file converted from software ======================= ==================== ======================== 33RO20131223_nc_hyd.zip 33RO20131223_hy1.csv hydro 0.8.0-128-g4494380 ======================= ==================== ======================== All converted files opened in JOA with no apparent problems. Directories =========== :working directory: /data/co2clivar/atlantic/a16/a16s_33RO20131223/original/2014.06.17_BTL _RJL :cruise directory: /data/co2clivar/atlantic/a16/a16s_33RO20131223 Updated Files Manifest ====================== ======================= ================= file stamp ======================= ================= 33RO20131223_nc_hyd.zip 20140617SIOCCHRJL 33RO20131223_hy1.csv 20140617SIOCCHRJL ======================= ================= • File Merge cchdo_admin a16s_final.sea (download) #e609a Date: 2014-06-06 Current Status: merged Notes BTL • File Merge Carolina Berys 33RO20131223su.txt (download) #c20ac Date: 2014-06-06 Current Status: dataset Notes SUM • File Merge cchdo_admin a16s_final_ct1.zip (download) #281fd Date: 2014-06-06 Current Status: merged Notes CTD • File Merge Carolina Berys a16s_hy1.csv (download) #c0e83 Date: 2014-06-06 Current Status: merged Notes SUM • File Merge Carolina Berys a16s_hy1.csv (download) #52436 Date: 2014-06-06 Current Status: merged Notes BTL • Exchange, netCDF, and WOCE files online. SUM, CTD, and bottle with updated CTDO Carolina Berys Date: 2014-06-06 Data Type: BTL-NUTS-CTDO-CTD Action: Website Update Note: ====================================================================== ======================================= A16S 2013 33RO20131223 processing - SUM/CTD/BTL/merge - CTDRAW, CTDPRS, CTDTMP, CTDSAL, CTDOXY, THETA, SALNTY ====================================================================== ======================================= 2014-06-06 C Berys .. contents:: :depth: 2 Submission ========== ================== ================ ========== ========= ==== filename submitted by date data type id ================== ================ ========== ========= ==== a16s_final_ct1.zip Kristy McTaggart 2014-04-10 CTD 1153 a16s_final.sea Kristy McTaggart 2014-04-10 BTL 1154 a16s_hy1.csv Alex Quintero 2014-05-02 BTL 1164 a16s_hy1.csv Alex Quintero 2014-05-13 BTL 1166 a16s.sum Alex Quintero 2014-05-13 SUM 1168 ================== ================ ========== ========= ==== Parameters ---------- a16s_final_ct1.zip ~~~~~~~~~~~~~~~~~~ - CTDPRS [1]_ - CTDTMP [1]_ - CTDSAL [1]_ - CTDOXY [1]_ - TRANSM [3]_ - FLUORM [3]_ a16s_final.sea ~~~~~~~~~~~~~~ - CTDPRS [4]_ - CTDTMP [4]_ - CTDSAL [1]_ [4]_ - SALNTY [1]_ [4]_ - CTDOXY [1]_ [4]_ - CTDRAW [3]_ [4]_ - THETA [3]_ [4]_ a16s_hy1.csv ~~~~~~~~~~~~ - CTDPRS [4]_ - CTDTMP [4]_ - CTDSAL [1]_ [4]_ - SALNTY [1]_ [4]_ - CTDOXY [1]_ [4]_ - OXYGEN [1]_ - SILCAT [1]_ - NITRAT [1]_ - NITRIT [1]_ - PHSPHT [1]_ - CFC-11 [1]_ - TCARBN [1]_ - ALKALI [1]_ - PCO2 [1]_ - PCO2TMP - PH_TOT [1]_ - PH_TMP - TRITUM [1]_ [2]_ - REFTMP [1]_ [3]_ - DOC [1]_ [2]_ - CTDRAW [3]_ - SALTREF [1]_ [3]_ - CFC-12 [1]_ - N2O [1]_ [3]_ - SF6 [1]_ - HELIUM [1]_ [2]_ - 14C_DIC [1]_ [2]_ [3]_ - OXY_18 [1]_ [2]_ [3]_ - SIG0 [3]_ - SIGMA-1 [3]_ - SIGMA-2 [3]_ - SIGMA-3 [3]_ - SIGMA-4 [3]_ a16s.sum ~~~~~~~~ .. [1] parameter has quality flag column .. [2] parameter only has fill values/no reported measured data .. [3] not in WOCE bottle file .. [4] merged, see merge_ Process ======= Changes ------- a16s_final_ct1.zip ~~~~~~~~~~~~~~~~~~ a16s_final.sea ~~~~~~~~~~~~~~ - NOTE: Station 48, Cast 1, Samples 24 - 20 not present in CTDO update, original values remain a16s_hy1.csv ~~~~~~~~~~~~ - CTDPRS units changed from âDBARSâ to âDBARâ - REFTMP units changed from âCâ to âDEG Câ, REFTMP_FLAG changed to REFTMP_FLAG_W - REFTMP_FLAG_W changed from â-999.0â to â9â where data was also empty value - PCO2 units changed from â/â to âUATMâthe - SIGMA-THETA changed to SIG0 - NOTE: Several unrecognized parameters and units not as expected in parameter list - NOTE: Station 48, Cast 1, Samples 24 - 20 not present in CTDO update, original values remain a16s.sum ~~~~~~~~ .. _merge: Merge ----- a16s_final.sea, a16s_hy1.csv ~~~~~~~~~~~~~~~~~~~~~~~~~~~~ Merged a16s_final.sea into a16s_hy1.csv using hydro 0.8.0-117- g2f13399. :New parameters: CTDRAW, CTDPRS, CTDTMP, CTDSAL, CTDOXY, THETA, SALNTY, CTDOXY_FLAG_W, SALNTY_FLAG_W All comment lines from original file copied back in following merge. 33RO20131223_hy1.csv opened in JOA with no apparent problems. Conversion ---------- ======================= ==================== ======================== file converted from software ======================= ==================== ======================== 33RO20131223_nc_hyd.zip 33RO20131223_hy1.csv hydro 0.8.0-117-g2f13399 33RO20131223hy.txt 33RO20131223_hy1.csv hydro 0.8.0-117-g2f13399 33RO20131223_nc_ctd.zip 33RO20131223_ct1.csv hydro 0.8.0-117-g2f13399 ======================= ==================== ======================== All converted files opened in JOA with no apparent problems. Directories =========== :working directory: /data/co2clivar/atlantic/a16/a16s_33RO20131223/original/2014.06.06_BTL -NUTS-CTDO-CTD_CBG :cruise directory: /data/co2clivar/atlantic/a16/a16s_33RO20131223 Updated Files Manifest ====================== ======================= =================== file stamp ======================= =================== 33RO20131223_nc_hyd.zip 20140604CCHSIOCBG 33RO20131223hy.txt 33RO20131223su.txt 33RO20131223_nc_ctd.zip 20140410PMELNOAAKEM 33RO20131223_hy1.csv 20140604CCHSIOCBG 33RO20131223_ct1.zip 20140410PMELNOAAKEM ======================= =================== • File Submission Carolina for Alex Quintero 33RO20131223su.txt (download) #c20ac Date: 2014-05-13 Current Status: dataset Notes SUM file • File Submission Carolina for Alex Quintero 33RO20131223su.txt (download) #c20ac Date: 2014-05-13 Current Status: dataset Notes Expocode: 33RO20131223 Ship: RONALD H. BROWN Woce Line: A16S Note: SUM file from Alex Quintero submitted via email on 2014-05-12 • File Submission Alex Quintero a16s_hy1.csv (download) #c0e83 Date: 2014-05-13 Current Status: merged Notes Exchange bottle. Fixed Oxygen Flags. • File Submission Alex Quintero a16s_hy1.csv (download) #c0e83 Date: 2014-05-13 Current Status: merged Notes Expocode: 33RO20131223 Ship: NOAAS Ronald H. Brown Woce Line: None Note: Fixed Oxygen Flags. • to go online Alex Quintero Date: 2014-05-13 Data Type: SUM Action: Submitted Note: SUM file from Alex Quintero submitted via email on 2014-05-12 • Available under 'Files as received' CCHDO Staff Date: 2014-05-13 Data Type: SUM Action: Website Update Note: The following files are now available online under 'Files as received', unprocessed by the CCHDO. a16s.sum • Available under 'Files as received' CCHDO Staff Date: 2014-05-13 Data Type: SUM Action: Website Update Note: The following files are now available online under 'Files as received', unprocessed by the CCHDO. a16s_hy1.csv • Fixed Oxygen Flags. Alex Quintero Date: 2014-05-13 Data Type: BTL Action: Submitted • File Merge Carolina Berys A16S_Doc.pdf (download) #eec5c Date: 2014-05-08 Current Status: merged Notes CrsRpt • Maps created Rox Lee Date: 2014-05-08 Data Type: maps Action: Website Update Note: ============================== 33RO20131223 processing - Maps ============================== 2014-05-08 R Lee .. contents:: :depth: 2 Process ======= Changes ------- - Maps created from a16s_hy1.csv Directories =========== :working directory: /data/co2clivar/atlantic/a16/a16s_33RO20131223/original/2014.05.08_map s_RJL :cruise directory: /data/co2clivar/atlantic/a16/a16s_33RO20131223 Updated Files Manifest ====================== ==================== ===== file stamp ==================== ===== 33RO20131223_trk.gif 33RO20131223_trk.jpg ==================== ===== • File Submission Alex Quintero a16s_hy1.csv (download) #52436 Date: 2014-05-02 Current Status: merged Notes Updated bottle file with final CTD parameters from .sea file • File Submission Alex Quintero a16s_hy1.csv (download) #52436 Date: 2014-05-02 Current Status: merged Notes Expocode: 33RO20131223 Ship: NOAAS Ronald H. Brown Woce Line: None Note: This is the bottle file with the updated ".sea" parameters merged in. • to go online Alex Quintero Date: 2014-05-02 Data Type: BTL Action: Submitted Note: This is the bottle file with the updated ".sea" parameters merged in. • Available under 'Files as received' CCHDO Staff Date: 2014-05-02 Data Type: BTL Action: Website Update Note: The following files are now available online under 'Files as received', unprocessed by the CCHDO. a16s_hy1.csv • File Submission Alex Quintero A16S_Doc.pdf (download) #eec5c Date: 2014-05-01 Current Status: merged Notes Updated cruise report. • File Submission Alex Quintero A16S_Doc.pdf (download) #eec5c Date: 2014-05-01 Current Status: merged Notes Expocode: 33RO20131223 Ship: NOAAS Ronald H. Brown Woce Line: None Note: Updated cruise report. • updated Alex Quintero Date: 2014-05-01 Data Type: CrsRpt Action: Submitted Note: Updated cruise report. • Available under 'Files as received' CCHDO Staff Date: 2014-05-01 Data Type: CrsRpt Action: Website Update Note: The following files are now available online under 'Files as received', unprocessed by the CCHDO. A16S_Doc.pdf • Available under 'Files as received' CCHDO Staff Date: 2014-04-24 Data Type: BTL Action: Website Update Note: The following files are now available online under 'Files as received', unprocessed by the CCHDO. a16s_final.sea • Available under 'Files as received' CCHDO Staff Date: 2014-04-24 Data Type: CTD Action: Website Update Note: The following files are now available online under 'Files as received', unprocessed by the CCHDO. a16s_final_ct1.zip • File Submission Kristy McTaggart a16s_final.sea (download) #e609a Date: 2014-04-10 Current Status: merged Notes CTDO and bottle data file in .SEA format • File Submission Kristy McTaggart a16s_final.sea (download) #e609a Date: 2014-04-10 Current Status: merged Notes Expocode: 33RO20131223 Ship: RONALD H. BROWN Woce Line: A16S Note: These final CTDO and bottle salinity data are in .SEA format and should be merged into the a16s_hy1.csv file. • File Submission Kristy McTaggart a16s_final_ct1.zip (download) #281fd Date: 2014-04-10 Current Status: merged Notes CTD data files • File Submission Kristy McTaggart a16s_final_ct1.zip (download) #281fd Date: 2014-04-10 Current Status: merged Notes Expocode: 33RO20131223 Ship: RONALD H. BROWN Woce Line: A16S Note: These CTD profiles should replace those submitted earlier today. These data files have been properly formatted. • final data, to go online Kristy McTaggart Date: 2014-04-10 Data Type: CTDOXY Action: Submitted Note: These final CTDO and bottle salinity data are in .SEA format and should be merged into the a16s_hy1.csv file. • revised data set, to go online Kristy McTaggart Date: 2014-04-10 Data Type: CTD Action: re-Submitted Note: These CTD profiles should replace those submitted earlier today. These data files have been properly formatted. • final data, to go online Kristy McTaggart Date: 2014-04-10 Data Type: CTD Action: Submitted Note: These are final CTD profiles for A16S 2014. The final bottle data and documentation will be submitted directly to Alex Q.