CRUISE REPORT: SR03 (Updated FEB 2019) Highlights Cruise Summary Information Section Designation SR03 (IN1801, IN2018_V01, P11S, S04) Expedition designation (ExpoCodes) 096U20180111 Chief Scientists Steve Rintoul / CSIRO Dates 2018 JAN 11 - 2018 FEB 22 Ship R/V Investigator Ports of call Hobart 44°0'5.4"S Geographic Boundaries 131°59'59"E 150°0'54.7"E 66°25'36"S Stations 108 CTD vertical profile stations Floats and drifters deployed 29 floats deployed Moorings deployed or recovered 0 Contact Information: Steve Rintoul GPO Box 1538 • Hobart, Tasmania • 7001 • Australia steve.rintoul@csiro.au ace CRC ANTARCTIC CLIMATE & ECOSYSTEMS Cooperative Research Centre RV Investigator Marine Science Cruise IN1801 (CSIRO Voyage Designation IN2018_V01), SR3 Plus Additional Southern Transects - Oceanographic Field Measurements and Analysis MARK ROSENBERG ACE CRC, Hobart, Australia STEVE RINTOUL CSIRO Marine and Atmospheric Research, Hobart, Australia unpublished September, 2018 LIST OF CONTENTS Page ABSTRACT 6 1 INTRODUCTION 6 2 CTD INSTRUMENTATION 8 3 PROBLEMS ENCOUNTERED 9 4 CTD DATA PROCESSING AND CALIBRATION 11 5 CTD AND BOTTLE DATA RESULTS AND DATA QUALITY 12 5.1 Conductivity/salinity 12 5.2 Temperature 14 5.3 Pressure 14 5.4 Dissolved oxygen 15 5.5 Fluorescence, backscatter, PAR, transmittance/beam attenuation, altimeter 16 5.6 Nutrients 17 5.7 Additional CTD data processing/quality notes 17 6 UNDERWAY MEASUREMENTS 18 7 INTERCRUISE COMPARISONS 18 8 FILE FORMATS 19 APPENDIX 1 HYDROCHEMISTRY LAB/VOYAGE REPORT 31 APPENDIX 2 HYDROCHEMISTRY DATA PROCESSING REPORT 39 APPENDIX 3 CFC LAB REPORT 69 REFERENCES 72 ACKNOWLEDGEMENTS 73 CCHDO Data Processing Notes 73 LIST OF TABLES Page Table 1: Summary of station information for cruise in1801. 20 Table 2: CTD calibration coefficients and calibration dates for cruise in1801. 21 Table 3: CTD conductivity calibration coefficients for cruise in1801. 22 Table 4: Station-dependent-corrected conductivity slope term (F2 + F3 . N), for station number N, and F2 and F3 the conductivity slope and station-dependent correction calibration terms respectively, for cruise in1801. 23 Table 5: Surface pressure offsets (i.e. poff in dbar) for cruise in1801. 24 Table 6: CTD dissolved oxygen calibration coefficients for cruise in1801. 24 Table 7: Missing data points in 2 dbar-averaged files for cruise in1801. 26 Table 8: Suspect CTD 2 dbar averages (not deleted from the CTD 2 dbar average files) for the indicated parameters, for cruise in1801. 26 Table 9: Obvious bad salinity bottle samples (not deleted from bottle data file) for cruise in1801. 27 Table 10: Suspect (qc flag=3) and bad (qc flag=4) dissolved oxygen bottle values for cruise in1801. 27 Table 11: Suspect (qc flag=3) and bad (qc flag=4) nutrient sample values for cruise in1801. 28 Table 12: Scientific personnel (cruise participants) for cruise in1801. 28 Table 13: Summary of float deployments on cruise in1801. 29 LIST OF FIGURES (see PDF version) Figure 1: CTD station positions and ship's track for cruise in1801. Figure 2: Conductivity ratio cbtl/ccal versus station number for cruise in1801. Figure 3: Salinity residual (sbtl - scal) versus station number for cruise in1801. Figure 4: Difference between secondary and primary temperature sensors with (a) pressure, and (b) temperature. Figure 5: Dissolved oxygen residual (obtl - ocal) versus station number for cruise in1801. Figure 6: Nitrate+nitrite versus phosphate data for cruise in1801. Figure 7a: Bulk plots showing intercruise comparisons of nitrate+ nitrite vs phosphate data for SR3 (low end of nutrient values not included in plot). Figure 7b: Bulk plots showing intercruise comparisons of nitrate+ nitrite vs phosphate data for south end of SR3 (includ- ing cruises au1402 and au1602). Figure 8: Bulk plots showing intercruise comparisons of silicate data for SR3, shown as bottle salinity vs silicate (low end of silicate values not included in plot). Figure 9: Bulk plots showing intercruise comparisons of dissolved oxygen data for SR3, shown as bottle salinity vs bottle dissolved oxygen (and only plotting data below 500 dbar). RV Investigator Marine Science Cruise IN1801 (CSIRO Voyage Designation IN2018_V01), SR3 Plus Additional Southern Transects - Oceanographic Field Measurements and Analysis MARK ROSENBERG (ACE CRC, Hobart) and STEVE RINTOUL (CSIRO CMAR) September, 2018 ABSTRACT Oceanographic measurements were collected aboard RV Investigator cruise in1801 (CSIRO voyage designation in2018_v01) from 11th January to 22nd February 2018, along CLIVAR Southern Ocean repeat meridional section SR3, followed by Adelie land shelf stations, small meridional sections along 150E (the south end of CLIVAR section P11S) and 132E, and several stations along CLIVAR zonal section S4. A total of 108 CTD vertical profile stations were taken on the cruise, most to within 14 metres of the bottom. Over 2800 Niskin bottle water samples were collected for the measurement of salinity, dissolved oxygen, nutrients (phosphate, nitrate+nitrite, silicate, ammonia and nitrite), CFC’s plus tracers (CFC- 11, CFC-12, SF6 and N2O), dissolved inorganic carbon (i.e. TCO2), alkalinity, pH, C13/C14, genomics, HPLC, POC, chlorophyll, radiogenic isotopes, helium, ice nucleation, and Ca/Mg, using a 36 bottle rosette sampler. Full depth current profiles were collected by an LADCP attached to the CTD package. Upper water column current profile data were collected by a ship mounted ADCP (75 kHz). Trace metal rosette and in situ pump deployments were done at some of the CTD stations. Meteorological and water property data were collected by the array of ship's underway sensors. A large assortment of 29 drifting floats was deployed throughout the cruise. A summary of all CTD data and data quality is presented in this report. 1 INTRODUCTION Marine science cruise in1801 (CSIRO voyage designation in2018_v01) was conducted aboard the RV Investigator from January to February 2018. The major constituent of the cruise was the tenth complete occupation of the CLIVAR SR3 CTD section south of Tasmania, completed from north to south, followed by CTD’s at (in order): * 6 Adelie Land shelf stations * a Ninja float deployment site * 11 stations south to north along 150E (the southern end of CLIVAR P11S section) * 10 stations east to west along CLIVAR S4 section * 18 stations north to south along 132E (including a station occupied by the Eltanin in the 1970’s) * 2 northern stations (part of the CAPRICORN meteorology project on the cruise) giving a total of 108 CTD stations (Figure 1, Table 1). The primary scientific objectives for the oceanography were: 1. to measure changes in water mass properties and inventories throughout the full ocean depth between Australia and Antarctica along SR3; 2. to estimate the transport of mass, heat and other properties south of Australia, and to compare the results to previous occupations of the SR3 line and other sections in the Australian sector; 3. to quantify changes in Antarctic Bottom Water in the Australian Antarctic Basin; 4. to quantify the evolving inventory of heat, freshwater, oxygen, CFCs, and carbon dioxide in the upper 2000 m and to infer changes in the ventilation rate of intermediate waters and ocean acidification; 5. to determine the distributions of trace metals and isotopes, their change with time, and the physical, chemical and biological processes controlling those evolving distributions. (the last of these was part of the trace metal project, not discussed further). This report describes the CTD and Niskin bottle data and data quality for this cruise. All information required for use of the data set is presented in tabular and graphical form. CTD station positions are shown in Figure 1, while CTD station information is summarised in Table 1. Float deployments are summarised in Table 13. The hydrochemistry lab report and detailed data processing report (by the cruise hydrochemists Christine Rees, Kendall Sherrin, Stephen Tibben and Kristina Paterson) are in Appendix 1 and 2 respectively. The CFC lab report (by Mark Warner) is in Appendix 3. Data from the LADCP and ADCP are not discussed further. Summary of cruise itinerary: Voyage Designation in1801 (CSIRO voyage in2018_v01) Chief Scientist Steve Rintoul (CSIRO CMAR) Ship RV Investigator Main projects Physical Oceanography, Trace Metal, CAPRICORN (meteorology) Ports of Call Hobart Cruise Dates Jan 11th – Feb 22nd 2018 2 CTD INSTRUMENTATION SeaBird SBE9plus CTD (CSIRO serial #24) was used, with dual temperature (SBE3Plus), conductivity (SBE4C) and dissolved oxygen (SBE43) sensors, mounted on a SeaBird 36 bottle rosette frame, together with a SBE32 36 position pylon and 36 x 12 litre Ocean Test Equipment Niskin bottles. A fin was mounted on the frame, to help minimize package spin. The following additional sensors/instruments were mounted: * Wetlabs FLBBRTD (scattering meter and fluorometer) serial 4799 * Biospherical Instruments PAR sensor QCP2300HP, serial 70111 * Wetlabs C-star transmissometer serial 1421DR * Teledyne RDI lowered ADCP (i.e. LADCP) workhorse monitor – 300 kHz head looking upward, 150 kHz head looking * Tritech 200 kHz altimeter serial 05300.313642 * Tritech 500 kHz altimeter serial 05301.228403 * CSIRO Intertial Motion Unit (data coming up serial line) 15 seal tags (from Clive McMahon, IMAS) were secured to the frame on stations 1 to 4 and 57 to 66, for calibration of the tags against CTD data. CTD data were transmitted up a 8 mm seacable to a SBE11plusV2 deck unit, at a rate of 24 Hz, and logged using SeaBird data acquisition software "Seasave" (version unknown). The CTD deployment method was as follows: * CTD initially deployed down to ~10 to 20 m * after confirmation of pump operation, CTD returned up to just below the surface (depth dependent on sea state, though in most cases it was on the conservative side) * after returning to just below the surface, downcast proper commenced Pre-cruise temperature, conductivity and pressure calibrations (Table 2, including calibration dates) were performed by CSIRO and SeaBird. For the SBE43 oxygen sensors, these calibrations were used for initial data display only. Manufacturer supplied calibrations were used for the transmissometer, PAR, altimeters and FLBB. “Dark” profiles for the FLBB were measured on stations 25 and 106 by taping over the FLBB sensors, and these dark values were used to correct backscatter and fluorescence data. Deck measurements of path open and path blocked voltages were used to correct transmissometer data. Final conductivity and dissolved oxygen calibrations derived from in situ Niskin bottle samples are listed later in the report. Final transmissometer data are referenced to a clean water value. 3 PROBLEMS ENCOUNTERED The main problem on the cruise was a medivac early on. After completing CTD 8 on day 3, all work was paused for a return to Hobart with a sick crewman. Back in the Derwent River the ship parked for a short time off Wrest Point while the crewman was taken ashore by FRC. The ship then returned south to resume work at CTD 9, with a total of 39 hours lost in the roundtrip. An extra day of ship time was granted to compensate. CTD winch spooling problems were a constant throughout the cruise. A small mismatch of the spooler with the wire feed occurs as the winch drum rapidly spins during heave compensation events. This mismatch cumulates throughout a cast, requiring several stops for spooler realignment. Over the whole cruise this added up to several hours lost. Heave compensation was engaged for most of the cruise, however it did not accurately match ship’s motion. There was clearly a lag between ship motion and response of the heave compensation, evident in the jagged CTD profile features in steep gradients in the upper water column. Heave compensation was briefly turned off during station 104 in an attempt to reduce tension spiking during a period of large ship rolls, but it became clear that the situation was better with heave compensation on – some evidence that at least heave compensation was having an effect in the right direction. Any errant profile features should mostly be removed during 2 dbar averaging. The dreaded winch software “e-stops” occurred on several stations – software error messages with an unknown cause, and requiring winch software reset. Additional winch software problems came and went throughout the cruise, including no tension display, and inability to enter wire speed. A spooling problem on the upcast of station 83 (possibly as deep as 3000 dbar) was not noticed in time, and as a result the spooling was a bit of a mess for the remainder of the upcast, with numerous bad wraps, particularly near the cheeks. This was fixed during the downcast of station 84 with a slow and cautious descent, making numerous stops for manual spooler repositioning. During periods of higher well with more rolling of the ship, wire tension problems often occurred when the rosette was near surface at the start and end of the cast. This appears to be a problem with the 36 bottle package, which has lots of drag through the water. The result is slackening and shock loading of the CTD wire, causing wire kinks. 65 kg of weight was added to the bottom of the frame prior to station 26 to try and improve things. Overall, this “snapping” of the wire with the rosette near surface meant caution was needed when returning the rosette close to the surface for commencement of the downcast proper. In general this near surface value was conservative, and as a result numerous casts are missing the top 8 to 10 dbar of data. In addition, on several occasions the shallowest Niskin had to be fired fast, without the usual wait for equilibration (e.g. stations 24 and 48). The following CTD wire reterminations were required, due to various degrees of wire kinking: mechanical only prior to station 20; mechanical and electrical prior to station 21. The trace metal rosette deployment method designed in port, using the coring winch below deck, failed early on in the cruise. The whole deployment method required changing, and the CTD winch used initially for CTD 1 to 5 was now needed for trace metal rosette deployments. CTD ops were changed to the second CTD winch for stations 6 onwards. The CTD door was often very slow moving during opening and closing. This sluggish behaviour was attributed to the effect of cold on the door hydraulics. Heaters were left on in the CTD room at agreed times, to try and improve things. For the hull mounted ADCP, the 150 kHz head was not working - only 75 kHz data were available. Niskin bottle leakage was a significant problem on the cruise. The main offender was top cap leakage, occurring frequently and for many bottles. The problem was traced to the non-standard large cylindrical floats on the top Niskin lanyards, combined with the tight long lanyard to the bottom cap – together these placed stress on the top caps during recovery of the rosette, causing frequent top cap leaks. Half the Niskins (the most common leakers) were relanyarded, using the standard small white balls for floats, and joining the long lanyard to the top lanyard at a more central position (thus avoiding the tight lanyard to the bottom cap after bottle closure). There were insufficient small white balls on board to relanyard all the Niskins. Top cap leakage was dramatically reduced after the relanyarding, with only the occasional leak occurring. Note that top cap leakers were still sampled, and in almost all cases the salinity, oxygen and CFC samples were good – showing that leakage occurred after the rosette left the water. Fortunately for the gas samples this premature top cap “opening” was insufficient to contaminate water drawn from the bottom of a Niskin; assisted also by CFC and oxygen sampling being at the start of the sampling order. Mobile pack ice was reasonably close to the ship during stations 69 and 70, so the ship was allowed to drift north with the pack at ~1 knot during these CTD’s, rather than holding station. Temperature sensor changes were required at stations 11 and 13, to first identify and then replace the sensor with calibration issues (serial 6189). A small amount of bad oxygen data (both primary and secondary) were first observed at station 86, an indicator of a developing fault. At station 88 both oxygen sensors went bad near the start of the downcast. The package was retrieved and the y-cable to the oxygen sensors replaced, fixing the problem. Primary salinity was fouled at ~307 dbar on the upcast of station 41, with values shifting and never coming good. Sea snot was removed from around the sensor inlet after the cast, however a small S2-S1 difference remained for station 42. After the cast the primary line was backflushed from the outlet end, fixing the problem. Secondary conductivity was fouled at ~3200 dbar on the upcast of station 92. The fouling mostly disappeared at ~3050 dbar on the upcast, however a subtle sensor difference remained, and it is unclear whether the tiny remnant fouling was ever fully removed. A small number of Niskins pre-tripped, the most obvious occasions being for Niskin 24 on stations 21 and 23, and Niskins 25 and 29 on stations 25 and 26. 4 CTD DATA PROCESSING AND CALIBRATION Preliminary CTD data processing was done at sea, to confirm correct functioning of instrumentation. Final processing of the data was done in Hobart. The first processing step is application of a suite of the SeaBird "Seasoft" processing programs to the raw data, in order to: * convert raw data signals to engineering units * remove the surface pressure offset for each station * realign the oxygen sensor with respect to time (note that conductivity sensor alignment is done by the deck unit at the time of data logging) * remove conductivity cell thermal mass effects * apply a low pass filter to the pressure data * flag pressure reversals * search for bad data (e.g. due to sensor fouling etc) Further processing and data calibration were done in a MS-Windows environment, using a suite of fortran and matlab programs. Processing steps here include: * forming upcast burst CTD data for calibration against bottle data, where each upcast burst is the average of 10 seconds of data centered on each Niskin bottle firing * merging bottle and CTD data, and deriving CTD conductivity calibration coefficients by comparing upcast CTD burst average conductivity data with calculated equivalent bottle sample conductivities * forming pressure monotonically increasing data, and from there calculating 2 dbar averaged downcast CTD data * calculating calibrated 2 dbar averaged salinity from the 2 dbar pressure, temperature and conductivity values * deriving CTD dissolved oxygen calibration coefficients by comparing bottle sample dissolved oxygen values (collected on the upcast) with CTD dissolved oxygen values from the equivalent 2 dbar downcast pressures Full details of the data calibration and processing methods are given in Rosenberg et al. (unpublished), referred to hereafter as the CTD methodology. Additional processing steps are discussed below in the results section. For calibration of the CTD oxygen data, split profile fits were used for most stations deeper than 1400 dbar, with the exception of stations 7, 13, 57 and 93, where whole profile fits were used (better results than the split profile fits). Whole profile fits were used for stations shallower than 1400 dbar (stations 1-3, 41, 58-66, 94-95, 107-108). Final station header information, including station positions at the start, bottom and end of each CTD cast, were obtained from underway data for the cruise (see section 6 below). Note the following for the station header information: * All times are UTC. * "Start of cast" information is at the commencement of the downcast proper, as described above. * "Bottom of cast" information is at the maximum pressure value. * "End of cast" information is when the CTD leaves the water at the end of the cast, as indicated by a drop in salinity values. * All start and end of cast bottom depth values are corrected for local sound speed, where sound speed values are calculated from the CTD data at each station. * "Bottom of cast" depths are calculated from CTD maximum pressure (converted to depth) and altimeter values at the bottom of the casts. Lastly, data were converted to MATLAB format, and final data quality checking was done within MATLAB. 5 CTD AND BOTTLE DATA RESULTS AND DATA QUALITY Data from the secondary CTD sensors (temperature, conductivity and dissolved oxygen) were used for the whole cruise. Suspect CTD 2 dbar averages are listed in Table 8, while suspect and bad nutrient data are listed in Table 11. Nutrient and dissolved oxygen comparisons to previous cruises are made in section 7. Hydrochemistry lab and data processing reports are in Appendices 1 and 2. The CFC lab report is in Appendix 3. 5.1 Conductivity/salinity The conductivity calibration and equivalent salinity results for the cruise are plotted in Figures 2 and 3, and the derived conductivity calibration coefficients are listed in Tables 3 and 4. Station groupings used for the calibration are included in Table 3. A single duplicate salinity sample was taken for most stations, usually from Niskin 2, as a quality check. International standard seawater batch numbers P161 (expiry date 03/05/2020) and P158 (expiry date 25/03/2018) were used for salinometer standardisations. Lab temperature for salinity analyses mostly ranged between 20 and 24°C over the course of the cruise (see lab temperature figure at the end of Appendix 1). Two Guildline Autosals serials 71613 and 72151 were used over the course of the cruise, with analyses taking place in the salinity lab. Salinometer performance overall was mostly good, though a few problems were encountered during the cruise, including: - bubble trouble when running the station 47 samples; - unstable performance of salinometer 71613 when analysing station 47 or 48 (unclear which from lab notes); anaylsis shifted to salinometer 72151 for remainder of the day; - cell flush/rinse problems for salinometer 72151 during analysis of station 99, due to build up of contamination at the end of the flow path. Full details can be found in the hydrochemistry reports (Appendices 1 and 2). Overall CTD salinity accuracy for the cruise is well within 0.002 (PSS78) (Figure 3). The following station groupings were used for CTD conductivity calibration: Group 1 = station 1-11 Group 2 = station 12-80 Group 3 = station 81-108 The initial group change after station 11 was due to temperature sensor changes. The large group sizes after that are an indication of reasonably stable CTD conductivity cell performance for the cruise. Subtle outlier stations in the post calibration salinity residuals (of the order 0.001 PSS78 e.g. stations 7 and 8) are more likely due to salinometer performance. For initial calibration of the CTD conductivity against bottle data, the CPCOR conductivity coefficient was set to the factory recommended value of -9.57e-8. Significant pressure dependence of the CTD-bottle residuals remained, with a maximum range of ~0.004 PSS78 over the deep profiles. Compressibility of the borosilicate glass in a CTD conductivity cell is individual to each cell (SeaBird, pers. comm.), meaning the recommended value is not suitable as a blanket application for all sensors. CPCOR for the secondary conductivity cell was changed to -8.45e-8 and the data recalibrated/reprocessed, thereby minimizing the pressure dependent salinity residual. Any remaining pressure dependency was insignificant. The 36 bottle package drags more water than the 24 bottle system, and as a result more sample equilibration time is required in steeper vertical gradients in the upper water column. The standard 30 second bottle stop (prior to firing) was adhered to for most of the cruise, but salinity residuals (i.e. bottle-CTD) were still high in the steep gradients, rendering those samples unusable for CTD conductivity calibration. For station 85 onwards 60 second bottle stops were adopted in the upper profile where a steep gradient was present. This dramatically improved the bottle-CTD salinity comparisons in those parts of the water column. Several inserts for the salinity sample bottles were damaged, going unnoticed and remaining in circulation until station 83, and resulting in several bad samples. Close inspection of the vertical profiles of the bottle-CTD salinity difference values reveals a slight biasing for a few stations, of the order 0.001 (PSS78) or less, as follows: station bottle-CTD bias (PSS78) station bottle-CTD bias (PSS78) ——————— ——————————————————————— ——————— ——————————————————————— 7 +0.001 48 +0.0005 above 2000 dbar 8 +0.001 57 -0.0005 11 -0.001 below ~1100 dbar 58 -0.001 13 -0.001 below ~1000 dbar 61 -0.0015 15 +0.0005 below ~1100 dbar 68 -0.0005 17 +0.0005 71 -0.0005 19 -0.001 below ~1100 dbar 81 +0.0005 21 -0.0005 below ~1100 dbar 82 -0.001 25 -0.0005 83 +0.0005 26 -0.0005 84 +0.0005 28 +0.0005 below ~1100 dbar 90 small p dependence remains, +0.001 at top, -0.001 at bottom 39 -0.0005 47 -0.001 below 2000 dbar 98 -0.0005 102 -0.0005 This is most likely due to a combination of factors, including salinometer performance. There is no significant diminishing of overall CTD salinity accuracy from this apparent biasing. Bad salinity bottle samples (not deleted from the data files) are listed in Table 9. 5.2 Temperature Temperature differences between the primary and secondary CTD temperature sensors (Tp and Ts respectively), from data at Niskin bottle stops, are shown in Figure 4. Temperature sensor changes were required at stations 11 and 13, to first identify and then replace the sensor with a calibration problem (serial 6189) (evident in Figure 4). For station 14 onwards, with 2 well calibrated temperature sensors in place, sensor difference is less than 0.0005°C over all depths, with no obvious pressure dependence (Figure 4a), and no obvious temperature dependence (Figure 4b). Despite these sensor changes, a good temperature sensor always remained in the secondary sensor position (serial 6180 for stations 1-11 and 14-108; serial 4522 for stations 12-13). 5.3 Pressure Surface pressure offsets for each cast (Table 5) were obtained from inspection of the data before the package entered the water. Pressure spiking, a problem on some previous cruises, did not occur. 5.4 Dissolved oxygen CTD oxygen data were calibrated as per the CTD methodology, with profiles deeper than 1400 dbar calibrated as split profile fits, and profiles shallower than 1400 dbar calibrated as whole profile fits – with the exception of stations 7, 13, 57 and 93, all deeper than 1400 dbar and for which whole profile fits were used (better results than the split profile fits). To summarise: whole profile fits used for stations 1-3, 7, 13, 41, 57-66, 93-95, 107-108 split profile fits used for stations 2-6,8-12, 14-40, 42-56, 67-92, 96-106 Calibration results are plotted in Figure 5, and the derived calibration coefficients are listed in Table 6. Oxygen bottle data were high quality, with only a minimum number of bad and suspect samples (Table 10) (many of the bad samples were due to pre-tripping Niskins, discussed in section 3). Overall, the calibrated CTD oxygen agrees with the bottle data to within 1% of full scale (where full scale is ~370 µmol/l above 750 dbar, and ~260 µmol/l below 750 dbar) i.e. from the standard deviation values in Figure 5. Cruise lab and data processing notes, including sample analysis method, are in the hydrochemistry reports (Appendices 1 and 2). * For some stations, the top of the upcast and downcast differ due to ocean variability, stations 4 and 5 in particular. Numerous bottle rejections were required to calibrate these two stations, and a meld point (between shallow and deep calibrations in the split profile fit) of 2000 dbar was used (usually 1500 dbar for stations of this depth, as per CTD methodology). * For station 21, the bottom 2 oxygen samples were not available for calibration (bottle 1 titration bad, and bottle 2 suspect); as a result, CTD oxygen is possibly low by ~2 µmol/l for 3600 to 3854 dbar i.e. the bottom part of the profile. * For station 107, the bottom oxygen sample was bad, so the bottom part of the CTD oxygen profile (850 to 1002 dbar) is suspect. * The small number of missing deep CTD oxygen data bins for stations 10, 12, 46 and 100 (Table 7) are due to sensor fouling. * Close comparison of CTD oxygen profiles with bottle data reveal a number of near surface CTD profile segments which are slightly low. The magnitude is ~1% or less of the expected CTD oxygen accuracy, and the data are therefore not flagged as suspect. Specifically: station pressure(dbar) CTD oxygen ——————— —————————————— —————————————————————— 1 6-14 low by up to ~5 µmol/l 20 8-12 low by up to ~4 µmol/l 25 10-12 low by ~3 µmol/l 59 6-18 low by up to ~4 µmol/l 63 6-12 low by up to ~4 µmol/l 67 8-16 low by up to ~3 µmol/l 68 6-20 low by up to ~4 µmol/l 73 8-12 low by up to ~4 µmol/l 82 6-20 low by up to ~4 µmol/l 83 8-22 low by up to ~4 µmol/l 100 4-18 low by up to ~4 µmol/l 105 10-28 low by up to ~4 µmol/l 5.5 Fluorescence, backscatter, PAR, transmittance/beam attenuation, altimeter Note that fluorescence and backscatter data come from the FLBB sensor; and transmittance and beam attenuation are different data calculations derived from the same transmissometer sensor voltage. All fluorescence, backscatter, PAR and transmittance/beam attenuation data have a manufacturer supplied calibration (Table 2) applied to the data, with transmittance/beam attenuation values referenced to clean water. For fluorescence and backscatter, “dark profiles” were collected on stations 25 and 106 by taping over the FLBB sensors. Fluorescence and backscatter data were recalculated using these field dark voltage values (and note that these are the dark voltages listed in Table 2). For transmittance/beam attenuation, an additional field correction was made to the calibration by measuring the on deck path open and path blocked voltage values. In the CTD 2dbar averaged data files, both downcast and upcast data are supplied for fluorescence, PAR and transmittance. Note that upcast 2 dbar backscatter data, with the sensor in the wake of the rosette package, are considered suspect, as particles are potentially broken up by the rosette (Emmanuel Boss, pers. com.). Backscatter CTD upcast burst average data in the bottle data files are on the other hand considered okay, as the package is in theory stationary (other than the obvious motion with the swell). Note that all 2 dbar data for these sensors are strictly 2 dbar averages (as distinct from other calculations used in previous cruises i.e. au0703, au0803 and au0806). For fluorescence and transmittance/beam attenuation, the 2 dbar averaged upcast data (in the CTD 2 dbar files) do not always match the upcast 10 second burst average data (in the bottle data file). This is due to the difference between 2 dbar and 10 second averaging on data with significant vertical structure. The PAR calibration coefficients in Table 2 were calculated from the manufacturer supplied calibration sheet, using the method described in the following SeaBird documents: page 53 of SeaSave Version 7.2 manual; Application Note No. 11 General; and Application Note No. 11 QSP-L. The usual altimeter “artefacts”, as seen on previous cruises (described in Rosenberg and Rintoul, unpublished-1), were observed on both the 200 and 500 kHz Tritech sensors, with false bottom readings often observed before coming within nominal altimeter range. While doing a cast at sea, these artefacts are easily identifiable by simultaneously plotting the 200 and 500 kHz data during logging – artefacts are identifiable by a mismatch between plots for the two altimeters. Maximum transmittance values are slightly more than the expected 100%, and beam attenuation values are equivalently slightly less than the expected 0 value, due to a small calibration error (possibly by referencing to clean water). * For stations 1, 3, 4, 5 and 6, suspect small segments of downcast transmittance/beam attenuation CTD 2 dbar data are listed in Table 8. * Fluorescence and backscatter data for stations 25 and 106 are not included in the files, as the FLBB sensors were taped over to collect dark profiles. 5.6 Nutrients Nutrients measured were phosphate, total nitrate (i.e. nitrate+nitrite), silicate, ammonia and nitrite, using a SEAL Autoanalyzer 3 HR (AA3) (a continuous segmented flower analyser). Samples were run within 12 hours of collection, either kept in the dark or refrigerated prior to analysis. Full lab and data processing details are in the hydrochemistry reports (Appendices 1 and 2). Laboratory temperatures for nutrient analyses ranged between 19 and 22°C over the course of the cruise, except for station 108 where the temperature was slightly higher at ~22.7°C. Suspect and bad nutrient data are listed in Table 11, and nitrate+nitrite versus phosphate data are shown in Figure 6. The following full scale values apply to the analyses: 3.0 µmol/l for phosphate; 42.0 µmol/l for nitrate+nitrite; 140 µmol/l for silicate; 2.0 µmol/l for ammonia; 1.4 µmol/l for nitrite. Phosphate depletion for shallow samples, consistent with previous cruises (Rosenberg et al., unpublished-1, 2 and 3), can be seen in Figure 6 as a tail of lower phosphate values around the 25 µmol/l nitrate+nitrite level. For cruise in1801, these lower phosphates all come from the top 100 dbar and south of 54oS. Further assessment of nutrient data quality is given in section 7 below, comparing the data to previous cruises. Overall nutrient data quality is considered very good, and possibly the best to date measured on the SR3 transect. Measurements within the cruise are consistent, profile shapes look good, and scatter is low. Note that flagging of ammonia and nitrite data may not be complete - at the low levels at which these nutrients are measured, suspect data can sometimes be hard to pick. Flag values have all been left at 2 for these two nutrients. 5.7 Additional CTD data processing/quality notes For some stations, heave compensation error of the CTD winch, discussed above in section 3, resulted in jagged features in the 24 Hz CTD profile data in steep gradients in the upper water column. Any errant profile features should mostly be removed during 2 dbar averaging. At station 71, the CTD was initially taken down to ~200 dbar then returned to near surface to check sensor performance. This initial yoyo down to 200 dbar was removed from the 24 Hz data prior to processing. 6 UNDERWAY MEASUREMENTS Underway data, logged by the full suite of Marine National Facility (MNF) underway water and meteorological sensors, are available on request. The MNF data file in2018_v01uwy.nc contains 5 sec instantaneous data in netcdf format, with data from all sensors merged and synchronised. For most sensors there has been no quality control, so there may be a few suspect data points (in particular for underway sea surface conductivity and salinity). Along track bathymetry data from the 18 kHz sounder (multibeam was not run on this voyage) are also available on request, as 5 sec instantaneous data in the files in1801bath.alf (text format) and in1801bathalf.mat (matlab format). Bottom depths in these files are from the water surface, and calculated using sound speed 1500 m/s. (Note that bottom depths in all CTD data files are corrected for local sound speed). At the time of writing, the 18 kHz data have not yet been quality controlled (i.e. by manually line-picking the bottom in bathymetry data processing software). 7 INTERCRUISE COMPARISONS Intercruise comparisons of nitrate+nitrite vs phosphate, silicate and dissolved oxygen bottle data compare data from cruise in1801 with previous cruises. For the whole SR3 line, comparisons are made to Aurora Australis cruises au9407, au9404, au9501, au9601, au0103, au0806 and au1121, ranging over the years 1994 to 2011 (i.e. former occupations of the entire SR3 line, with the omission of au9101 and au9309) (Figures 7a, 8 and 9). At the south end of SR3, comparisons are made to Aurora Australis cruises au9407, au9404, au0103, au0806, au1121, au1402 and au1602, ranging over the years 1994 to 2015 (Figure 7b). For au1402 and au1602, note that nutrients were frozen and returned home for analysis. For nitrate+nitrite vs phosphate, cruises au9407, au9404, au9501, au0806 and au1121 all approximately overlay in1801 (Figure 7a), with in1801 clearly showing the tightest spread of values. For au9501 and au0806, the spread is biased towards higher phosphate values; similarly for au9407, but to a lesser degree. Note that the axes in Figure 7a are curtailed at 1.3 µmol/l phosphate and 22 µmol/l nitrate+nitrite, to make comparisons easier to see (the trends continue in a similar fashion towards low nutrient values beyond the axes). Au0103 and au9601 are apparent outliers in Figure 7a, discussed in previous data reports. The same intercruise trends can be seen at the south end of SR3 (Figure 7b). Phosphates for au1402 and au1602 clearly lie between in1801 and au0103 values. For phosphates in general. intercruise variability is most likely due to variation in autoanalyser performance (specific reasons unknown); and for au1402 and au1602, due freezing of samples for later analysis back in Hobart. From this initial comparison, data quality for in1801 looks better than for previous cruises, though confirmation would require a future occupation of SR3, with nutrient analyses via the SEAL autoanalyser. Figure 8 shows intercruise comparisons of silicate, plotted against bottle salinity. Note that silicate values below 50 µmol/l are not shown in the plots. Good agreement is seen between in1801 au1121 (the latest SR3 occupation previous to in1801 with on board nutrient analysis). Au0103 also compares favourably with in1801, but there is increased scatter for the remaining cruises, with slightly lower silicates evident for au9404, au9501 and au9601 (the lower au9407 values are a small number of outliers). Figure 9 shows intercruise comparisons of bottle dissolved oxygen, plotted against bottle salinity. Note that only data deeper than 500 dbar are plotted. In1801 data are mostly tighter (i.e. less scattered) than for the other cruises (with the exception of au9407). There’s reasonable agreement between in1801 and au9407. Au9501 and au0806 also have reasonable agreement with in1801, though values for au9501 and au0806 are slightly biased on the high side, and there’s significantly more scatter for au0806 data. Au9404 and au1121 values are often higher than in1801, while au9601 and au0103 show the highest offset. Overall, nutrient data quality appears much improved for in1801, though confirmation requires a repeat SR3 occupation. 8 FILE FORMATS Data are supplied as column formatted text files, or as matlab files, with all details fully described in the README file included with the data set. Note that all dissolved oxygen and nutrient data in these file versions are in units of µmol/l. The data are also available in WOCE “Exchange” format files. In these file versions, dissolved oxygen and nutrient data are in units of µmol/kg. For density calculation in the volumetric to gravimetric units conversion, the following were used: dissolved oxygen – in situ temperature and CTD salinity at which each Niskin bottle was fired; zero pressure nutrients – laboratory temperature, and in situ CTD salinity at which each Niskin bottle was fired; zero pressure. Note that laboratory temperature for all the nutrient runs, run over several weeks, mostly ranged from ~19 to 22°C; a mean value of 21°C (over all the runs) was used. Table 1: Summary of station information for cruise in1801. All times are UTC; "alt" = minimum altimeter value (m), "maxp" = maximum pressure (dbar). ----------start of CTD----------------------------- -----------------bottom of CTD--------------- -------------------end of CTD---------- CTD station date time latitude longitude depth time latitude longitude depth time latitude longitude depth alt maxp 001 SR3 11 Jan 2018 081635 44 00.09 S 146 19.24 E 251 082356 44 00.09 S 146 19.24 E 253 085350 44 00.12 S 146 19.26 E 253 10.4 244 002 SR3 11 Jan 2018 113033 44 02.98 S 146 17.41 E 561 115907 44 02.98 S 146 17.41 E 568 123535 44 02.93 S 146 17.33 E 558 7.6 566 003 SR3 11 Jan 2018 135925 44 07.19 S 146 13.21 E 1019 142150 44 07.19 S 146 13.22 E 1028 151438 44 07.14 S 146 13.16 E 1014 9.7 1029 004 SR3 11 Jan 2018 184121 44 22.81 S 146 11.36 E 2321 192501 44 22.79 S 146 11.27 E 2327 204427 44 22.77 S 146 11.23 E 2321 9.7 2349 005 SR3 11 Jan 2018 231414 44 43.20 S 146 02.57 E 3205 001257 44 43.13 S 146 02.43 E 3219 014740 44 43.24 S 146 02.60 E 3205 9.3 3261 006 SR3 12 Jan 2018 123729 45 13.31 S 145 51.14 E 2847 132826 45 13.56 S 145 51.13 E 2853 151100 45 13.73 S 145 51.08 E 2837 7.5 2888 007 SR3 12 Jan 2018 181943 45 42.24 S 145 39.38 E 2043 190524 45 42.64 S 145 38.93 E 2146 201538 45 43.00 S 145 38.29 E 2403 13.7 2161 008 SR3 13 Jan 2018 010739 46 10.16 S 145 28.33 E 2713 015928 46 10.18 S 145 28.34 E 2724 032642 46 10.13 S 145 28.30 E 2714 8.3 2756 009 SR3 14 Jan 2018 233315 46 39.04 S 145 15.22 E 3312 003543 46 39.03 S 145 15.23 E 3327 022900 46 38.96 S 145 15.13 E 3319 8.6 3373 010 SR3 15 Jan 2018 143119 47 08.95 S 144 54.64 E 4796 160720 47 09.03 S 144 54.64 E 4810 181412 47 08.95 S 144 54.67 E 4798 11.4 4895 011 SR3 15 Jan 2018 202031 47 28.19 S 144 53.96 E 4389 214043 47 28.12 S 144 53.98 E 4401 234008 47 28.23 S 144 53.98 E 4391 11.3 4473 012 SR3 16 Jan 2018 044621 48 00.00 S 144 40.21 E 4338 061545 48 00.06 S 144 40.19 E 4378 082621 48 00.02 S 144 40.22 E 4268 3.9 4457 013 SR3 16 Jan 2018 104619 48 19.24 S 144 31.79 E 4022 120957 48 19.31 S 144 31.78 E 4081 142253 48 19.51 S 144 31.70 E 4076 7.1 4149 014 SR3 16 Jan 2018 210918 48 46.87 S 144 19.13 E 4130 222642 48 47.11 S 144 19.18 E 4122 002923 48 47.29 S 144 19.22 E 4095 9.4 4189 015 SR3 17 Jan 2018 053900 49 16.23 S 144 05.48 E 4227 065922 49 16.34 S 144 06.26 E 4375 091224 49 16.70 S 144 07.36 E 4381 6.7 4452 016 SR3 17 Jan 2018 202448 49 36.51 S 143 55.84 E 3654 213616 49 36.56 S 143 55.76 E 3697 232537 49 36.59 S 143 55.73 E 3667 12.0 3749 017 SR3 18 Jan 2018 012437 49 53.47 S 143 47.90 E 3668 023643 49 53.41 S 143 48.02 E 3725 044018 49 53.41 S 143 48.02 E 3663 7.5 3783 018 SR3 18 Jan 2018 082601 50 09.56 S 143 39.46 E 3657 093912 50 09.50 S 143 38.98 E 3816 114527 50 09.57 S 143 38.52 E 3706 9.6 3874 019 SR3 18 Jan 2018 134525 50 24.05 S 143 31.69 E 3542 145136 50 23.97 S 143 31.81 E 3509 163629 50 23.92 S 143 31.88 E 3493 9.7 3559 020 SR3 19 Jan 2018 033735 50 40.69 S 143 25.04 E 3471 044121 50 40.72 S 143 25.03 E 3483 063943 50 40.68 S 143 25.07 E 3470 11.9 3530 021 SR3 19 Jan 2018 112246 51 00.56 S 143 16.31 E 3787 124426 51 00.72 S 143 16.19 E 3801 144955 51 01.04 S 143 15.92 E 3772 13.7 3855 022 SR3 19 Jan 2018 172020 51 15.67 S 143 07.95 E 3740 183408 51 15.94 S 143 07.88 E 3789 202715 51 16.30 S 143 07.78 E 3620 6.4 3850 023 SR3 20 Jan 2018 003340 51 33.12 S 143 00.03 E 3632 014720 51 33.29 S 142 59.96 E 3609 032550 51 33.42 S 142 59.92 E 3594 9.2 3663 024 SR3 20 Jan 2018 141346 51 48.63 S 142 50.42 E 3688 153022 51 48.88 S 142 50.18 E 3690 172323 51 49.38 S 142 49.89 E 3654 11.3 3744 025 SR3 20 Jan 2018 191829 52 04.86 S 142 42.68 E 3472 202848 52 05.30 S 142 43.01 E 3461 221808 52 05.90 S 142 43.05 E 3521 11.8 3509 026 SR3 21 Jan 2018 004030 52 22.30 S 142 31.95 E 3368 020556 52 22.55 S 142 31.82 E 3427 040740 52 22.47 S 142 31.88 E 3344 11.3 3475 027 SR3 21 Jan 2018 082028 52 40.10 S 142 23.42 E 3353 093524 52 40.29 S 142 23.20 E 3388 112909 52 40.89 S 142 22.13 E 3396 10.8 3435 028 SR3 21 Jan 2018 142201 53 07.76 S 142 08.42 E 3082 152141 53 07.77 S 142 08.46 E 3104 165209 53 07.78 S 142 08.68 E 3102 12.8 3142 029 SR3 21 Jan 2018 233115 53 34.75 S 141 51.73 E 2495 002036 53 34.63 S 141 51.84 E 2488 014159 53 34.53 S 141 51.92 E 2419 11.7 2514 030 SR3 22 Jan 2018 064756 54 04.26 S 141 35.87 E 2496 073725 54 04.25 S 141 35.88 E 2531 091042 54 04.24 S 141 35.93 E 2510 8.7 2561 031 SR3 22 Jan 2018 193751 54 31.67 S 141 19.76 E 2769 203800 54 31.54 S 141 19.96 E 2823 220202 54 31.50 S 141 20.04 E 2782 11.1 2857 032 SR3 23 Jan 2018 041538 55 01.28 S 141 01.27 E 3139 052407 55 01.24 S 141 01.30 E 3318 070603 55 01.24 S 141 01.31 E 3162 12.4 3362 033 SR3 23 Jan 2018 134700 55 29.97 S 140 43.81 E 4048 150956 55 29.95 S 140 43.79 E 4176 170630 55 29.98 S 140 43.89 E 4062 11.4 4245 ----------start of CTD----------------------------- -----------------bottom of CTD--------------- -------------------end of CTD---------- CTD station date time latitude longitude depth time latitude longitude depth time latitude longitude depth alt maxp 034 SR3 23 Jan 2018 200321 55 55.81 S 140 24.56 E 3569 211700 55 55.80 S 140 24.56 E 3656 225829 55 55.80 S 140 24.59 E 3600 11.6 3710 035 SR3 24 Jan 2018 050932 56 25.82 S 140 06.05 E 3843 062639 56 25.80 S 140 06.01 E 3927 082435 56 25.81 S 140 06.05 E 3843 11.7 3989 036 SR3 24 Jan 2018 112749 56 55.78 S 139 50.93 E 4097 124741 56 55.76 S 139 50.93 E 4127 144014 56 55.76 S 139 51.09 E 4102 12.2 4194 037 SR3 24 Jan 2018 205021 57 21.04 S 139 53.08 E 4090 220630 57 20.94 S 139 53.45 E 4095 235059 57 21.06 S 139 53.06 E 4087 10.6 4163 038 SR3 25 Jan 2018 024825 57 50.99 S 139 51.02 E 3971 040124 57 50.99 S 139 50.98 E 3992 060143 57 51.01 S 139 51.01 E 3971 11.8 4055 039 SR3 25 Jan 2018 103255 58 21.11 S 139 51.14 E 3953 114544 58 21.06 S 139 51.04 E 3994 135330 58 21.07 S 139 51.01 E 3944 9.7 4060 040 SR3 25 Jan 2018 184621 58 51.00 S 139 50.33 E 3879 200048 58 51.00 S 139 50.31 E 3893 213622 58 51.04 S 139 50.30 E 3880 9.3 3957 041 SR3 26 Jan 2018 023630 58 50.74 S 139 50.38 E 3860 030030 58 50.72 S 139 50.41 E 3860 034147 58 50.72 S 139 50.38 E 3859 - 1004 042 SR3 26 Jan 2018 101856 59 21.02 S 139 51.02 E 4125 113947 59 21.02 S 139 51.10 E 4166 133951 59 21.02 S 139 50.90 E 4121 11.4 4236 043 SR3 26 Jan 2018 164740 59 50.96 S 139 51.59 E 4441 180955 59 50.99 S 139 51.53 E 4455 200536 59 51.02 S 139 51.51 E 4441 11.0 4534 044 SR3 27 Jan 2018 010338 60 21.05 S 139 51.13 E 4404 022650 60 20.99 S 139 50.99 E 4416 044020 60 20.94 S 139 50.84 E 4403 11.5 4494 045 SR3 27 Jan 2018 092040 60 50.98 S 139 50.94 E 4366 104255 60 51.05 S 139 51.10 E 4379 124440 60 51.11 S 139 51.34 E 4367 12.4 4454 046 SR3 28 Jan 2018 002523 61 21.01 S 139 50.44 E 4305 014550 61 21.09 S 139 50.42 E 4317 034344 61 21.11 S 139 50.45 E 4304 12.4 4391 047 SR3 28 Jan 2018 063729 61 51.05 S 139 50.31 E 4253 075541 61 51.05 S 139 50.38 E 4266 101333 61 51.04 S 139 50.36 E 4254 12.5 4338 048 SR3 28 Jan 2018 203525 62 21.61 S 139 50.38 E 3908 215759 62 21.74 S 139 50.75 E 3920 235140 62 21.89 S 139 51.27 E 3914 7.0 3988 049 SR3 29 Jan 2018 031655 62 51.01 S 139 51.11 E 3168 042236 62 50.99 S 139 51.05 E 3179 060556 62 50.98 S 139 51.02 E 3169 11.1 3223 050 SR3 29 Jan 2018 130506 63 20.99 S 139 49.67 E 3759 141715 63 20.99 S 139 49.72 E 3774 160431 63 20.97 S 139 49.93 E 3763 8.6 3837 051 SR3 29 Jan 2018 211350 63 51.88 S 139 51.94 E 3686 222301 63 51.58 S 139 52.31 E 3703 235442 63 51.17 S 139 52.92 E 3694 11.4 3761 052 SR3 30 Jan 2018 115914 64 12.81 S 139 50.19 E 3482 130355 64 12.86 S 139 49.96 E 3495 144638 64 12.86 S 139 49.84 E 3481 10.2 3549 053 SR3 30 Jan 2018 172842 64 33.08 S 139 51.01 E 3039 182547 64 33.05 S 139 50.83 E 3052 194414 64 32.99 S 139 50.65 E 3044 11.4 3093 054 SR3 30 Jan 2018 213823 64 48.66 S 139 51.62 E 2556 223009 64 48.61 S 139 51.56 E 2566 234242 64 48.65 S 139 51.57 E 2557 11.7 2596 055 SR3 31 Jan 2018 041844 65 04.19 S 139 51.56 E 2458 050332 65 04.16 S 139 51.56 E 2475 063220 65 04.19 S 139 51.52 E 2459 11.6 2503 056 SR3 31 Jan 2018 100512 65 23.95 S 139 51.17 E 2390 105444 65 23.93 S 139 51.19 E 2399 122432 65 23.89 S 139 51.24 E 2394 10.2 2426 057 SR3 31 Jan 2018 212221 65 25.78 S 139 51.06 E 1797 220253 65 25.79 S 139 51.01 E 1939 230701 65 25.76 S 139 51.07 E 1794 13.5 1953 058 SR3 01 Feb 2018 015231 65 31.81 S 139 51.03 E 1289 021748 65 31.85 S 139 51.00 E 1317 030122 65 31.78 S 139 50.94 E 1296 10.3 1324 059 SR3 01 Feb 2018 051552 65 34.19 S 139 51.18 E 800 053427 65 34.21 S 139 51.19 E 819 061919 65 34.24 S 139 51.17 E 782 10.0 818 060 SR3 01 Feb 2018 073939 65 42.70 S 139 51.69 E 283 074720 65 42.70 S 139 51.69 E 283 081821 65 42.67 S 139 51.67 E 285 7.8 278 061 shelf 01 Feb 2018 234040 66 25.60 S 145 04.19 E 423 235012 66 25.59 S 145 04.22 E 424 001752 66 25.58 S 145 04.24 E 421 10.0 418 062 shelf 02 Feb 2018 063107 66 20.84 S 144 39.53 E 414 064119 66 20.85 S 144 39.55 E 419 070940 66 20.83 S 144 39.50 E 414 12.0 411 063 shelf 02 Feb 2018 081037 66 19.25 S 144 23.46 E 432 082147 66 19.17 S 144 23.29 E 434 085305 66 19.11 S 144 23.02 E 433 8.3 431 064 shelf 02 Feb 2018 110336 66 14.50 S 144 01.33 E 439 111409 66 14.47 S 144 01.36 E 442 114758 66 14.44 S 144 01.42 E 435 10.0 437 065 shelf 02 Feb 2018 130425 66 07.24 S 143 49.78 E 432 131522 66 07.22 S 143 49.84 E 437 134740 66 07.20 S 143 49.88 E 432 9.7 432 066 shelf 02 Feb 2018 145858 65 59.99 S 143 38.44 E 424 150745 66 00.00 S 143 38.41 E 423 153126 66 00.01 S 143 38.39 E 422 9.4 418 ----------start of CTD----------------------------- -----------------bottom of CTD--------------- -------------------end of CTD---------- CTD station date time latitude longitude depth time latitude longitude depth time latitude longitude depth alt maxp 067 Ninja 02 Feb 2018 231547 64 59.90 S 145 29.73 E 3301 001613 64 59.90 S 145 29.86 E 3312 014615 64 59.89 S 145 30.16 E 3307 12.1 3359 068 P11S 03 Feb 2018 122048 65 23.99 S 150 00.05 E 2853 131345 65 23.99 S 150 00.01 E 2866 145327 65 23.98 S 149 59.98 E 2854 6.6 2908 069 P11S 03 Feb 2018 171310 65 35.49 S 149 59.87 E 2478 180138 65 35.12 S 149 59.42 E 2494 191305 65 34.72 S 149 58.24 E 2522 11.3 2522 070 P11S 04 Feb 2018 034754 65 38.32 S 150 00.91 E 2328 043552 65 38.10 S 150 00.83 E 2345 055216 65 37.22 S 149 59.36 E 2401 10.2 2371 071 P11S 04 Feb 2018 093618 64 59.96 S 149 59.75 E 3254 104434 64 59.97 S 149 59.90 E 3274 121901 65 00.00 S 150 00.31 E 3264 10.0 3322 072 P11S 04 Feb 2018 144722 64 35.99 S 150 00.01 E 3423 155018 64 36.00 S 150 00.04 E 3434 172606 64 36.01 S 150 00.09 E 3425 11.9 3484 073 P11S 04 Feb 2018 223939 64 17.97 S 149 59.98 E 3525 234608 64 18.04 S 150 00.13 E 3549 012105 64 18.10 S 150 00.26 E 3527 14.1 3600 074 P11S 05 Feb 2018 034355 63 54.01 S 150 00.03 E 3628 044945 63 54.02 S 150 00.08 E 3639 064111 63 54.04 S 150 00.17 E 3629 11.8 3695 075 P11S 05 Feb 2018 091006 63 29.96 S 150 00.00 E 3690 102716 63 29.96 S 150 00.02 E 3703 122502 63 30.09 S 150 00.18 E 3692 11.2 3761 076 P11S 05 Feb 2018 184038 62 59.99 S 150 00.02 E 3807 195028 63 00.02 S 150 00.05 E 3817 213250 63 00.04 S 150 00.08 E 3805 11.5 3878 077 P11S 06 Feb 2018 002818 62 30.01 S 150 00.01 E 3834 013737 62 30.01 S 150 00.01 E 3851 034006 62 30.13 S 150 00.07 E 3846 11.6 3912 078 P11S 06 Feb 2018 064253 62 00.02 S 149 59.98 E 3707 074933 62 00.02 S 149 59.98 E 3722 100259 62 00.08 S 149 59.95 E 3705 11.3 3780 079 S4 06 Feb 2018 215412 63 11.37 S 147 49.91 E 3871 230552 63 11.44 S 147 49.88 E 3881 004815 63 11.43 S 147 49.90 E 3869 11.1 3944 080 S4 07 Feb 2018 042848 63 03.01 S 146 26.86 E 3910 054114 63 03.00 S 146 26.97 E 3920 073445 63 02.99 S 146 27.00 E 3909 11.5 3984 081 S4 07 Feb 2018 150634 62 54.00 S 145 01.79 E 3982 162157 62 54.03 S 145 01.76 E 3995 180351 62 54.55 S 145 01.20 E 3979 11.0 4061 082 S4 07 Feb 2018 220108 62 45.02 S 143 37.18 E 4074 231737 62 45.05 S 143 37.15 E 4086 010148 62 45.05 S 143 37.16 E 4076 11.4 4155 083 S4 08 Feb 2018 092211 62 36.01 S 142 12.03 E 4090 103906 62 36.02 S 142 12.01 E 4101 125444 62 36.07 S 142 11.89 E 4088 11.3 4170 084 S4 08 Feb 2018 161921 62 28.81 S 141 01.76 E 4124 174701 62 28.80 S 141 01.80 E 4138 192836 62 28.82 S 141 01.73 E 4123 11.4 4207 085 S4 09 Feb 2018 141146 62 10.31 S 138 24.57 E 3948 153325 62 10.19 S 138 24.61 E 3959 171818 62 10.15 S 138 24.73 E 3947 11.5 4024 086 S4 09 Feb 2018 215510 61 59.93 S 137 00.04 E 3846 231118 61 59.61 S 137 00.56 E 3863 005334 61 59.51 S 137 00.82 E 3851 9.4 3927 087 S4 10 Feb 2018 053917 62 00.00 S 135 34.87 E 4286 065731 62 00.02 S 135 34.84 E 4300 091225 62 00.02 S 135 34.87 E 4285 13.5 4373 088 S4 10 Feb 2018 163024 62 01.19 S 134 10.27 E 4327 174953 62 01.21 S 134 10.02 E 4340 194449 62 01.22 S 134 10.11 E 4327 11.2 4416 089 132E 11 Feb 2018 013846 62 29.98 S 132 02.98 E 4427 030145 62 29.99 S 132 02.98 E 4441 050218 62 30.01 S 132 02.99 E 4430 11.1 4521 090 132E 11 Feb 2018 093151 63 05.05 S 132 06.08 E 4242 105032 63 05.06 S 132 06.10 E 4254 125942 63 05.04 S 132 05.97 E 4243 9.4 4330 091 132E 11 Feb 2018 173525 63 29.99 S 132 04.81 E 4015 185032 63 30.01 S 132 04.77 E 4028 202850 63 30.04 S 132 04.75 E 4017 11.3 4095 092 132E 11 Feb 2018 231824 63 58.48 S 132 06.38 E 3204 001745 63 58.52 S 132 06.33 E 3218 014423 63 58.63 S 132 06.50 E 3206 11.1 3264 093 132E 12 Feb 2018 063708 64 26.93 S 132 04.60 E 1465 071342 64 26.90 S 132 04.57 E 1471 082303 64 26.87 S 132 04.55 E 1469 11.3 1479 094 132E 12 Feb 2018 182930 64 50.27 S 132 05.41 E 862 184812 64 50.27 S 132 05.53 E 863 191509 64 50.24 S 132 05.70 E 855 7.4 866 095 132E 12 Feb 2018 202939 64 58.76 S 132 03.87 E 292 203654 64 58.74 S 132 03.85 E 293 205514 64 58.76 S 132 03.86 E 292 8.3 288 096 132E 13 Feb 2018 180521 61 59.70 S 132 00.20 E 4466 192615 61 59.71 S 132 00.02 E 4479 212239 61 59.69 S 131 59.60 E 4465 10.8 4559 097 132E 14 Feb 2018 020013 61 29.99 S 131 59.99 E 4521 032137 61 30.00 S 131 59.96 E 4533 055647 61 30.01 S 132 00.25 E 4520 8.4 4618 098 132E 14 Feb 2018 091032 60 59.94 S 132 00.17 E 4572 103444 60 59.98 S 132 00.52 E 4582 125306 61 00.17 S 132 00.50 E 4570 11.2 4665 099 132E 14 Feb 2018 160416 60 31.54 S 132 07.75 E 4612 173012 60 31.50 S 132 07.82 E 4626 192526 60 31.49 S 132 07.82 E 4611 11.2 4710 100 132E 14 Feb 2018 222318 60 01.94 S 132 13.00 E 4648 235057 60 01.91 S 132 13.06 E 4662 014809 60 01.89 S 132 13.01 E 4649 10.7 4748 101 132E 15 Feb 2018 045852 59 30.00 S 132 06.01 E 4672 062431 59 30.01 S 132 06.06 E 4684 082534 59 29.98 S 132 05.99 E 4671 11.5 4770 102 132E 15 Feb 2018 112236 58 58.27 S 132 01.51 E 4663 124949 58 58.32 S 132 01.69 E 4676 150026 58 58.31 S 132 01.75 E 4663 10.0 4763 103 132E 15 Feb 2018 174716 58 29.97 S 132 00.47 E 4655 192152 58 30.01 S 132 00.65 E 4667 212621 58 30.05 S 132 00.70 E 4653 9.9 4753 104 132E 16 Feb 2018 002512 58 00.00 S 131 59.98 E 4656 015126 58 00.00 S 131 59.94 E 4670 042149 58 00.04 S 131 58.73 E 4656 11.4 4754 105 132E 16 Feb 2018 071142 57 31.03 S 132 00.15 E 4656 083549 57 31.00 S 132 00.20 E 4672 110506 57 30.95 S 132 00.20 E 4658 10.9 4757 106 132E 16 Feb 2018 141327 56 57.92 S 132 09.18 E 4529 153627 56 57.92 S 132 09.21 E 4553 173819 56 57.91 S 132 09.22 E 4533 10.5 4634 107 eddy 18 Feb 2018 085930 56 32.99 S 141 29.63 E 3592 092143 56 32.99 S 141 29.63 E 3609 100328 56 33.00 S 141 29.66 E 3664 - 1003 108 eddy 19 Feb 2018 045536 53 37.73 S 142 58.78 E 2999 051737 53 37.75 S 142 58.79 E 3003 060631 53 37.75 S 142 58.79 E 3003 - 1003 Table 2: CTD calibration coefficients and calibration dates for cruise in1801. Note that platinum temperature calibrations are for the ITS-90 scale. Pressure slope/offset, temperature, conductivity and oxygen values are from CSIRO and SeaBird pre cruise calibrations. Fluorometer and PAR values are manufacturer supplied. Transmissometer values are a rescaling of the manufacturer supplied coefficients to give transmittance as a %, referenced to clean water. For oxygen, the final calibration uses in situ bottle measurements (the manufacturer supplied coefficients are not used). Note the revised CPcor value used for primary and secondary conductivity, which reduces the depth dependent calibration error due to compressibility of the borosilicate glass cell. For FLBB fluorometer and backscatter, dark value derived from “dark profiles” at stations 25 and 106. Primary Temperature, serial 6189, 04/04/2017 Secondary Temperature, serial 6180, 19/04/2017 (station 1 to 13) (station 1 to 11, 14 to 108) G :4.38623631e-003 G :4.33710187e-003 H :6.41207874e-004 H :6.34603081e-004 I :2.30415384e-005 I :2.17586153e-005 J :2.14398355e-006 J :1.99921954e-006 F0 :1000.000 F0 :1000.000 Slope :1.0000000 Slope :1.0000000 Offset :0.0000 Offset :0.0000 Primary Temperature, serial 4522, 15/12/2017 Secondary Temperature, serial 4522, 15/12/2017 (station 14 to 108) (station 12 to 13) G :4.33235720e-003 G :4.33235720e-003 H :6.34643520e-004 H :6.34643520e-004 I :1.98678350e-005 I :1.98678350e-005 J :1.55527340e-006 J :1.55527340e-006 F0 :1000.000 F0 :1000.000 Slope :1.0000000 Slope :1.0000000 Offset :0.0000 Offset :0.0000 Primary Conductivity, serial 4685, 02/05/2017 Secondary Conductivity, serial 4664, 02/05/2017 G :-9.99847835e+000 G :-9.89576006e+000 H :1.34567880e+000 H :1.34531130e+000 I :2.26080131e-004 I :-2.43201518e-004 J :3.94289636e-005 J :7.66668505e-005 CTcor :3.2500e-006 CTcor :3.2500e-006 CPcor :-8.4500000e-008 CPcor :-8.4500000e-008 Slope :1.00000000 Slope :1.00000000 Offset :0.00000 Offset :0.00000 CTD704 Pressure, serial 1332, 21/08/2017 C1 :-4.143143e+004 C2 :-3.307590e-001 C3 :1.332300e-002 D1 :3.552400e-002 D2 :0.000000e+000 T1 :3.046230e+001 T2 :-4.100470e-004 T3 :3.894920e-006 T4 :4.633350e-009 T5 :0.000000e+000 Slope :1.000000 Offset :0.5800 (dbar) AD590M :1.279750e-002 AD590B :-9.342582e+000 Primary Oxygen, serial 3534, 26/04/2017 Secondary Oxygen, serial 3542, 26/04/2017 (for display at time of logging only) (for display at time of logging only) Soc :4.75400e-001 Soc :5.01200e-001 Voffset :-4.97900e-001 Voffset :-5.22300e-001 A :-4.35090e-003 A :-3.60190e-003 B :2.23240e-004 B :1.95170e-004 C :-3.44950e-006 C :-3.06820e-006 E :3.60000e-002 E :3.60000e-002 Tau20 :1.34000e+000 Tau20 :1.97000e+000 D1 :1.92634e-004 D1 :1.92634e-004 D2 :-4.64803e-002 D2 :-4.64803e-002 H1 :-3.30000e-002 H1 :-3.30000e-002 H2 :5.00000e+003 H2 :5.00000e+003 H3 :1.45000e+003 H3 :1.45000e+003 Transmissometer, serial 1421DR, 07/08/2017 PAR, serial 70111, QCP2300HP, 26/06/2017 (referenced to clean water) M :1.000 M :21.2815 B :0.000 B :-0.1277 Cal. Constant :2.1834061e+010 Path length :0.25 (m) Multiplier :1.0 Offset :-4.6362e-002 FLBBRTD, serial 4799, 09/08/2017 Fluorometer Backscatter Dark output :0.0500 Dark output :0.0615 Scale factor :6.000e+000 Scale factor :1.429e-003 Wavelength :700 Table 3: CTD conductivity calibration coefficients for cruise in1801. F1, F2 and F3 are respectively conductivity bias, slope and station-dependent correction calibration terms. n is the number of samples retained for calibration in each station grouping; σ is the standard deviation of the conductivity residual for the n samples in the station grouping. stn grouping F1 F2 F3 n σ ———————————— —————————————— —————————————— ——————————————— ———— ———————— 001 to 011 -0.34912601E-02 0.10002407E-02 -0.25260120E-08 216 0.000675 012 to 080 -0.19948864E-03 0.10001028E-02 0.43004868E-09 1499 0.000623 081 to 108 0.10274673E-01 0.99966219E-03 0.13331931E-08 638 0.000702 Table 4: Station-dependent-corrected conductivity slope term (F2 + F3 . N), for station number N, and F2 and F3 the conductivity slope and station-dependent correction calibration terms respectively, for cruise in1801. station (F2 + F3 . N) station (F2 + F3 . N) station (F2 + F3 . N) number number number ——————————————————————— —————————————————————— —————————————————————— 1 0.10002382E-02 37 0.10001187E-02 73 0.10001342E-02 2 0.10002357E-02 38 0.10001191E-02 74 0.10001346E-02 3 0.10002332E-02 39 0.10001196E-02 75 0.10001351E-02 4 0.10002306E-02 40 0.10001200E-02 76 0.10001355E-02 5 0.10002281E-02 41 0.10001204E-02 77 0.10001359E-02 6 0.10002256E-02 42 0.10001209E-02 78 0.10001363E-02 7 0.10002230E-02 43 0.10001213E-02 79 0.10001368E-02 8 0.10002205E-02 44 0.10001217E-02 80 0.10001372E-02 9 0.10002180E-02 45 0.10001222E-02 81 0.99977018E-03 10 0.10002155E-02 46 0.10001226E-02 82 0.99977151E-03 11 0.10002129E-02 47 0.10001230E-02 83 0.99977284E-03 12 0.10001080E-02 48 0.10001234E-02 84 0.99977418E-03 13 0.10001084E-02 49 0.10001239E-02 85 0.99977551E-03 14 0.10001088E-02 50 0.10001243E-02 86 0.99977684E-03 15 0.10001093E-02 51 0.10001247E-02 87 0.99977818E-03 16 0.10001097E-02 52 0.10001252E-02 88 0.99977951E-03 17 0.10001101E-02 53 0.10001256E-02 89 0.99978084E-03 18 0.10001105E-02 54 0.10001260E-02 90 0.99978218E-03 19 0.10001110E-02 55 0.10001265E-02 91 0.99978351E-03 20 0.10001114E-02 56 0.10001269E-02 92 0.99978484E-03 21 0.10001118E-02 57 0.10001273E-02 93 0.99978618E-03 22 0.10001123E-02 58 0.10001277E-02 94 0.99978751E-03 23 0.10001127E-02 59 0.10001282E-02 95 0.99978884E-03 24 0.10001131E-02 60 0.10001286E-02 96 0.99979017E-03 25 0.10001136E-02 61 0.10001290E-02 97 0.99979151E-03 26 0.10001140E-02 62 0.10001295E-02 98 0.99979284E-03 27 0.10001144E-02 63 0.10001299E-02 99 0.99979417E-03 28 0.10001148E-02 64 0.10001303E-02 100 0.99979551E-03 29 0.10001153E-02 65 0.10001308E-02 101 0.99979684E-03 30 0.10001157E-02 66 0.10001312E-02 102 0.99979817E-03 31 0.10001161E-02 67 0.10001316E-02 103 0.99979951E-03 32 0.10001166E-02 68 0.10001320E-02 104 0.99980084E-03 33 0.10001170E-02 69 0.10001325E-02 105 0.99980217E-03 34 0.10001174E-02 70 0.10001329E-02 106 0.99980351E-03 35 0.10001179E-02 71 0.10001333E-02 107 0.99980484E-03 36 0.10001183E-02 72 0.10001338E-02 108 0.99980617E-03 Table 5: Surface pressure offsets (i.e. poff in dbar) for cruise in1801. For each station, these values are subtracted from the pressure calibration "offset" value in Table 2. stn poff stn poff stn poff stn poff stn poff stn poff ——— ————— ——— ————— ——— ————— ——— ————— ——— ————— ——— ————— 001 -0.24 019 -0.55 037 -0.35 055 -0.51 073 -0.47 091 -0.67 002 -0.23 020 -0.33 038 -0.35 056 -0.49 074 -0.48 092 -0.70 003 -0.24 021 -0.36 039 -0.39 057 -0.40 075 -0.44 093 -0.65 004 -0.35 022 -0.36 040 -0.48 058 -0.39 076 -0.45 094 -0.52 005 -0.37 023 -0.30 041 -0.56 059 -0.37 077 -0.45 095 -0.53 006 -0.36 024 -0.27 042 -0.45 060 -0.39 078 -0.42 096 -0.59 007 -0.41 025 -0.29 043 -0.45 061 -0.38 079 -0.49 097 -0.60 008 -0.38 026 -0.32 044 -0.41 062 -0.45 080 -0.53 098 -0.54 009 -0.13 027 -0.32 045 -0.43 063 -0.38 081 -0.48 099 -0.52 010 -0.10 028 -0.43 046 -0.73 064 -0.44 082 -0.50 100 -0.47 011 -0.12 029 -0.55 047 -0.86 065 -0.47 083 -0.47 101 -0.46 012 -0.16 030 -0.58 048 -0.65 066 -0.49 084 -0.52 102 -0.48 013 -0.18 031 -0.59 049 -0.59 067 -0.46 085 -0.59 103 -0.50 014 -0.21 032 -0.66 050 -0.48 068 -0.51 086 -0.61 104 -0.55 015 -0.23 033 -0.54 051 -0.43 069 -0.55 087 -0.61 105 -0.65 016 -0.28 034 -0.53 052 -0.42 070 -0.41 088 -0.52 106 -0.65 017 -0.33 035 -0.45 053 -0.50 071 -0.47 089 -0.60 107 -0.20 018 -0.40 036 -0.41 054 -0.49 072 -0.47 090 -0.62 108 -0.05 Table 6: CTD dissolved oxygen calibration coefficients for cruise in1801: slope, bias, tcor ( = temperature correction term), and pcor ( = pressure correction term). dox is equal to 2.8σ, for σ as defined in the CTD Methodology. For deep stations, coefficients are given for both the shallow and deep part of the profile, according to the profile split used for calibration (see section 5.4 in the text); whole profile fit used for stations shallower than 1400 dbar (i.e. stations with only "shallow" set of coefficients in the table) (see section 5.4 for exceptions). ----------------------shallow----------------------------- ----------------------deep-------------------------- stn slope bias tcor pcor dox slope bias tcor pcor dox 1 0.709093 -0.627685 -0.007671 0.000116 0.074810 2 1.134027 -1.205114 -0.030850 0.000017 0.125380 3 0.499810 -0.296171 0.004628 0.000227 0.084345 4 0.495413 -0.227123 0.000071 0.000123 0.089076 0.606878 -0.384455 -0.005512 0.000148 0.032341 5 0.551999 -0.319929 -0.001389 0.000147 0.133773 0.396292 -0.105922 0.005163 0.000124 0.014800 6 0.490131 -0.226701 0.002200 0.000126 0.103328 0.483104 -0.249410 0.016116 0.000153 0.029972 7 0.501120 -0.226831 0.000235 0.000110 0.140051 8 0.494991 -0.226034 0.001354 0.000116 0.115084 0.345230 -0.086060 0.028373 0.000156 0.019862 9 0.514558 -0.265847 -0.000201 0.000142 0.098784 0.721823 -0.452590 -0.048065 0.000108 0.026115 10 0.511081 -0.261538 0.000322 0.000140 0.087704 0.492506 -0.186540 -0.021769 0.000108 0.022974 11 0.497222 -0.240383 0.002468 0.000138 0.129674 0.450343 -0.107375 -0.029335 0.000093 0.045070 12 0.550091 -0.336700 -0.001891 0.000179 0.080386 0.502941 -0.175235 -0.032700 0.000098 0.044229 13 0.554933 -0.296494 -0.006077 0.000123 0.080305 14 0.489782 -0.232446 0.003770 0.000137 0.109942 0.485390 -0.244160 0.017125 0.000145 0.046903 15 0.543642 -0.281502 -0.005000 0.000123 0.102582 0.523869 -0.233119 -0.020946 0.000115 0.058348 16 0.492830 -0.216458 0.000921 0.000117 0.121193 0.550769 -0.314064 0.001429 0.000144 0.038747 17 0.492498 -0.215635 0.000668 0.000117 0.110306 0.538958 -0.269344 -0.013742 0.000125 0.032062 18 0.497023 -0.219673 0.000761 0.000110 0.088014 0.562819 -0.311112 -0.010519 0.000134 0.027950 19 0.512231 -0.252161 -0.000334 0.000132 0.078896 0.506831 -0.261339 0.007677 0.000143 0.029020 20 0.495379 -0.261468 0.005875 0.000170 0.109040 0.608817 -0.380791 -0.006316 0.000142 0.029399 21 0.511507 -0.309571 0.006602 0.000210 0.085618 0.743902 -0.452456 -0.060886 0.000094 0.052206 22 0.509788 -0.289455 0.004832 0.000188 0.087803 0.608924 -0.377428 -0.008765 0.000141 0.043013 23 0.406392 -0.087341 0.011126 0.000077 0.094383 0.605107 -0.382466 -0.005476 0.000147 0.037306 24 0.510442 -0.291727 0.004672 0.000192 0.131895 0.604461 -0.386859 -0.000790 0.000150 0.056012 25 0.524595 -0.281221 -0.001065 0.000151 0.095463 0.490138 -0.222256 0.002764 0.000131 0.049667 26 0.545832 -0.294204 -0.005917 0.000134 0.111469 0.560066 -0.339158 0.010721 0.000151 0.050995 27 0.461197 -0.190630 0.010510 0.000125 0.118564 0.605434 -0.389465 -0.002973 0.000151 0.048830 28 0.510490 -0.253664 0.001005 0.000140 0.080402 0.405757 -0.098418 0.010210 0.000117 0.031034 29 0.517210 -0.268364 0.000640 0.000148 0.042756 0.698103 -0.500655 -0.021813 0.000143 0.015449 30 0.536610 -0.290428 -0.004525 0.000144 0.044117 0.699202 -0.499638 -0.028841 0.000142 0.011877 31 0.521820 -0.277616 0.000277 0.000155 0.093576 0.481750 -0.156752 -0.024899 0.000097 0.016571 32 0.500655 -0.246255 0.005958 0.000139 0.105586 0.451270 -0.112710 -0.021395 0.000093 0.025011 33 0.499849 -0.244736 0.005105 0.000142 0.096232 0.600174 -0.403236 0.008915 0.000165 0.019475 34 0.529495 -0.279120 -0.000804 0.000143 0.091344 0.697589 -0.496648 -0.025959 0.000147 0.037855 35 0.516209 -0.262705 0.002562 0.000139 0.056744 0.583164 -0.354774 -0.001974 0.000144 0.023805 36 0.510957 -0.253334 0.003322 0.000137 0.080036 0.433891 -0.096910 -0.017232 0.000098 0.023800 37 0.511298 -0.255871 0.003755 0.000139 0.076315 0.404480 -0.099555 0.016318 0.000120 0.029387 38 0.522191 -0.268248 0.000088 0.000139 0.042243 0.698042 -0.497542 -0.028990 0.000148 0.025218 39 0.521381 -0.267445 -0.001037 0.000140 0.090227 0.403721 -0.100009 0.016545 0.000120 0.029864 40 0.525332 -0.279482 0.000372 0.000151 0.105738 0.405162 -0.098055 0.015692 0.000119 0.028572 41 0.516446 -0.251790 0.000069 0.000119 0.114305 42 0.520233 -0.275634 0.006966 0.000146 0.077000 0.402748 -0.099707 0.020339 0.000122 0.027079 43 0.518161 -0.274096 0.008219 0.000150 0.088765 0.404546 -0.098322 0.019864 0.000121 0.029332 44 0.523618 -0.279798 0.005875 0.000148 0.110171 0.695168 -0.499442 -0.032451 0.000150 0.029923 45 0.533589 -0.292723 0.004394 0.000148 0.114991 0.348560 0.012168 -0.004547 0.000098 0.026705 46 0.515282 -0.262933 0.006766 0.000140 0.104404 0.401612 -0.100556 0.025607 0.000125 0.023061 47 0.523353 -0.275468 0.004088 0.000145 0.053110 0.403183 -0.099727 0.022251 0.000124 0.029287 48 0.528013 -0.280755 0.002163 0.000147 0.041316 0.696122 -0.501946 -0.028695 0.000146 0.019713 49 0.529768 -0.275554 -0.003294 0.000142 0.071005 0.401867 -0.098909 0.023840 0.000134 0.015471 50 0.541600 -0.321111 0.020951 0.000163 0.065903 0.401767 -0.101060 0.024397 0.000134 0.024396 51 0.548028 -0.315427 -0.005411 0.000163 0.119708 0.491148 -0.211795 0.002606 0.000129 0.029108 52 0.473284 -0.154562 -0.030278 0.000105 0.090771 0.404037 -0.096492 0.024391 0.000132 0.028694 53 0.558745 -0.357213 0.035685 0.000179 0.065744 0.408498 -0.089334 0.009972 0.000124 0.034577 54 0.522752 -0.264220 0.002730 0.000139 0.096748 0.493406 -0.209440 -0.007390 0.000127 0.015079 55 0.543285 -0.307222 0.008888 0.000156 0.108826 0.339152 0.078220 -0.088387 0.000066 0.017838 56 0.532706 -0.283737 0.002375 0.000148 0.102698 0.464079 -0.156548 -0.018589 0.000116 0.019528 57 0.583623 -0.385123 0.026551 0.000183 0.090631 58 0.527170 -0.269540 0.003479 0.000141 0.094280 59 0.537021 -0.290998 0.014607 0.000171 0.155403 60 0.498319 -0.192782 0.012196 0.000117 0.043574 61 0.523013 -0.267371 0.001429 0.000179 0.132414 62 0.501716 -0.218162 -0.003458 0.000109 0.112257 63 0.509702 -0.215402 0.015172 0.000152 0.108634 64 0.601828 -0.414234 0.028989 0.000272 0.091321 65 0.486093 -0.198652 -0.016456 0.000107 0.095527 66 0.523323 -0.262507 -0.000540 0.000148 0.085874 67 0.515332 -0.237537 -0.008401 0.000117 0.110292 0.405806 -0.093689 0.023275 0.000128 0.024162 68 0.547669 -0.314049 0.003841 0.000156 0.122370 0.606365 -0.390516 -0.009269 0.000145 0.021951 69 0.517301 -0.248839 -0.001490 0.000128 0.093823 0.424794 -0.041734 -0.124109 0.000061 0.018162 70 0.533134 -0.284080 -0.004472 0.000146 0.099304 0.376946 0.004715 -0.068832 0.000081 0.019936 71 0.534375 -0.297227 0.005665 0.000157 0.059422 0.696757 -0.503283 -0.037048 0.000139 0.018771 72 0.527723 -0.304915 0.028685 0.000166 0.075009 0.697499 -0.502310 -0.037131 0.000139 0.015100 73 0.532210 -0.304946 0.018856 0.000163 0.029445 0.695664 -0.503527 -0.032484 0.000144 0.020585 74 0.532710 -0.324635 0.041288 0.000173 0.044780 0.404988 -0.095442 0.020255 0.000124 0.018318 75 0.507196 -0.196693 -0.037312 0.000103 0.081028 0.697840 -0.501484 -0.035911 0.000141 0.015552 76 0.525201 -0.356876 0.081402 0.000206 0.094769 0.695334 -0.502524 -0.029458 0.000147 0.019828 77 0.529672 -0.288294 0.006728 0.000151 0.047482 0.406140 -0.095017 0.015367 0.000120 0.024758 78 0.528670 -0.316181 0.031071 0.000170 0.046321 0.694208 -0.503084 -0.028745 0.000149 0.020427 79 0.510261 -0.299300 0.044864 0.000175 0.062647 0.403564 -0.097571 0.021391 0.000126 0.019131 80 0.533949 -0.303146 0.013213 0.000155 0.086478 0.546219 -0.278738 -0.018208 0.000124 0.017746 81 0.515015 -0.308336 0.050301 0.000177 0.067253 0.610754 -0.383798 -0.012959 0.000139 0.032684 82 0.529629 -0.285982 0.006538 0.000147 0.067988 0.539262 -0.268001 -0.011846 0.000124 0.039949 83 0.527093 -0.314831 0.033276 0.000174 0.074984 0.508246 -0.230029 -0.011202 0.000124 0.020360 84 0.511384 -0.305312 0.047343 0.000188 0.096424 0.401982 -0.101189 0.033118 0.000130 0.031398 85 0.525139 -0.261187 -0.005724 0.000132 0.036417 0.402024 -0.099964 0.027658 0.000128 0.023893 86 0.524287 -0.264370 -0.005172 0.000138 0.048846 0.696135 -0.501323 -0.029260 0.000147 0.020725 87 0.520158 -0.280838 0.015097 0.000150 0.088778 0.699553 -0.497109 -0.040580 0.000141 0.029837 88 0.510239 -0.246543 0.002648 0.000135 0.117525 0.492521 -0.211418 -0.000154 0.000126 0.041384 89 0.525248 -0.276246 0.001478 0.000145 0.094025 0.490557 -0.200943 -0.005772 0.000119 0.016534 90 0.526587 -0.277618 0.001493 0.000146 0.061147 0.505303 -0.231421 0.002853 0.000127 0.020581 91 0.531627 -0.287823 0.004230 0.000150 0.111040 0.699135 -0.497025 -0.040304 0.000139 0.033962 92 0.523437 -0.282810 0.014655 0.000154 0.109164 0.609480 -0.451085 0.065802 0.000197 0.091676 93 0.506874 -0.222908 0.004907 0.000107 0.111116 94 0.520519 -0.259221 -0.000479 0.000137 0.081166 95 0.501916 -0.194606 0.018539 0.000138 0.088159 96 0.522640 -0.272849 0.003129 0.000145 0.060961 0.492670 -0.208094 -0.007246 0.000123 0.025981 97 0.519180 -0.283234 0.014917 0.000154 0.082959 0.698237 -0.499422 -0.035920 0.000147 0.042723 98 0.534042 -0.275915 -0.006591 0.000135 0.083320 0.446371 -0.128621 -0.007465 0.000109 0.013784 99 0.522605 -0.270201 0.000893 0.000144 0.067569 0.406044 -0.100526 0.020403 0.000121 0.042262 100 0.522584 -0.266143 0.001110 0.000139 0.066456 0.405076 -0.098248 0.020449 0.000120 0.038391 101 0.520815 -0.270435 0.001967 0.000145 0.087136 0.693192 -0.498866 -0.027377 0.000154 0.031291 102 0.525651 -0.270329 -0.000469 0.000141 0.098838 0.469901 -0.160608 -0.011017 0.000110 0.035693 103 0.524404 -0.263961 -0.001334 0.000136 0.075948 0.406946 -0.096948 0.016400 0.000117 0.031326 104 0.518365 -0.266535 0.003285 0.000142 0.069254 0.428853 -0.095954 -0.010602 0.000102 0.028232 105 0.528976 -0.269413 -0.002078 0.000134 0.104911 0.691892 -0.499306 -0.021879 0.000156 0.031926 106 0.518852 -0.255249 -0.000274 0.000134 0.052223 0.430564 -0.098886 -0.010768 0.000102 0.025899 107 0.542638 -0.286916 -0.005663 0.000133 0.142384 108 0.527812 -0.279738 -0.000353 0.000154 0.046445 Table 7: Missing data points in 2 dbar-averaged files for cruise in1801. "x" indicates missing data for the indicated parameters: T=temperature; S/C=salinity and conductivity; O=oxygen; F=fluorescence downcast; PAR=photosynthetically active radiation downcast; TR=transmittance/beam attenuation downcast; BS=backscatter downcast; F_up=fluorescence upcast; PAR_up=photosynthetically active radiation upcast; TR_up=transmittance/beam attenuation upcast. Note: 2 to 8 dbar values (i.e. first four bins) not included here as they’re missing for many casts. pressure (dbar) station where data T S/C O F PAR TR BS F_up PAR_up TR_up missing ——————— ——————————————— — ——— — — ——— —— —— ———— —————— ————— 6 10 x x x x x x x 10 4520 x 10 4682-4698 x 12 4458 x x x x x x x x x x 13 10 x x x x x x x 21 10-14 x x x x x x x 25 whole profile x x x 35 10 x x x x x x x 41 10-12 x x x x x x x 46 4392 x x x x x x x x x x 48 10 x x x x x x x 85 10-14 x x x x x x x 100 2428-2430 x x 106 whole profile x x x Table 8: Suspect CTD 2 dbar averages (not deleted from the CTD 2 dbar average files) for the indicated parameters, for cruise in1801. stn suspect 2 dbar parameters comment value (dbar) ——— —————————————— —————————————————————————— ——————————————————————————————— 1 66-104 downcast trans/beam atten. suspect profile shape, does not match upcast 3 26-90 downcast trans/beam atten. suspect profile shape, does not match upcast 4 168-678 oxygen bottles flagged out for calibration due to significant downcast to upcast profile difference 4 2-114 downcast trans/beam atten. suspect profile shape, does not match upcast 5 80-690 oxygen bottles flagged out for calibration due to significant downcast to upcast profile difference 5 50-70, 80-120 downcast trans/beam atten. suspect profile shape, does not match upcast 6 46-64 downcast trans/beam atten. suspect profile shape, does not match upcast 21 3600-3854 oxygen may be low by ~2µmol/l as bottom 2 bottles flagged out for calibration 107 850-1002 oxygen suspect as bottom bottle flagged out for calibration Table 9: Obvious bad salinity bottle samples (not deleted from bottle data file) for cruise in1801 (note: there may be other less obvious ones). station rosette position station rosette position station rosette position ——————— ———————————————— ——————— ———————————————— ——————— ———————————————— 8 12 42 22 78 23 13 32 42 5 78 19 14 25 43 22 78 18 14 24 43 21 79 23 14 8 43 17 79 9 15 1 43 10 79 8 19 29 43 1 79 7 20 11 44 18 79 5 21 24 44 10 79 3 22 13 44 7 80 11 23 24 45 6 83 22 24 11 47 29 83 17 24 10 47 26 84 14 25 29 49 25 84 9 25 25 49 2 84 3 25 11 50 27 86 12 26 29 50 3 87 14 26 25 51 23 88 10 26 18 51 14 89 21 27 11 52 25 90 9 28 15 53 14 90 4 29 19 54 15 91 7 29 3 55 17 96 7 31 5 55 15 97 20 33 36 56 9 98 14 33 10 58 13 98 10 34 34 62 23 98 7 34 20 62 13 99 18 34 13 67 14 99 13 34 8 69 1 99 10 35 3 72 13 100 16 36 4 73 11 102 20 37 7 74 14 104 26 40 21 74 12 106 18 40 6 75 11 107 3 41 12 77 15 Table 10: Suspect (qc flag=3) and bad (qc flag=4) dissolved oxygen bottle values for cruise in1801. suspect samples (qc flag=3) bad samples (qc flag = 4) station rosette position station rosette position ——————— ———————————————— ——————— ———————————————— 1 33 13 32 21 2 19 24 92 28 21 24 107 2 23 24 25 25, 29 26 25, 29 97 6 102 20 Table 11: Suspect (qc flag=3) and bad (qc flag=4) nutrient sample values for cruise in1801. For the nutrients, P=phosphate, N=nitrate+nitrite, S=silicate. In the comments, % refers to % of full scale (as listed in section 5.6). Note that nitrite and ammonia are difficult to QC, due to the low concentrations (approaching precision levels) station rosette position nutrient comment flag ——————— ———————————————— ———————— ————————————————————— ———— 9 18 P,N,S high by at least ~10% 4 36 31 P possibly high by ~4% 3 56 31 N possibly low by ~6% 3 81 7 S possibly low by ~3% 3 102 32 P possibly high by ~4% 3 Table 12: Scientific personnel (cruise participants) for cruise in1801. Sophie Bestley CTD Benoit Legresy CTD Steve Rintoul chief scientist, CTD Mark Rosenberg CTD, float deployments Katherine Tattersall CTD Esmee van Wijk CTD, float deployments Dan Anderson CFC Mark Warner CFC Kate Berry carbon Joshua Denholm carbon Leo Mahieu carbon Craig Neill carbon Paula Conde Pardo carbon Abe Passmore carbon Andrew Bowie GEOTRACES Matt Corkill GEOTRACES, most of everything and then some Melanie East GEOTRACES Tom Holmes GEOTRACES Pauline Latour GEOTRACES Pier van der Merwe GEOTRACES Morgane Perron GEOTRACES Christine Weldrick GEOTRACES Swan Li San Sow genomics Kristina Paterson hydrochemistry Christine Rees hydrochemistry Kendall Sherrin hydrochemistry Stephen Tibben hydrochemistry Dan Buonome CAPRICORN, radiosondes Ruhi Humphries CAPRICORN, co-chief scientist Jay Mace CAPRICORN, co-chief scientist Kathryn Moore CAPRICORN, monumental endeavour in aerosol lab Alexander Norton CAPRICORN Chiemeriwo Godday Osuagwu CAPRICORN Isabel Suhr CAPRICORN, radiosondes Francis Chui programmer Matt Eckersley doctor, CTD sampling Ian McRobert electronics Peter Shanks programmer Tegan Sime voyage manager Aaron Tyndall electronics Table 13: Summary of float deployments on cruise in1801. float type serial latitude longitude UTC time depth CTD (m) ———————————————— —————— ————————————— —————————————— ———————————————— ————— ——— APEX APF-11 8156 45° 13.787' S 145° 50.734' E 1525, 12/01/2018 2850 6 APEX APF-11 8155 49° 36.726' S 143° 55.663' E 2338, 17/01/2018 3683 16 NAVIS 0688 48° 19.229' S 144° 30.747' E 1824, 16/01/2018 4076 13 SOCCOM 12736 53° 35.285' S 141° 51.457' E 0200, 22/01/2018 2690 29 SOCCOM 12779 55° 30.261' S 140° 43.212' E 1722, 23/01/2018 4180 33 SOCCOM 12784 58° 21.637' S 139° 51.055' E 1413, 25/01/2018 3996 39 SOCCOM 12769 60° 21.810' S 139° 51.251' E 0503, 27/01/2018 4420 44 SOCCOM 12782 62° 51.266' S 139° 50.917' E 0946, 29/01/2018 3200 49 SOCCOM 12709 64° 48.6’ S 139° 51.6’ E 0243, 31/01/2018 2590 54 SOCCOM 12702 65° 24.617' S 149° 59.995' E 2018, 03/02/2018 2890 68 SOCCOM 12741 62° 00.410' S 149° 59.260' E 1342, 06/02/2018 3769 78 SOCCOM 12748 63° 30.140' S 132° 05.520' E 2044, 11/02/2018 4047 91 SOCCOM 12370 58° 29.60’ S 132° 00.58’ E 2142, 15/02/2018 4664 103 BIO FLOAT ?? 60° 50.674' S 139° 51.088' E 2120, 27/01/2018 4389 45 pCO2 float 16003 60° 21.810' S 139° 51.251' E 0504, 27/01/2018 4420 44 pCO2 float 16011 63° 54.18’ S 149° 59.83’ E 0656, 05/02/2018 3660 74 pCO2 float 16001 60° 01.53’ S 132° 12.93’ E 0201, 15/02/2018 4660 100 pCO2 float 16009 56° 58.036' S 132° 09.574' E 1752, 16/02/2018 4532 106 deep SOLO 6042 60° 50.660' S 139° 51.968' E 2136, 27/01/2018 4388 45 deep SOLO 6041 61° 29.83’ S 132° 00.12’ E 0616, 14/02/2018 4538 97 deep SOLO 6040 60° 01.70’ S 132° 12.94’ E 0159, 15/02/2018 4660 100 deep SOLO 6039 58° 29.84’ S 132° 00.58’ E 2140, 15/02/2018 4664 103 deep SOLO 6038 56° 57.98’ S 132° 09.50’ E 1750, 16/02/2018 4532 106 Ninja (with O2 ) 24 63° 21.31’ S 139° 49.83’ E 1642, 29/01/2018 3792 50 Ninja 22 65° 00.039' S 145° 30.106' E 0212, 03/02/2018 3340 67 Ninja 25 63° 30.157' S 149° 59.839' E 1556, 05/02/2018 3724 75 ARVOR 005 64° 13.274' S 139° 49.899' E 1524, 30/01/2018 3508 52 ARVOR 104 64° 36.226' S 149° 59.631' E 2042, 04/02/2018 3453 72 ARVOR 004 63° 05.287' S 132° 05.893' E 1510, 11/02/2018 4267 90 Figure 1: CTD station positions and ship's track for cruise in1801. Figure 2: Conductivity ratio cbtl/ccal versus station number for cruise in1801. The solid line follows the mean of the residuals for each station; the broken lines are vvthe standard deviation of the residuals for each station. ccal = calibrated CTD conductivity from the CTD upcast burst data; cbtl = ‘in situ’ Niskin bottle conductivity, found by using CTD pressure and temperature from the CTD upcast burst data in the conversion of Niskin bottle salinity to conductivity. Figure 3: Salinity residual (sbtl - scal) versus station number for cruise in1801. The solid line is the mean of all the residuals; the broken lines are ± the standard deviation of all the residuals. scal = calibrated CTD salinity; sbtl = Niskin bottle salinity value. Figure 4: Difference between secondary and primary temperature sensors with (a) pressure, and (b) temperature. Data are from the upcast CTD data bursts at Niskin bottle stops. Figure 5: Dissolved oxygen residual (obtl - ocal) versus station number for cruise in1801. The solid line follows the mean residual for each station; the broken lines are ± the standard deviation of the residuals for each station. ocal=calibrated downcast CTD dissolved oxygen; obtl=Niskin bottle dissolved oxygen value. Figure 6: Nitrate+nitrite versus phosphate data for cruise in1801. Figure 7a: Bulk plots showing intercruise comparisons of nitrate+nitrite vs phosphate data for SR3 (low end of nutrient values not included in plot). Figure 7b: Bulk plots showing intercruise comparisons of nitrate+nitrite vs phosphate data for south end of SR3 (including cruises au1402 and au1602). Figure 8: Bulk plots showing intercruise comparisons of silicate data for SR3, shown as bottle salinity vs silicate (low end of silicate values not included in plot). Figure 9: Bulk plots showing intercruise comparisons of dissolved oxygen data for SR3, shown as bottle salinity vs bottle dissolved oxygen (and only plotting data below 500 dbar). APPENDIX 1 – HYDROCHEMISTRY LAB/VOYAGE REPORT Marine National Facility RV INVESTIGATOR HYDROCHEMISTRY VOYAGE REPORT Voyage: in2018_v01 Chief Scientist: Steve Rintoul Voyage title: Detecting Southern Ocean change from repeat hydrography, deep Argo and trace element biogeochemistry & CAPRICORN Report compiled by: Christine Rees, Kendall Sherrin, Stephen Tibben, Kristina Paterson Contents MNF - Highlights, issues, incidents & near misses 32 Itinerary 32 Key personnel list 32 Hydrochemistry 33 CTD stations 33 Water sample bottles 33 Nutrient analysis 34 Salinity analysis 35 Oxygen analysis 36 HyPro 5.3 36 Milli-Q Systems 37 General Labs 37 Consumables given 37 Freight to ship 38 Freight from ship 38 Recommendations for next voyage 38 Chemistry inventory 38 Temperature Plot (see .pdf version) Miscellaneous 38 Appendix 38 MNF - Highlights, issues, incidents & near misses The main objective of the voyage was to quantify changes in Antarctic Bottom Water in the Australian Antarctic Basin by analysing nutrients, salinity and dissolved oxygen samples. The samples were collected along the GO-SHIP hydrographic reference sections SR3 and S4, on the Antarctic shelf near the Mertz glacier and along two transect lines at 150° E and 132° E. Five nutrients were analysed; silicate, phosphate, nitrate + nitrite, nitrite and ammonium. This was the first time ammonium has been measured successfully on every station for a hydrographic voyage. High quality data was produced for the three measured parameters. Certified reference materials for nutrients in seawater were within the specified limits of the certified value. The chief scientist highlighted to all participants that it is the best quality data ever collected along the SR3 transect and congratulated the hydrochemistry team on their efforts. A large amount of time was spent during the voyage trouble shooting the Niskin bottles for leaks. The Guild line salinometers were also problematic during the voyage, with one instrument needing a fan replaced which made the instrument unstable for the remainder of the voyage. The other instrument had a blockage on the inlet tubing within the water bath requiring a small amount of tubing to be removed where the blockage occurred. There was one incident within the lab where the drain pipe leading from the Auto-Analyser-3 was knocked out of the scupper and the waste spilled over the laboratory floor. This caused slightly lower quality ammonium data for the samples being analysed at the time due to the Milli-Q water container becoming contaminated from ammonia fumes. The pipe was fixed and the lab floor was washed with a mop. A freezing experiment for nutrient samples to determine how freezing affects nutrient concentrations over time was conducted on board during the voyage, the experiment is continuing on shore in Hobart. Itinerary Depart Date Time Hobart 11/01/2018 0900 Arrive Date Time Hobart 22/02/2018 1000 Key personnel list Name Role Organisation ————————————————— ——————————————— ———————————— Tegan Sime Voyage Manager CSIRO Steve Rintoul Chief Scientist CSIRO Christine Rees Hydrochemist CSIRO Kendall Sherrin Hydrochemist CSIRO Stephen Tibben Hydrochemist CSIRO Kristina Paterson Hydrochemist CSIRO Hydrochemistry Analysis parameter Total Processing Status Samples at voyage end taken ————————————————————— ———————— ————————————————— Nutrients 2825 CTD Completed (Seal AA3) 63 UWY Completed 108 EXP Completed Salinity (Guildline 2819 CTD Completed salinometer) 30 TSG Completed Dissolved Oxygen 2824 CTD Completed (automated titration) 38 UWY Completed 1 EXP Completed Analysis Data files ————————————————— ——————————————————————————— AA3 Files in 2018_v01nut001 to nut103 00 files in 2018_v01oxy001 to oxy103 Salinometer Files ln2018 _v01sal001 to sal108 CTD stations Total No. of CTD Stations 108 Water sample bottles • 36 bottle rosette used, 12 L Niskin bottles. • Bottles were labelled next to the spigots to minimise confusion for samplers. • Many issues were reported with the bottle end caps seating incorrectly. Members of the science perso nnel attr ibuted this to the t ightness of the tripped lanyards, and presence of large, heavy floats which could be pulled around in t urbulent water or being brought on deck. In most cases this was a superf icial issue, with bottles failing a leak test but their samples remaining unaffected. Large floats were removed and the lanyards were altered to better reflect the stock OTE configuration. • Mark Rosenberg will provide a copy of the Logbook as to what repairs were done to each niskin bottle, as the sampling teams took on the majority of this responsibility. Nutrient analysis Nutrient seawater samples assayed using a Seal AA3HR segmented flow instrument. • Standards prepared were for Antarctic concentrations, Calibrant 6 used for NOx and Silicate. Two sets of stock standards were prepared and compared to the old set of stocks on board the ship (see appendix for results). The 2 sets were deemed good to use. Only stock set 1 were used during the voyage. • Working standards were prepared one at a time and decanted immediately into the 30 ml polypropylene tubes, this was to minimize silicate contamination. • Intermediate standards were prepared approximately every 3 days. • CTD Samples were collected in 30 ml HDPE bottles with screw cap, underway samples were collected in 10 ml polypropylene tubes with screw cap and experimental samples were collected in 30 ml polypropylene tubes with screw caps. • A Reference Material Nutrient Seawater (RM NS CC, CB & CD) was analysed initially on first run. Thereafter CC was run in every analytical run and CB and CD ran intermittently. • All samples assayed within 12 hours of collection, samples were kept in the dark or refrigerated until analysis. Samples were taken out of fridge at least 2 hours before analysis. • Tray protocol consisted of after each Drift, a Null (LNSW), Null (wash), Baseline (MQ) - this improves the ammonium analysis and helps stop the low ammonium samples from going negative. • The concentrated sulphuric acid (H2S04) trap for ammonium (NH4) analysis was changed to 10% H2SO4, as the pH is still low enough to trap NH4 and it is safer. • The standard cleaning protocol after each run was performed. This consisted of MQ water for 10 minutes and then 10% Hypochlorite for each channel except NH4 and 10% HCl through the NH4 channel for 10 minutes followed by MQ for 10 minutes. • If there was noise seen in the phosphate or silicate channel then they were given an extra clean with NaOH and EDTA. • The MQ containers and wash pot were also cleaned regularly with 10% Hypochlorite. • The pump tubes were changed approximately every 70 hours, pharmed air tubing was changed twice during the voyage. • The Cd column was changed when the conversion efficiency dropped to 98%. • The CTD samples were warmed in the sink in 16-20°C water. • The lids were kept on the samples until all the standards and QC's had been analysed. Then they were removed and covered individually with foil. • All data files on Nutrient PC - AACE software saved in voyage folder (in2018_v01) • For run nut021, the ammonia results are slightly lower than expected due to a higher than usual background. The cause of the higher background was identified after the run, the culprit being the drainage pipe had become misaligned with the scupper. This caused the AA3 waste, containing high concentrations of ammonium, to be spilt across the lab and under the benches. This was immediately cleaned up, with the floors being completely cleaned before the next analysis. The background was significantly lower for the next analysis. The drain pipe was fixed before the end of the day to ensure this same issue could not happen again. It was likely caused by the rough sea conditions and a tote box sliding into the pipe and knocking it from the scupper. • Nitrite analysis was repeated on CTD25 and 26 due to the RMN S, internal QC and BQC all stepping up, the waterfall profiles also showed the samples were offset from previous CTD's. The repeated results were better, the cause may have been the NEDD colour reagent. • On CTD 56 run Nut056 the nitrite baseline stepped up on sample 5627 and 5625, then stepped back down on 5624 and 5623 but then stepped back up on 5622 and stayed elevated. Drift s are also elevated and end baselines. Flagged all data for NO2 as bad. • Communication was a problem to the auto-sampler, however once the serial/usb cable was changed to a different type this problem no longer occurred. Salinity analysis • Guildline 71613 was calibrated with OSIL P161. • 21/1/2018. The salinometer started up as usual and a new file was created. Before a sample could be run the software displayed the error message that comms had been lost. Reconnecting the software using the connect button on the top right resulted in a 'run time error 5' message and the software shutting down. This was resolved by restarting the computer twice and did not recur on the 21/1. The salinometer had previously lost comms twice during the same run (a few days prior), each time it was thought to be due to flushing the cell while still in the read position. The two errors may or may not be related • 24/1/2018 06:30 UTC prior to new run (during the set up phase) the fan of salinometer 71613 failed (partial failure) characterized by very loud buzzing noise and vibrations as it rattled the external case. Possibly bearings? It was replaced and sampling resumed. • 30/01/2018 salinometer 71613 began 'wandering' throughout analyses. Sample conductivity measurements would drift to lower values during each reading. Samples were analysed on the backup instrument, 72151, with on issues. • 31/01/2018 salinometer 71613 bath was drained and conductivity cell removed from inside. Cell removed from electronics and cleaned with a mixture of 85% ethanol (methanol suggested but not available), 15% Milli-Q water, and 5% Decon-90. The cell was left to soak in this solution for 24 hours before being flushed with Milli-Q and reassembled inside the instrument. The lamp globes were replaced and the bath was refilled with new Milli-Q water before the instrument was powered back on. • 08/02/18 - after a few runs of sporadic bad readings that were not also reflected in sensor or oxygen/nutrient their cause was investigated. It was noted that some inserts were split very close to the cap-side edge and thus likely not sealing the sample correctly. The clean inserts were then inspected between analysis and being handed to the samplers and any compromised pieces removed. In addition, the container for the clean inserts was also rinsed clean and wiped dry to remove any salt that may have accumulated during the voyage. • Cast 103 sampled without using sampling tube. • 15/2/2018 During analysis of CTD 099 salinometer 72151 began to struggle with flushing/rinsing the cell. More speed on the pump was needed to push the sample through the cell and noticeable back pressure built up on occasions leading to leaks after the peristaltic pump and the tubing popping off at that location. Cleaning with ethanol helped for a short time. The next day the salinometer was opened, tubing relating to the air flush of the cell and sample water flow path was cleaned with fine copper wire. This did not resolve the problem and SITS (Ian McRoberts) attended found there was a build-up of material at the end of the inlet flow path where it connects to a stainless steel through to the temperature controlled bath. Cutting out the affected part of tubing and reattaching was enough to solve the problem. • The second (and final) TSG calibration samples run on 21 Feb 2018 ran under filename in2018_v01SalTSGcalibrationfilebatch2. This file name was too long for the export.csvexcel file function of the software and caused an error. A print screen of the results is located with the other TSG calibration data in V:\current\hydrochem\hypro\Salinity\TSG Cal Results. Oxygen analysis • Water bath started leaking quite severely out the front, where the clear acrylic joins to rest of the water bath. The brown adhesive used to seal the join had become brittle and cracked under slight pressure from a flask. This was fixed by using some Aquafix, a waterproof epoxy. It is flexible and should resist cracking and forming leaks. • DO instrument lost connection to computer, the standardisation information was lost from the day, reverting to the previous day's standardisation. Standardisation information was written down in log book however, so samples were analysed using old standardisation. The results were then recalculated using the macro and results copied back into the. LST for HyPro to read in. This affected files oxy008-009. • 31/01/2018 UV lamp would not power on before analysis of CTD 54, so it was replaced. CTD 54 was analysed the following day. Detector voltages were more stable after the installation of a new lamp. • 14/02/2018 sample line from bottle to burette split. Air was dispensed into one sample (CTD97 RP06) which gave a bad result. This was apparently due to over-tightening of the connection which had damaged the sample line. The damaged piece of sample line was re moved and the new opening flanged to provide a functional seal. HyPro 5.3 • Version of HyPro 5.3 was used for the voyage. • Initially Log editor was not functioning due to scripts between seasave and CAPPro not working. However Dap fixed this issue on the 12/01/2018. • Issue arose where nutrient run nut011, did not have a CC for NOx due to restart of analysis. HyPro did not have the capability to deal with this scenario, Francis however fixed this issue by checking if a CC exists, if not it proceeds without producing a plot for column efficiency. See AA3Analysis.m line 2494. • Occasionally for NOx placing the # at the beginning of the peak start column did not flag the data as BAD, and a # would need to be placed in front of the AD value column for the data to be flagged as BAD. • Salinity and the CTD salinity was incorrectly plotted at times within the waterfall plots. It looked like there was an offset when there wasn't one. • Suggestions for HyPro updates: o HyPro to have same flagging system as "WOCE" o Option to export BAD data within the deployment data to csv o Option to not export BAD data to netcdf file Milli - Q Systems • No issues, routine maintenance was performed during mobilisation for in2018_v01. See maintenance log for more information. General Labs • 12/02/18 Lime boxes were low on limestone. Refilled by Kendall with new limestone. This new limestone seemed to be a higher purity than the previous batch. New batch is completely white. Old batch was mottled and left undissolved gravel pieces which were cleared out of the boxes in the Hydrochemistry lab. • HyPro matlab processing computer is suspected to have a Trojan/adware and kept on downloading, processing data and sending data back to unknown IP addresses. It was using the majority of the ships bandwidth so was switched off from the internet. • The folder in2018_v01_AA3_files for storing a backup copy of the AACE run files also had the master .anl and a few other files copied and placed into it. These do not automatically get copied to this folder. The master .anl file is required if you want to process the run files through AACE. • The master .anl file was accidently deleted twice from the AACE folder in2018_v01, which meant the run files would not work. The file was restored the first time from the bin on the desktop and the second time from the backup copy in the in2018_v01_AA3_files folder. Consumables given • Order more tubing for the AA3: 116-0536-18c • Order more of inlet tubing on guildlines • Order 100 ml plastic measuring cylinder • Order 1 litre plastic conical flask with screw lid for nutrients • 2 litre amber coloured bottle for OPA reagent Freight to ship • N/A Freight from ship • N/A Recommendations for next voyage Chemistry inventory Available to view in Hydrochemistry confluence: https://confluence.csiro.au/display/HYD/Hydrochemistry Temperature Plot The AC in the nutrient lab was set to cool at 21°C and the salinity lab cool at 24°C on leaving Hobart. AC in salinity lab was set on heat 24°C while the main laboratory AC was set to cool 21°C. The salt lab was still being cooled however, indicating that the slave control unit is the one in the salt lab. Once the main laboratory AC was switched to heat 20°C, the salt lab was heated. This change occurred on the 16/01 at approximately 0630 local time. The main lab was changed to heat at 19°C a couple hours after the initial change and the fan was set at 2. On the 19/01/2018 the temperature in the salt lab was too hot and the AC's were switched to cool again. Main lab was cool at 22°C initially and then later 21°C as it was still over 22°C. The salt lab was set to cool at 24°C. On the 31/01/2018 the AC in ma in lab was set back to heat at 18°C as the room was still too warm. Along with the Hobo temperature profiles, laboratory temperature was logged into Grafana. Hydrochemistry Lab (file located in voyage folder): Scale is 18°C to 24.5°C Salinity Lab (located in salinity folder): Scale is l8°C to 27°C Miscellaneous Appendix Table 1: Mean concentrations after 10 measurements of a Cal 3 produced from each stock standard. The percentage difference between the new stock standard mean and the old stock standards means is shown. Old Stock(A/D) New Stock 1 (A/D) New Stock 2 (A/D) —————————————— ————————————————— ————————————————— NOx 36958.7 36978.5 37018.59 Difference to Old 0.054% 0.162% Phosphate 37653.2 37698.2 37665.6 Difference to Old 0.119% 0.033% Silicate 16459.1 16466.1 16432.5 Difference to Old 0.042% -0.162% Nitrite 19550.5 19506.2 19468.8 Difference to Old -0.227% -0.420% Ammonia 33390.8 32840.8 32642.0 Difference to Old -1.67% -2.29% APPENDIX 2 – HYDROCHEMISTRY DATA PROCESSING REPORT Marine National Facility RV INVESTIGATOR HYDROCHEMISTRY DATA PROCESS REPORT Voyage: IN2018_v01 Chief Scientist: Dr. Steve Rintoul Voyage title: Detecting Southern Ocean change from repeat hydrography, deep Argo and trace element biogeochemistry & CAPRICORN Report compiled by: Christine Rees, Kendall Sherrin, Stephen Tibben & Kristina Paterson Contents 1 Executive Summary 41 2 Itinerary 41 3 Key personnel list 41 4 Summary 42 4.1 Hydrochemistry Samples Analysed 42 4.2 Rosette and CTD 42 4.3 Data Procedure Summary 42 5 Salinity Data Processing 43 5.1 Salinity Parameter Summary 43 5.2 Salinity Method 43 5.3 CTD Salinities vs Hydrochemistry Salinities Plot 44 5.4 Missing or Flagged Salinity Data and Actions taken 44 6 Dissolved Oxygen Data Processing 47 6.1 Dissolved Oxygen Parameter Summary 47 6.2 Dissolved Oxygen Method 47 6.3 CTD Dissolved Oxygen vs Hydrochemistry Dissolved Oxygen Plot 48 6.4 Dissolved Oxygen thiosulphate normality and blanks across voyage 48 6.5 Missing or Flagged Dissolved Oxygen Data and Actions taken 48 7 Nutrient Data Processing 48 7.1 Nutrient Parameter Summary 48 7.2 Nutrient Methods 49 7.3 Instrument Calibration and Data Parameter Summary 49 7.4 Accuracy - Reference Material for Nutrient in Seawater (RMNS) Plots 51 7.4.1 Silicate RMNS Plot (see .pdf version) 7.4.2 Phosphate RMNS Plot (see .pdf version) 7.4.3 Nitrate + Nitrite (NOx) RMNS Plot (see .pdf version) 7.4.4 Nitrite RMNS Plot (see .pdf version) 7.5 Internal Quality Control 52 7.6 Analytical Precision 53 7.7 Sampling Precision 54 7.7.1 Silicate Duplicate/Replicates Plot (see .pdf version) 7.7.2 Phosphate Duplicate/Replicates Plot (see .pdf version) 7.7.3 Nitrate + Nitrite (NOx) Duplicate/Replicates Plot (.pdf) 7.7.4 Nitrite Duplicate/Replicates Plot (see .pdf version) 7.7.5 Ammonia Duplicate/Replicates Plot (see .pdf version) 7.7.6 Redfield Ratio Plot (14.0) (see .pdf version) 7.8 Flagged Nutrient Calibration and Quality Control Data 54 7.9 Missing or Flagged Nut ri ent Data and Actio ns taken 58 7.10 Temperature & Humidity Changeover Nutrient Analyses 62 8 Appendix 62 8.1 Salinity Reference Matrial 62 8.2 HyPro Flag Key for CSV & NetCDF file 62 8.3 GO-SHIP Specifications 63 8.4 RMNS Values for each CTD Deployment 64 8.5 Internal Quality Control Values for each CTD Deployment 67 9 References 68 1 Executive Summary Nutrients, dissolved oxygen and salinity samples were collected and analysed through the full depth for climate studies and to quantify changes in the Antarctic Bottom Water in the Australian Antarctic Basin. The samples were collected along the GO-SHIP hydrographic reference sections SR3 and S4, on the Antarctic shelf near the Mertz glacier and along two transect lines at 150°E and 132°E. Five nutrients were analysed: silicate, phosphate, nitrate + nitrite, nitrite and ammonium. This was the first time ammonium has been measured successfully on every station for a hydrographic voyage. High quality data was produced for the three measured parameters. Certified reference materials for nutrients in seawater were within the specified limits of the certified value. All finalized data can be obtained from the CSIRO data centre Contact: DataLibrariansOAMNF@csiro.au. 2 Itinerary Hobart to Hobart 11 January 2018 to 22 February 2018 3 Key personnel list Name Role Organisation ————————————————— —————————————————————— ————————————————————— Steve Rintoul Chief Scientist CSIRO & ACE CRC Tegan Sime Voyage Manager CSIRO Alain Protat Principal Investigator Bureau of Meteorology Andrew Bowie Principal Investigator IMAS-UTAS/ACE CRC Bronte Tilbrook Principal Investigator CSIRO & ACE CRC Lev Bodrossy Principal Investigator CSIRO Christine Rees Hydrochemist CSIRO Kendall Sherrin Hydrochemist CSIRO Stephen Tibben Hydrochemist CSIRO Kristina Paterson Hydrochemist CSIRO 4 Summary 4.1 Hydrochemistry Samples Analysed Analysis Number of Samples —————————————————————————————————————— ————————————————— Salinity (Guildline Salinometer) 2819 CTD 30TSG Dissolved Oxygen (automated titration) 2824 CTD 38 UWY 1 EXP Nutrients (AA3) 2825 CTD 63 UWY 108 EXP Note: • Conductivity Temperature Density (CTD); samples collected from NISKIN bottles on the CTD rosette. • Underway (UWY); samples collected from underway clean instrument seawater supply in the PCO2 lab. • Experimental (EXP): sample from microcosm experiments • For sample information on UWY and EXP samples refer to the Hydrochemistry ELog from the voyage. 4.2 Rosette and CTD • 108 CTD stations were sampled with a 36 bottle rosette (12 L). • See in2018_v01_HYD_VoyageReport.pdf (voyage report) for more details on sample collection. 4.3 Data Procedure Summary The procedure for data processing is outlined below. Figure 1: The processing steps for hydrology data following sample assay. 5 Salinity Data Processing 5.1 Salinity Parameter Summary Details ———————————————————————— —————————————————————————————————————————————— HyPro Version 5.3 Instrument Guildline Autosal Laboratory Salinometer 8400(8) - SN 72151 and SN 71613 Software OSIL Data Logger ver 1.2 Methods Hydrochemistry Operations Manual + Quick Reference Manual Accuracy + 0.001 practical salinity units Analyst(s) Kristina Paterson Lab Temperature (±0.5°C) 21.5 - 23.5°C during analysis. Bath Temperature 24.0l°C Reference Material Osil IAPSO - Batch P161 and P158 (see appendix 8.1) Sampling Container type 200 ml volume OSIL bottles made of type II glass (clear) with disposable plastic insert and plastic screw cap. Sample Storage Samples held in Salt Room for 6 - 12 hrs to reach 22°C before analsis Comments Both instruments were used interchangeably 5.2 Salinity Method The method uses a high precision laboratory salinometer (Guildline Autosal 8400B) which is operated in accordance with its technical manual. Practical salinity (S) is defined in terms of the ratio (K_15) of the electrical conductivity measured at 15°C 1atm of seawater to that of a potassium chloride (KCI) solution of mass fraction 32.4356 x 10^-3. The Autosal is calibrated with standard seawater (OSIL, IAPSO) of known conductivity ratio against which the samples are measured. The Autosal is calibrated before each batch run of samples. Salinity samples are collected into 200ml OSIL bottles - from the bottom via a PTFE straw filled till overflowing. The sample is decanted to allow a headspace of approximately 25cm^3. A plastic insert is fitted, the bottle inverted and rinsed then capped and stored cap-down until measured. To measure, the salinometer cell is flushed three times with the sample and then measured after the fourth and fifth flush. Further flush-measurement cycles are done where the initial values are more than 3 digits different. The conductivity ratio data is captured by the Osil data logger vl.2 program which then calculates the practical salinity. 5.3 CTD Salinities vs Hydrochemistry Salinities Plot 5.4 Missing or Flagged Salinity Data and Actions taken Data is flagged based on notes from CTD sampling log sheet, observations during analysis, and examination of depth profile and waterfall plots. CTD RP Run Flag Reason for Flag or Action ——— ——— ——— ———— ———————————————————————————————————————————————————— 008 D12 8 133 Salinometer measurement was good, potentially sampled from the wrong niskin (niskin 11). 021 K16 021 133 Bottle was dropped/some sample spilled. The subsequent reading was at first unstable (poor agreement between readings) then stable but comparatively low salinity/out of profile. 021 K24 021 133 Salinometer measurement was good. Comparatively low salinity/out of profile. 023 E24 023 133 Comparatively high Salinity/out of profile, unusual nutrient and cfc data points suggests bottle fired at wrong depth 024 K10 024 69 First effort to sample was unstable, second effort was comparatively stable across 3 readings but high compared to CTD/out of profile. 025 C25 025 133 Out of profile (as is nuts and possibly other measurements) likely fired at wrong depth 025 C29 025 133 Out of profile (as is nuts and possibly other measurements) likely fired at wrong depth 026 E29 026 69 Sample was unstable during analysis (three attempts to make a stable measurement), cause unknown 026 E25 026 133 Sample was analysed ok, result out of profile cause unknown 033 C10 033 133 Salinometer measurement was good, high/ out of profile. 033 C36 033 133 The first sample attempt was variable with a large difference between the two readings, the second sample was comparatively stable between the two readings but in comparison to the rest of the cast is out of profile/high 034 M34 034 133 Result is out of profile and comparatively high. 035 G03 035 133 Analysis was good and agreement good, sample is out of profile (high) cause unknown 043 E17 043 133 The sample was unstable and the result constantly increasing during analysis. The sample is high and out of profile 043 E10 043 133 Salinometer measurement was good. Result is high/ out of profile. 043 E0l 043 133 Salinometer measurement was good. Result is high/out of profile. 047 C26 045 133 Salinometer measurement was good. The result is out of profire, cause unknown, The measurement over the entire CTD was the most problematic to date, small bubbles forming on the electrodes and other unknown problems causing jumps of up to .003 units 047 C29 046 133 Salinometer measurement was good. The result is out of profile, cause unknown, The measurement over the entire CTD was the most problematic to date, small bubbles forming on the electrodes and other unknown problems causing jumps of up to .003 units 050 A03 050 133 High salinity/out of profile, measurement was erratic and difficult to obtain two readings within QC accepted range of each other. 052 E25 052 069 Salinity is comparatively high for the profile, but mimics/exaggerates a feature (spike/increase) seen in the CTD data. The sample needed two measurements, the first was low with poor agreement over two readings, the second reading was ok 055 M31 055 133 The sample ran poorly 2 times (significant difference between the two readings, internally stable for each of the 5 sub-readings within a read- ing), third try was stable but the value is high 055 M15 055 133 The sample ran poorly on the first attempt stepping up from 34.7044 to 34.7080, and remaining stable at the higher reading on the second attempt. Both results were significantly higher than the CTD. 056 G09 056 133 The sample analysed poorly on four attempts - one was within or close to acceptable limits but the final result is high/out of profile. Could be related to salt inserts (conclusion post discovery of the lid holes on CTD 083). It was APPROXIMATELY at this point that inserts from the reserve bag of good/new inserts were introduced into circulation and which were later found to have approximately 50 with punctures near the top lip due to the insertion of a screwdriver to remove the inserts from the sample bottle. Some inserts with this problem may have been in circulation for the entire voyage, and may be the reason for anomalous high salinity readings. 058 C13 058 69 The sample had poor agreement during the first analysis attempt, and was low/out of profile. 067 E14 067 133 Salinometer measurement was good, high salinity/out of profile cause unknown. Could be related to salt inserts (conclusion post discovery of the lid holes after CTD 083) 069 C0l 069 133 High salinity, cause unknown. Sample was run twice due to instability second reading was stable (but high compared to the rest of the profile and CTD salinity). Could be related to salt inserts (conclusion post discovery of the lid holes on CTD 083) 073 Ell 073 133 Salinometer measurement was good. Results is low/ out of profile. Could be related to salt inserts (conclusion post discovery of the lid holes on CTD 083) 074 M12 074 133 The sample analysed poorly on the first attempt and well on the second attempt, but the value is high/out of profile. Could be related to salt inserts (conclusion post discovery of the lid holes on CTD 083) 077 Gl5 077 133 Salinometer measurement was good. Results is low/out of profile. Could be related to salt inserts (conclusion post discovery of the lid holes on CTD 083) 078 M23 078 69 The sample analysed poorly and took 4 tries. Consensus was reached finally but there were significant differences between readings. 078 M18 078 133 The sample analysed poorly and took 3 tries. Consensus was reached but high compared to the CTD profile. Could be related to salt inserts (conclusion post discovery of the lid holes on CTD 083) 079 A23 079 133 Low/out of profile, sample ran poorly (three attempts). Could be related to salt inserts (conclusion post discovery of the lid holes on CTD 083) 083 M17 083 133 Analysed poorly. A hole was found in one insert from this CTD, not confirmed to be from this sample, but likely was from this sample based on the cluster of recent "off" samples 086 C12 086 113 High salinity caused by small slit in insert. 087 J14 087 133 High salinity caused by small slit in insert. 101 M16 101 69 Sample analysed poorly on 1st attempt. High/out of profile (not caused by hole in insert) 102 B20 201 133 High/out of profile , potentially a misfire, suspect nutrient results also 6 Dissolved Oxygen Data Processing 6.1 Dissolved Oxygen Parameter Summary Details —————————————————————— ————————————————————————————————————————————————— HyPro Version 5.3 Instrument Automated Photometric Oxygen system Software SCRIPPS Methods SCRIPPS Accuracy 0.01 ml/L + 0.5% Analyst(s) Stephen Tibben & Kendall Sherrin Lab Temperature (±l°C) Variable, 20.0 - 23.0°C Sample Container type Pre-numbered glass 140 ml glass vial w/stopper, sorted into 18 per box and boxes labelled A to S. Sample Storage Samples were stored within Hydrochemistry lab under the forward starboard side bench until analysis. All samples were analysed within 48 hrs Comments 8 - 34 samples were collected from each deployment 6.2 Dissolved Oxygen Method SCRIPPS method used. The method is based on the whole-bottle modified Winkler titration of Carpenter (1965) plus modifications by Culberson et al (1991). Manganese chloride followed by alkaline iodide, is added to the sample, and the precipitated manganous hydroxide is distributed evenly throughout the bottle by shaking. At this stage, the dissolved oxygen oxidizes an equivalent amount of Mn (II) to Mn (IV). Just before titration, the sample is acidified, converting the Mn (IV) back to the divalent state liberating an amount of Iodine equivalent to the original dissolved oxygen content of the water. The Iodine is auto-titrated with a standardised thiosulphate solution using a Met Rohm 665 Dosimat with a 1 ml burette. The endpoint is determined by measuring changes in the UV absorption of the tri-iodide ion at 365 nm. The point at which there is no change in absorbance is the end point. The thiosulphate solution is standardised by titrating a 10ml aliquot of potassium iodate primary standard. The blank correction is determined from the difference between two consecutive titres for 1 ml aliquots of the same potassium iodate solution. 6.3 CTD Dissolved Oxygen vs Hydrochemistry Dissolved Oxygen Plot 6.4 Dissolved Oxygen thiosulphate normality and blanks across voyage 6.5 Missing or Flagged Dissolved Oxygen Data and Actions taken Data is flagged as Good, Suspect or Bad in HyPro based on notes from CTD sampling log sheet, observations during analysis, and examination of depth profile and waterfall plots. 7 Nutrient Data Processing 7.1 Nutrient Parameter Summary Details HyPro Version 5.3 Instrument AA3 Software Seal AACE 6.10 Methods AA3 Analysis Methods internal manual Nutrients analysed Silicate Phosphate Nitrate+Nitrite Nitrite Ammonia ------------- -------------- --------------- -------------- -------------- Concentration Range 140 µmol l^-1 3 µmol l^-1 42.0 µmol l^-1 1.4 µmol l^-1 2.0 µmol l^-1 Method Detection 0.2 µmol l^-1 0.02 µmol l^-1 0.02 µmol l^-1 0.02 µmol l^-1 0.02 µmol l^-1 Limit* (MDL) Matrix Corrections N N N N N Analyst(s) Christine Rees, Kendall Sherrin, Stephen Tibben Lab Temperature Variable, 19.0 - 22.0°C (±1°C) Reference MateriaI RMNS - CC, CB, CD Sampling Container 50 ml HOPE screw cap lids for CTD samples type 30 ml polypropylene sample tubes for experimental samples 10 m l polypropylene sample tubes for underway samples Sample Storage < 2 hrs at room temperature or ≤ 12 hrs @ 4°C Pre-processing of None Samples Comments 7.2 Nutrient Methods CSIRO Oceans and Atmosphere Hydrochemistry nutrient analysis is performed with a segmented flow auto-analyser - Seal AA3 HR - to measure silicate, phosphate, nitrite, nitrate plus nitrite (NOx), and ammonium Silicate: colourimetric, molybdenum blue method. Based on Armstrong et al. (1967). Silicate in seawater is reacted with acidified ammonium molybdate to produce silicomolybdic acid. Tartaric acid is added to remove the phosphate molybdic acid interference. Tin (II) chloride is then added to reduce the silicomolybdic acid to silicomolybdous acid and its absorbance is measured at 660nm. Phosphate: colourimetric, molybdenum blue method. Based on Murphy and Riley (1962) with modifications from the NIOZ-SGNOS Practical Workshop 2012 optimizing the antimony catalyst/phosphate ratio and the reduction of silicate interferences by pH. Phosphate in seawater forms a phosphomolybdenum complex with acidified ammonium molybate. It is then reduced by ascorbic acid and its absorbance is measured at 880nm. Nitrate: colourimetric analysis, Cu-Cd reduction - Naphthylenediamine photometric method. Based on Wood et.al (1967). Nitrate is reduced to nitrite by first adding an ammonium chloride buffer then sending it through a copper-cadmium column. Sulphanilamide is added under acidic conditions to form a diazo compound. This compound is coupled with 1-N- naphthly-ethylenediamine di-hydrochloride to produce a reddish purple azo complex and its absorbance is measured at 520 nm. Nitrite: colourimetric analysis, Naphthylenediamine photometric method. As per nitrate method without the copper cadmium reduction column and buffer. Ammonium: fluorescence analysis, ortho-phtaldiadehyde method. Based on Roger Kerouel and Alain Arninot, IFREMER (1997 Mar.Clhem.57). Ammonium reacted with ortho­phtaldialdehyde and sulphite at a pH of 9.0-9.5 to produce an intensely fluorescent product. Its emission is measured at 460nm after excitation at 370nm. Detailed SOPs can be obtained from the CSIRO Oceans and Atmosphere Hydro chemistry Group on request. 7.3 Instrument Calibration and Data Parameter Summary All instrument parameters and reagent batch compositions are logged for each analysis run. This information is available on request. The raw data from each analysis run on the Seal AA3HR is imported in to HyPro for peak height determination, constructing the calibration curve, deriving the sample results and applying drift and carry-over corrections. Following standard procedures, the operator may choose to not include bad calibration points (see section 7.8 for edited data). Below are the corrections and settings that HyPro applied to the raw data. All runs have a corresponding "AA3_Run_Analysis_sheet" to record the following: sample details, LNSW batch, cadmium column, working standards, reagent information, instrumentation settings, and pump tube hours. The NUT### file numbers that correspond to each analytical run and the CTD samples analysed are in table 8.4. The NUT### file numbers for underway and experimental samples are available upon request. Calibration summary data for each analysis run are in the voyage documentation and available upon request. Result Details Silicate Phosphate Nitrate + Nitrite Ammonia Nitrite ————————————————————— ————————— ————————— ————————— ————————— ————————— Data Reported as µmo1 1^-1 µmo1 1^-1 µmo1 1^-1 µmo1 1^-1 µmo1 1^-1 Calibration Curve Linear Linear Quadratic Quadratic Quadratic degree Forced through zero? N N N N N # of points in 7 6 7 6 6 Calibration Matrix Correction N N N N N Blank Correction N N N N N Carryover Correction Y Y Y Y Y (HyPro) Baseline Correction Y Y Y Y Y (HyPro) Drift Correction y y y y y (HyPro) Data Adj for RMNS N N N N N Window Defined* HyPro HyPro HyPro HyPro HyPro Medium of Standards LNSW (bulk on deck of Investigator) collected on 28/9/2016. Sub-lot passed through a 10 micron filter and stored in 20 L carboys in the clean dry laboratory at 22°C. Medium of Baseline 18.2 ΩMQ Proportion of samples Samples were collected in duplicate at the greatest depth either RPOl or RP02 on the CTD rosette. in duplicate? Comments Calibration and QC data that was edited or removed is located in the table within section 7.8. The reported data is not corrected to the RMNS. Per deployment RMNS data can be found in appendix 8.4. 7.4 Accuracy - Reference Material for Nutrient in Seawater (RMNS) Plots Japanese KANSO certified reference materials (RMNS) for silicate, phosphate, nitrate and nitrite in sea water was used in each nutrient analysis run to determine the accuracy. For each analysis run, a new RMNS bottle was opened and used. The RMNS was assayed in quadruplicate after the calibration standards. RMNS lots CB, CC and CD were used. Their stated values in µmol/kg are converted to µmol/^-1 at 21°C and are listed below. RMNS do not have certified ammonium values. Table 1: RMNS CB, CC and CD concentrations with expanded uncertainty (µmol/L) at 21°C RMNS NO_3 NO_x NO_2 PO_4 SiO_4 ———— ———————————— ———————————— ————————————— ———————————— ————————————— CB 36.65 ± 0.28 36.77 ± 0.28 0.119 ± 0.006 2.58 ± 0.02 111.82 ± 0.64 CC 31.62 ± 0.25 31.74 ± 0.25 0.119 ± 0.006 2.13 ± 0.02 88.23 ± 0.49 CD 5.63 ± 0.05 5.65 ± 0.06 0.018 ± 0.005 0.46 ± 0.008 14.26 ± 0.10 The submitted nutrient results do NOT have RMNS corrections applied. ————————————————————————————————————————————————————————————————————————— RMNS Correction Ratio = Certified RMNS Concentration/Measured RMNS Concentration in each run Corrected Concentration = Ratio x Measured Nutrient Concentration Or for smoothing data Ratio = Average RMNS Concentration across voyage/Measured RMNS Concentration in each run Corrected Concentration = Ratio x Measured Nutrient Concentration ————————————————————————————————————————————————————————————————————————— The following plots show RMNS values within 1% (green lines), 2% (pink lines) and 3% (red lines) of the published RMNS value except for nitrite. The nitrite limit is set to ±0.020 µM (MDL) as 1% is below the method MDL. The GO-SHIP criteria (Hyde et al., 2010), appendix 8.3, specifies using 1-3% of full scale (depending on the nutrient) as accept able limits of accuracy. The assayed RMNS values per CTD deployment are reported in the table in appendix 8.4. 7.4.1 Silicate RMNS Plot 7.4.2 Phosphate RMNS Plot 7.4.3 Nitrate + Nitrite (NOx) RMNS Plot 7.4.4 Nitrite RMNS Plot 7.5 Internal Quality Control The internal quality control samples were prepared on the 28/9/2017 by filtering more than 2 litres of low nutrients seawater (LNSW) from a carboy through a 0.2µM Acropak filter into HDPE square 1L bottles and then autoclaving. A LNSW control was prepared to account for any nutrients already in the LNSW and also any nutrients picked up in the autoclaving. The autoclaved LNSW was well mixed and poured into an acid cleaned and dry HDPE square lL bottle and lid screwed shut and wrapped with parafilm around the lid and stored at 4°C. The Spiked internal quality control was prepared by spiking nutrients into the autoclaved LNSW from an OSIL kit containing 5 nutrients each in separate bottles containing 50 ml. The concentrations of each bottle were as follows: Silicate 1000 µmol/L, Phosphate 100 µmol/L, Nitrate 1000 µmol/L, Nitrite 100 µmol/L and Ammonia 10,000 µmol/L. The following amounts were pipetted into a calibrated 1L volumetric flask. 10 ml of phosphate 100 µmol/L = 1 uM 5 ml of Nitrate 1000 µmol/L = 5 µM 10 ml of silicate 1000 µmol/L= 10 µM 5 ml of nitrite 100 µmol/L= 0.5 µM 0.1 ml of ammonium 10,000 = l µM The flask was then made to volume with the autoclaved LNSW. It was mixed well and poured into an acid-cleaned and dry HDPE square lL bottle with the lid screwed shut and parafilm wrapped around the lid and stored at 4°C. An initial measurement was made in October 2017 and another measurement was made in December 2017. It was determined that the standards were stable to be used on the voyage. The internal QC's were decanted into a number of 10 ml polypropylene screw lid sample tubes on three separate occasions and stored at 4°C. A sample tube of the control and the spike were analysed with the CTD samples, due to limited volume not all analytical runs contained an internal quality control. 7.6 Analytical Precision The CSIRO Hydrochemistry method measurement uncertainty (MU) has been calculated for each nutrient based on variation in the calibration curve, calibration standards, pipette and glassware calibration, and precision of the RMNS over time (Armishaw 2003). Silicate Phosphate Nitrate + Nitrite Nitrite Ammonia (NOx) ———————— ————————— ————————————————— ——————— ——————— Calculated MU* ±0.017 ±0.024 ±0.019 ±0.137 ±0.296¥ @ 1 µmo1 1^-1 * The reported uncertainty is an expanded uncertainty using a coverage factor of 2 giving a 95% level of confidence. ¥ The ammonia MU precision component does not include data on the RMNS. Method detection limits (MDL) achieved during the voyage were much lower than the nominal detection limits, indicating high analytical precision at lower concentrations. RMNS and MDL precision data listed below. Results are µmol l^-1. MDL Silicate Phosphate Nitrate + Nitrite Nitrite Ammonia (NOx) ———————— ————————— ————————————————— ——————— ——————— Nominal MDL* 0.20 0.02 0.02 0.02 0.02 Standard Dev. Min 0.00 0.00 0.00 0.000 0.00 Standard Dev. Max 0.057 0.010 0.0057 0.0040 0.0057 Standard Dev. Mean 0.023 0.003 0.0053 0.0010 0.0007 Standard Dev. Median 0.00 0.005 0.00 0.0005 0.00 Precision of MDL (stdev) 0.186 0.012 0.012 0.004 0.030 *MDL is based on 3 times the standard deviation of Low Nutrient Seawater (LNSW) analysed in each nutrient run. Published RMNS CD (µmol 1^-1) 14.26 0.46 5.65 0.018 w/std deviation ± 0.009 ± 0.001 ± 0.004 ± 0.001 RMNS Min 13.6 0.44 5.51 0.028 1.43 RMNS Max 14.2 0.47 5.61 0.044 1.91 RMNS Mean 13.90 0.46 5.56 0.033 1.61 RMNS Median 13.90 0.46 5.57 0.033 1.56 RMNS Std Dev 0.16 0.006 0.03 0.003 0.14 Published RMNS CC (µmol 1^-1) 88.23 2.13 31.74 0.119 w/std deviation ± 0.053 ± 0.005 ± 0.029 ± 0.002 RMNS Min 86.8 2.10 31.67 0.121 1.22 RMNS Max 88.5 2.18 32.45 0.141 2.35 RMNS Mean 87.74 2.14 31.92 0.132 1.60 RMNS Median 87.8 2.15 31.92 0.130 1.60 RMNS Std Dev 0.29 0.01 0.095 0.003 0.19 Published RMNS CB (µmol 1^-1) 111.82 2.58 36.768 0.119 w/std deviation ± 0.053 ± 0.004 ± 0.020 ± 0.002 RMNS Min 110.5 2.57 36.59 0.131 1.16 RMNS Max 111.9 2.63 37.08 0.147 1.66 RMNS Mean 111.24 2.60 36.82 0.138 1.39 RMNS Median 111.25 2.60 36.83 0.138 1.38 RMNS Std Dev 0.32 0.01 0.12 0.004 0.13 7.7 Sampling Precision Duplicate samples were collected during CTD deployments from the NISKIN bottle in rosette position 01 or 02 to measure the sample precision. The multiple measurements are reported in the data as an average, when all measurements are flagged GOOD. The sampling precision is deemed good if the difference between the concentrations is below the MDL for silicate, phosphate and nitrite and within 0.06 µM for nitrate. 7.7.1 Silicate Duplicate/Replicates Plot 7.7.2 Phosphate Duplicate/Replicates Plot 7.7.3 Nitrate + Nitrite (NOx) Duplicate/Replicates Plot 7.7.4 Nitrite Duplicate/Replicates Plot 7.7.5 Ammonia Duplicate/Replicates Plot 7.7.6 Redfield Ratio Plot (14.0) Plots consists of phosphate versus NOx, best fit ratio = 14.47. 7.8 Flagged Nutrient Calibration and Quality Control Data The table below identifies all flagged data by HyPro. The calibration curve is fitted to the standards by performing several passes over each standard point and weighting its contribution to the curve depending on the magnitude of the difference between its measured and calculated value. The larger the difference, the less weighting is given to the standard's contribution towards the curve construction. The cut-off limits for good calibration data are • ±0.5% of the concentration of the top standard for silicate and nitrate +nitrite (as per WOCE). • 0.02uM for phosphate, nitrite and ammonium. CTD Peak Run Analysis Reason for Flag or Action ——— —————————— —————— ———————— ————————————————————————————————————— 1 Cal 4 Nut001 NH4 Both points BAD as greater than calibration error, not used in calibration. 1 BQC Nut001 All Suspect (MAD) peak shape, placed test in front so not to be used in calculations. 3 Cal 4 Nut002 NH4 Both points BAD as greater than calibration error, not used in calibration. 4 BQC Nut003 SiO2 3rd point flagged BAD (soft), large error compared to other 2 points. 5 Cal 2 Nut004 PO4 2nd Point suspect less weighting in calibration curve. 5 Cal 2&4 Nut004 NH4 <70% of calibration peaks are within calibration limits. Cal 2 & 4 suspect less weighting in calibration curve. 5 Duplicate Nut004 SiO2 Suspect, duplicate difference >0.2 µM. RP02 [First peak (lower concentration) is noisier than second]. 5 Duplicate Nut004 NOx Second sample flagged as BAD (mad) peak shape. Duplicates much greater than 0.06 µM, due to bad peak shape exceed A/D value, peak window on side of peak. 5 Duplicate Nut004 NH4 First sample flagged as BAD (op) peak window slipped down side of peak. 6 Cal 3&4 Nut005 NH4 <70% of calibration peaks are within calibration limits. Cal 3 & 4 suspect less weighting in calibration curve. 7 Cal 4 Nut006 NH4 Cal 4 both point s suspect, less weighting in calibration curve. 8 CC RMNS Nut007 NO2 Base off set was higher than normal all results looked too high. Re-run samples for NO2 only in Nut008, results good. Also No High low sample for analysis Nut 008 due to running out of volume. Hypro used previous high low measurement. 8 CC RMNS Nut007 PO4 1st point suspect, greater than 2% 8 CD RMNS Nut007 SiO2 All points greater than 3% 9 Cal 3 Nut009 NH4 Both points BAD as greater than calibration error, not used in calibration. 10 Cal 2&3 Nut010 NH4 Cal 2 1st point and cal 3 both points suspect less weighting in calibration curve. 11 Cal 3 Nut011 NH4 Both points BAD as greater than calibration error, not used in calibration. 12 Cal 3 Nut012 NH4 Both points BAD as greater than calibration error, not used in calibration. 16 Cal 5&6 Nut016 NOx 2nd points suspect, less weighting in calibration curve. 19 Cal 5 Nut019 NH4 Both points BAD greater than calibration error, not used in calibration. 21 Duplicate Nut021 NOx Suspect, duplicate difference greater RP0l than 0.06 µM 22 CD RMNS Nut022 SiO2 All points greater than 3% 24 Duplicate Nut024 NOx First duplicate Suspect (MAD) peak RP01 shape. 25 All Nut025 NO2 Bad data, hashed out of file, re-run in nut027, processed as nut027b 26 All Nut026 NO2 Bad data, hashed out of file, re-run in nut028, processed as nut028b 26 Cal 4 Nut026 NH4 1st point suspect, less weighting in calibration curve. 28 Duplicates Nut028 NOx Suspect, duplicate difference greater RP01 than 0.06 µM. 30 Cal 2,3&4 Nut030 NH4 Cal 2 suspect (both points), Cal 3 suspect (2nd point)-less weighting in calibration curve. Cal 4 BAD both points - not used in calibration. 30 CD RMNS Nut030 SiO2 All points greater than 3%. 32 Cal 3 Nut032 NH4 Cal 3 suspect, less weighting in calibration curve. 35 Cal 2 Nut035 NOx Cal 2, 1st point suspect, less weighting in calibration curve. 38 Duplicates Nut038 SiO2 Suspect duplicate difference greater RP01 than 0.2 µM. 42 Cal 2 Nut042 NOx Cal 2 suspect, less weighting in calibration curve. 43 Cal 2 Nut043 NOx Cal 2 suspect, less weighting in calibration curve. 44 Cal 2 Nut044 NOx Cal 2 suspect, less weighting in calibration curve. 45 Cal 2 Nut045 NOx Cal 2 suspect, less weighting in calibration curve. 45 Cal 6 Nut045 SiO2 Cal 6 2nd point greater than calibration error. 48 Cal 3 Nut048 NH4 Cal 3 2nd point suspect, less weighting in calibration curve. 51 Cal 2 Nut051 PO4 Cal 2 1st point suspect, less weighting in calibration curve. 52 Cal 2 Nut052 PO4 Cal 2 1st point suspect, less weighting in calibration curve. 54 Cal 5 Nut054 PO4 Cal 5 2nd point suspect, less weighting in calibration curve. 54 BQC Nut054 SiO2 1st point Suspect (MAD) peak shape. 54 Cal 4 Nut054 NH4 Cal 4 both points suspect, less weighting in calibration curve. 54 Drift Nut052 NO2 Last drift has large spike in plateau, swapped the drift and drift sample check peaks around. 55 Cal 4 Nut055 NH4 Cal 4 both points suspect, less weighting in calibration curve. 56 Ca1 4 Nut056 NH4 Cal 4 1st point suspect, less weighting in calibration curve. 58 RMNS Nut058 NOx 2nd last RM NS peak is suspect (mad) peak shape. 61 Drift Nut060 NOx Last drift has large spike in plateau, swapped the drift and drift sample check peaks around. 70 Baseline Nut066 NO2 Baseline stepped up on the Null before the BQC samples and then stepped down again on the uwy sample. # out all of those samples and stds etc. #peak start of NO2 and it didn't work, had to # the AD value column. 70 Drift Nut066 NO2 2nd Drift is BAD. Baseline stepped up on the Null before the BQC samples and then stepped down again on the uwy and ctd samples. # out all of the BQC and drift stds. All samples good. 71, Cal 3 Nut067 NH4 Cal 3 both points suspect (MAD), less 72 weighting in calibration curve. 75 Duplicates Nut070 NOx & Bad peak shapes, re-ran samples RPOl SiO2 at end of the run and they were OK. 76 Cal 6 Nut071 NOx Cal 6 2nd point was flagged Bad (MAD) peak shape, not used in calibration. 78 Cal 2 Nut073 NO2 Cal 2 2nd point BAD greater than calibration error. 80 Cal 1 Nut075 NH4 Cal 1 2nd point suspect, less weighting in calibration curve. 81 Cal 1 & Nut076 NH4 Cal 1 both points suspect and Cal 3 Cal 3 1st point suspect, greater than calibration error. 82 Cal 1 & Nut077 NH4 Cal 1 both points suspect and Cal 3 Cal 3 1st point suspect, less weighting in calibration curve. 83 Cal 3 Nut078 NH4 Cal 3 both points suspect, less weighting in calibration curve. 84 Cal 4 & 5 Nut079 NOx Blockage occurred during the cats (cal 4-2 and 5-1 bad, rest perfect), this offset the timing, meaning the peaks were shifted. This only really affected the carryover (use from last run) and the first two RMNS (hashed out).... RMNS values good on peaks that are good. Magical. Second MDL also hashed out - the rest are good. 85 Cal 3 Nut080 NH4 Cal 3 both points Bad greater than calibration error. 86 RMNS Nut081 SiO2 RMNS CD, 1 point flagged suspect outside of 3% line 87 Cal 3 & Nut082 NH4 Cal 3 2nd point and Cal 4 both points Cal 4 suspect greater than calibration error. 87 Cal 2 Nut082 NOx Cal 2 both points suspect, less weighting in calibration curve. 88 Cal 4 Nut083 NH4 Cal 4 both points suspect, less weighting in calibration curve. 88 Cal 2 Nut083 NOx Cal 2 both points suspect, less weighting in calibration curve. 89 Cal 2 Nut084 NOx Cal 2 both points suspect, less weighting in calibration curve. 89 Cal 2 Nut084 NOx Cal 5 2nd point suspect, less weighting in calibration curve. 89 Cal 3 Nut084 NH4 Cal 3 both points suspect, less weighting in calibration curve. 89 Cal 5 Nut084 NOx Cal 5 2nd point suspect, less weighting in calibration curve. 89 Cal 3 Nut084 NH4 Cal 3 both points suspect, less weighting in calibration curve. 89 Cal 4 Nut084 NH4 Cal 4 both points suspect, less weighting in calibration curve. 90 Cal 2 Nut085 NOx Cal 2 both points suspect, less weighting in calibration curve. 90 Cal 3 Nut085 NH4 Cal 3 both points suspect, less weighting in calibration curve. 91 Cal 3 Nut086 NH4 Cal 3 first point suspect, less weighting in calibration curve. 93 Cal 3 Nut088 NH4 Cal 3 both points are suspect, less weighting in calibration curve. 93 Cal 5 Nut088 NOx Cal 5 2nd point suspect, less weighting in calibration curve. 94, Cal 3 Nut089 NH4 Cal 3 first point suspect, less 95 weighting in calibration curve. 96 Cal 3 Nut090 NOx Cal 3 both points suspect greater than calibration error. 96 RMNS Nut090 NOx Fourth peak is suspect (mad) peak shape. 99 Cal 5 Nut093 NOx Cal 5 2nd point suspect, less weighting in calibration curve. 100 Cal 2 Nut094 PO4 Cal 2 1st point suspect greater than calibration error. 101 Cal 5 nut095 NOx Cal 5 lst point bad shape, 2nd point greater than calibration error. 102 Cal 6 Nut096 PO4 Cal 5 2nd point is suspect, less weighting in calibration curve. uwy Cal l Nut103 NH4 Cal l both points suspect, less weighting in calibration curve. 7.9 Missing or Flagged Nutrient Data and Actions taken. The table below identifies all flagged data and any samples that had repeated analyses performed to obtain GOOD data. Data that falls below the detection limit, Flag 63, is not captured in this tab le. All GOOD data is flagged 0 in the .csv and .netcdf files. Data that is flagged BAD is not exported within the .csv files. Suspect data (Flag 69) is exported in the .csv file. Refer to Appendix 8.2 for flag explanations. CTD RP Run Analysis Flag Reason for Flag or Action ————— ———— —————— ———————— ———— ——————————————————————————————— 4 18 Nut003 All 133 Outliers on profiles, sampled from wrong Niskin. 5 02 Nut004 SiO2 69 Duplicates greater than MDL 0.2 [First peak (lower concentra- tion) is noisier than second]. 5 02 Nut004 NOx 129 Duplicates much greater than 0.06 µM, due to bad peak shape exceed A/D value, peak window on side of peak. 5 02 Nut004 PO4 133 BAD air spikes. 5 02 Nut004 NH4 133 First sample flagged as BAD peak window slipped down side of peak. 9 18 Nut009 NOx, 69 Outlier on profile [not seen on PO4, salinity or dissolved oxygen - SiO2 same value as RP16, possible duplicate or sampled from wrong Niskin) 15 12 Nut012 SiO2, 133 Outliers on profiles. NO2 16 25 Nut016 All 141 Sample missing accidently not collected. 21 All Nut021 NH4 N/A Higher than usual background caused these samples to be slightly lower than expected, resulting in slightly negative values instead of 0. However results are good. 21 01 Nut021 NOx 69 Duplicates greater than 0.06 µM 21 24 Nut021 All 133 Outliers on profiles, Niskin misfire. Also seen in salinity data. 23 24 Nut023 All 133 Outliers on profiles, Niskin misfire. Also seen in salinity data. 24 01 Nut024 NOx 69 1st duplicate suspect peak shape. 25 All Nut025 NO2 133 Bad data# out of file and re- run in nut027, processed as nut027b, this data is good. 25 25, 29 Nut025 All 133 Outliers on profiles, Niskin misfire. Also seen in salinity data. 26 29 Nut026 All 133 Outliers on profiles, Niskin misfire. Also seen in salini ty data. 26 All Nut026 NO2 N/A The rmns, BQC and intQC all stepped up. The sample profiles were also offset from previous ctd profiles. CTD 25 & 26 were re-run for NO2 in the nut027b & nut028b. The initial NO2 results were # out of original files and second results used as they were good. 28 01 Nut028 NOx 69 Duplicates greater than 0.06 µM 28 29 Nut028 NOx 141 It's marked as Bad (soft) in trace. However error given in HyPro is exceeds A/D value 129, we do not have value for this one. 28 26, 27 Nut028 NOx N/A BAD peak shapes but were re- run at end of analysis and results OK. 29 21 Nut029 NOx 133 Bad peak shape, repeated in nut030 and result good. The repeated measurement for other nutrient data was # out of file as original results were good. 36 33 Nut036 PO4 133 Bad peak shape repeated in nut037 and result is good. The repeated measurement for other nutrient data was # out of file as original results were good. 38 01 Nut038 SiO2 69 Duplicates greater than 0.2 µM 44 23 Nut044 PO4 133 Bad peak shape repeated in nut045, and result is good. The repeated measurement for other nutrient data was # out of file as original results were good. 49 17 Nut049 NO2 69 Outlier on profile, bump on peak plateau. 56 All Nut056 NO2 133/ Nitrite baseline stepped up on 141 sample 5627 and 5625, then stepped back down on 5624 and 5623 but then stepped back up on 5622 and stayed elevated. Drifts are also elevated and end baselines. Flagged all data for NO2 as bad. 75 02 Nut070 SiO4 133 Bad peak shape, repeated during run and result is OK, # out bad results. 75 02 Nut070 NOx 133 Bad peak shape, repeated during run and result is OK, # out bad results. 79 08 Nut074 SiO2 133 Bad peak shape, repeated in Nut075 and result is good. The repeated measurement for other nutrients data was # out of file as original results were good. 81 07 Nut076 SiO4, 69 Outlier on profile, peak shapes NOx, good - not seen in salinity or PO4 dissolved oxygen. 89 09 Nut084 SiO4 133 Bad peak shape. Outlier on pro file. Re-run and replaced as new result is good. The repeated measurement for other nutrient data was # out of file as original results were good. 89 04 Nut084 SiO4 133 Bad peak shape. Outlier on profile. Re-run and replaced. The repeated measurement for other nutrient data was # out of file as original results were good. 96 23 Nut090 NOx 69 Suspect peak shape was re-run later in the run and result was OK used that result for all nutrients and "tested" first one out. 97 06 Nut091 SiO4 133 Bad peak shape, re-run at end of the run and this result was OK and used. The repeated measurement for other data was # out of file as original results were good. 98 18, 19 Nut092 NO2 133 Outliers on profile, re-run in Nut094 results ok in nut094. The repeated measurement for other data was # out of file as original results were good. 98 34, 35 Nut092 All 141 Samples missing accidently not collected. 99 14 Nut093 NOx 133 Bad outlier on profile, repeated in Nut94 this result good. The repeated measurement for other data was # out of file as original results were good. 102 20 Nut096 All 133 Bad, outlier in vertical profile plot (also when repeated in following run). Also seen as outlier in salinity and D.O. data. 104 29 Nut098 NOx 133 Bad peak shape, repeated and measurement OK. The repeated measurement for other nutrient data was # out of file as original results were good. 104 36 Nut098 All 141 Sample missing accidently not collected. Uwy 08 Nut026 NO2 133 The rmns, BQC and intQC all stepped up. The sample profiles were also offset from previous ctd profiles. CTD 25, 26 and uwy were re-run and for NO2 in the nut027b & nut028b. The initial NO2 results were # out of original files and second results used as they were good. 7.10 Temperature & Humidity Change over Nutrient Analyses The temperature and humidity within the AA3 chemistry module was logged using a temperature/humidity logger QP6013 (Jaycar) placed on the deck of the chemistry module. Refer to "in2018_v01_hyd_voyagereport.docx" for room temperature graphs, nutrient samples were placed on XY3 auto sampler at the average room temperature of 21.7°C. 8 Appendix 8.1 Salinity Reference Material Osil IAPSO Standard Seawater ——————————————————————————————————— Batch P161 P158 Use by date 03/05/2020 25/03/2018 K_15 0.99987 0.99970 8.2 HyPro Flag Key for CSV & NetCDF file Flag Meaning ———— ——————————————————————————————————————————————————————————————————— 0 Data GOOD - nothing detected. 192 Data not processed. 63 Below nominal detection limit. 69 Data flagged suspect by operator. Set suspect by software if Calibration or Duplicate data is outside of set limits but not so far out as to be flagged bad. 65 Peak shape is suspect. 133 Error flagged by operator. Data bad - operator identified by # in slk file or by clicking on point. 129 Peak exceeds maximum A/D value. Data bad. 134 Error flagged by software. Peak shape bad - Median Absolute Deviation (MAD) analysis used. Standards, MDL's and Duplicates deviate from the median, Calibration data falls outs ide set limits. 141 Missing data, no result for sample ID. Used in netcdf file as an array compiles results. Not used in csv file. 79 Method Detection Limit (MDL) during run was equal to or greater than nominal MDL. Data flagged as suspect. 8.3 GO-SHIP Specifications Salinity Accuracy of 0.001 is possible with Autosal™ salinometers and concomitant attention to methodology, e.g., monitoring Standard Sea Water. Accuracy with respect to one particular batch of Standard Sea Water can be achieved at better than 0.001 PSS-78. Autosal precision is better than 0.001 PSS-78. High precision of approximately 0.0002 PSS-78 is possible following the methods of Kawano (this manual) with great care and experience. Air temperature stability of ± 1°C is very important and should be recorded.* O2 Target accuracy is that 2 sigma should be less than 0.5% of the highest concentration found in the ocean. Precision or reproducibility (2 sigma) is 0.08% of the highest concentration found in the ocean. SiO2 Approximately 1-3% accuracy †,** and 0.2% precision, full - scale. PO4 Approximately 1-2% accuracy †,** and 0.4% precision, full scale. NO3 Approximately 1% accuracy †,** and 0.2% precision, full scale. Notes: † If no absolute standards are available for a measurement then accuracy should be taken to mean the reproducibility presently obtainable in the better laboratories. * Keeping constant temperature in the room where salinities are determined greatly increases their quality. Also, room temperature during the salinity measurement should be noted for later interpretation, if queries occur. Additionally, monitoring and recording the bath temperature is also recommended. The frequent use of IAPSO Standard Seawater is endorsed. To avoid the changes that occur in Standard Seawater, the use of the most recent batches is recommended. The bottles should also be used in an interleaving fashion as a consistency check within a batch and between batches. ** Developments of reference materials for nutrients are underway that will enable improvements in the relative accuracy of measurements and clearer definition of the performance of laboratories when used appropriately and the results are reported with the appropriate meta data. 8.4 RMNS Values for each CTD Deployment Analysis Run CTD # SiO4 PO4 NO2 NOx measured measured measured measured ———————————— —————————— ———————— ———————— ———————— ———————— CB reported 111.821 2.580 0.199 36.649 1 1,2 111.367 2.603 0.144 36.713 7 8 111.100 2.590 36.730 8 8 0.135 17 17 110.967 2.590 0.140 36.737 23 23 111.200 2.573 0.135 36.640 30 30 111.100 2.620 0.136 36.753 36 36 110.633 2.613 0.145 36.833 44 44 111.267 2.600 0.145 36.917 51 51 110.900 2.610 0.138 36.843 59 60 111.767 2.623 0.139 37.057 67 71 111.567 2.593 0.141 36.983 81 86 111.433 2.600 0.132 36.823 99 105 111.600 2.610 0.135 36.900 CC reported 88.228 2.130 0.119 31.740 1,2 1,2 87.767 2.130 0.133 31.787 3 3 87.600 2.120 0.140 31.893 4 4 87.533 2.130 0.130 31.857 5 5 87.663 2.114 0.129 31.836 6 6 87.775 2.138 0.133 31.788 7 7 87.600 2.123 0.137 31.860 8 8 87.600 2.128 31.858 8 8 0.133 9 9 87.400 2.138 0.135 31.S63 10 10 81.925 2.145 0.130 31.828 11 11 87.425 2.143 0.138 31.868 12 12 87.850 2.150 0.133 31.908 13 13 87.625 2.140 0.138 31.848 14 14 87.925 2.145 0.131 31.925 15 15 87.625 2.140 0.132 31.798 16 16 87.875 2.150 0.131 31.810 17 17 87.400 2.125 0.133 31.815 18 18 87.325 2.118 0.131 31.778 19 19 87.375 2.135 0.130 31.825 20 20 87.375 2.125 0.130 31.845 21 21 87.425 2.120 0.130 31.883 22 22 87.525 2.110 0.130 31.868 23 23 87.450 2.118 0.131 31.878 24 24 87.225 2.128 0.133 31.875 25 25 87.750 2.128 31.923 26 26 87.375 2.130 31.738 27 27 87.375 2.120 0.130 31.820 28 28 87.425 2.130 0.134 31.700 29 29 87.475 2.128 0.133 31.835 30 30 87.450 2.153 0.130 31.835 31 31 87.667 2.160 0.130 31.877 32 32 87.975 2.160 0.140 31.930 33 33 88.025 2.155 0.131 31.898 34 34 87.500 2.155 0.133 31.925 35 35 87.225 2.160 0.132 31.905 36 36 87.175 2.153 0.136 32.005 37 37 87.050 2.163 0.134 31.915 38 38 87.475 2.155 0.133 31.885 39 39 87.675 2.160 0.131 31.943 40 40 87.775 2.146 0.131 31.966 41 41 87.800 2.143 0.138 31.970 42 42 87.925 2.150 0.141 32.038 43 43 87.857 2.139 0.129 31.904 44 44 87.675 2.140 0.139 31.953 45 45 87.625 2.140 0.129 31.895 46 46 87.850 2.150 0.131 31.880 47 47 87.517 2.140 0.136 31.882 48 48 87.625 2.143 0.128 32.060 49 49 87.650 2.150 0.131 32.013 50 50 87.960 2.168 0.135 31.836 51 51 86.975 2.145 0.135 31.963 52 52 87.586 2.156 0.133 31.897 53 53 87.925 2.145 0.132 32.005 54 54 87.775 2.160 0.139 31.908 55 55 87.775 2.165 0.129 31.960 56 56 87.825 2.150 0.128 31.933 57 57 87.650 2.150 0.133 32.013 58 58, 59 88.025 2.168 0.130 32.000 59 60 88.175 2.168 0.131 32.035 60 61 88.050 2.163 0.133 32.153 61 62, 63, 64 88.250 2.175 0.133 31.935 62 65, 66 88.175 2.158 0.136 31.993 63 67 87.575 2.155 0.134 31.988 64 68 88.233 2.165 0.131 32.048 65 69 88.167 2.152 0.133 32.057 66 70 88.000 2.168 0.129 32.082 67 71, 72 87.880 2.132 0.143 32.022 68 73 87.925 2.140 0.130 31.960 69 74 87.825 2.148 0.138 32.020 70 75 87.900 2.148 0.132 32.058 71 76 88.025 2.135 0.130 32.008 72 77 87.775 2.150 0.129 31.868 73 78 87.975 2.153 0.129 31.993 74 79 87.275 2.138 0.128 31.915 75 80 87.750 2.150 0.131 31.875 76 81 88.000 2.150 0.133 31.995 77 82 87.800 2.150 0.132 32.090 78 83 87.900 2.158 0.133 31.880 79 84 87.800 2.145 0.131 31.890 80 85 87.667 2.155 0.134 31.863 81 86 87.800 2.140 0.128 31.780 82 87 87.875 2.168 0.138 32.018 83 88 87.825 2.163 0.134 31.995 84 89 87.800 2.173 0.134 32.000 85 90 88.000 2.160 0.132 32.140 86 91 88.250 2.148 0.128 32.050 87 92 88.000 2.158 0.133 31.973 88 93 88.100 2.158 0.131 31.938 89 94, 95 88.200 2.158 0.134 31.945 90 96 87.950 2.157 0.129 31.938 91 97 88.150 2.160 0.130 31.933 92 98 87.950 2.160 0.130 31.930 93 99 87.175 2.155 0.130 31.963 94 100 87.675 2.155 0.132 31.998 95 101 87.600 2.150 0.128 32.010 96 102 87.500 2.160 0.135 31.990 97 103 87.950 2.148 0.132 31.953 98 104 87.850 2.158 0.135 31.875 99 105 87.925 2.150 0.134 31.910 100 106 87.875 2.160 0.131 31.888 101 107 88.125 2.158 0.135 32.030 102 108 87.700 2.160 0.133 31.860 103 uwy 87.775 2.158 0.134 31.910 CC reported 14.264 0.457 0.018 5.648 1 1, 2 14.100 0.447 0.447 5.527 7 8 13.725 0.463 0.463 5.573 17 17 14.000 0.460 0.460 5.540 23 23 13.800 0.460 0.460 5.597 30 30 13.600 0.460 0.460 5.553 36 36 13.700 0.463 0.463 5.590 44 44 13.800 0.463 0.463 5.547 51 51 13.875 0.470 0.470 5.590 59 60 14.125 0.470 0.470 5.570 67 71 14.050 0.455 0.455 5.610 81 86 13.950 0.460 0.460 5.512 99 105 14.025 0.460 0.460 5.592 8.5 Internal Quality Control Values for each CTD Deployment Measured concentrations (µM) of the internal quality control and the low nutrient seawater that were produced in the shore laboratory. CTD Date LNSW Spike LNSW Spike LNSW Spike LNSW Spike LNSW Spike NOx NOx PO4 PO4 SiO2 SiO2 NO2 NO2 NH4 NH4 ———————— ———— ————— —————— ————— ———— ————— ————— ————— ———— ————— Prepared Concen- NA 5.5 NA 1.0 NA 10 NA 0.5 NA 1.0 tration ———————— ———— ————— —————— ————— ———— ————— ————— ————— ———— ————— Measured concentrations (µM) ———————— ———— ————— —————— ————— ———— ————— ————— ————— ———— ————— Oct-17 0.07 5.59 -0.001 0.99 0.9 11.3 0.06 0.55 0.34 1.31 Dec-17 0.1 5.46 0.017 1.02 1.0 11.4 0.041 0.56 0.39 1.36 CTD 1&2 0.09 5.43 0.01 1.01 0.7 11.2 0.037 0.537 0.35 1.31 CTD 3 0.09 5.44 0.01 1 0.5 10.9 0.04 0.54 0.36 1.31 CTD 4 0.09 5.43 0.02 1.01 0.4 10.8 0.037 0.535 0.37 1.31 CTD 5 0.09 5.44 0.01 0.99 0.5 10.9 0.037 0.534 0.34 1.28 CTD 6 0.1 5.47 0.02 1.01 0.5 11 0.043 0.536 0.34 1.3 CTD 7 0.09 5.48 0.01 1 0.4 10.5 0.046 0.548 0.36 1.31 CTD 8 0.09 5.46 0.01 1 0.4 10.9 0.34 1.29 CTD 9 0.1 5.45 0.02 1.01 0.4 10.8 0.038 0.538 0.39 1.33 CTD 10 0.1 5.48 0.01 1.01 0.4 10.9 0.038 0.525 0.39 1.32 CTD 11 0.11 5.45 0.01 1.01 0 10.5 0.043 0.537 0.36 1.32 CTD 12 0.1 5.45 0.02 1.01 0.5 11 0.035 0.53 0.36 1.32 CTD 13 0.11 5.48 0.02 1.01 0.2 10.7 0.042 0.538 0.37 1.33 CTD 14 0.1 5.5 0.01 1.01 0.5 11 0.034 0.538 0.36 1.33 CTD 15 0.11 5.49 0.01 1.01 0.2 10.7 0.036 0.535 0.37 1.34 CTD 16 0.11 5.46 0.03 1.02 0.7 11.1 0.033 0.527 0.38 1.34 CTD 17 0.09 5.44 0.02 1.01 0.6 11 0.038 0.535 0.37 1.33 CTD 18 0.1 5.44 0.02 1 0.5 10.9 0.04 0.527 0.37 1.32 CTD 19 0.1 5.45 0.02 1.01 0.5 10.9 0.041 0.527 0.37 1.31 CTD 20 0.1 5.43 0.01 1 0.4 10.9 0.032 0.53 0.36 1.32 CTD 21 0.1 5.44 0.02 1.01 0.5 10.9 0.037 0.528 0.32 1.26 CTD 22 0.09 5.49 0.02 0.99 0.5 10.9 0.039 0.532 0.38 1.35 CTD 23 0.09 5.48 0.02 0.99 0.4 10.9 0.038 0.526 0.36 1.3 CTD 24 0.09 5.48 0.02 1.01 0.4 10.8 0.039 0.526 0.36 1.31 CTD 25 0.09 5.49 0.02 1.01 0.4 10.9 0.048 0.545 0.36 1.31 CTD 26 0.1 5.43 0.01 1 0.1 10.8 0.046 0.543 0.36 1.31 CTD 27 0.09 5.43 0.01 0.99 0.4 10.9 0.034 0.523 0.37 1.33 CTD 28 0.11 5.4 0.02 1 0.5 10.9 0.038 0.529 0.37 1.31 CTD 29 0.1 5.43 0.02 1 0.6 11 0.04 0.533 0.38 1.35 CTD 30 0.1 5.48 0.01 1.02 0.1 10.6 0.033 0.532 0.36 1.29 CTD 31 0.09 5.45 0.02 1.02 0.5 10.9 0.041 0.542 0.38 1.34 CTD 32 0.09 5.46 0.02 1.02 0.5 11 0.044 0.543 0.35 1.32 CTD 33 0.09 5.44 0.03 1.02 0.6 11.1 0.033 0.527 0.37 1.33 CTD 34 0.12 5.5 0.02 1.02 0.6 11 0.043 0.539 0.36 1.34 CTD 35 0.13 5.48 0.02 1.01 0.4 10.8 0.039 0.539 0.37 1.34 CTD 36 0.12 5.49 0.01 1.01 0.4 10.8 0.044 0.552 0.38 1.34 CTD 37 0.12 5.49 0.02 1.02 0.1 10.5 0.045 0.548 0.37 1.33 CTD 38 0.11 5.45 0.02 1.02 0.5 10.9 0.04 0.535 0.37 1.33 CTD 39 0.12 5.48 0.01 1.02 0.4 10.9 0.038 0.535 0.37 1.33 CTD 40 0.11 5.45 0.01 1.01 0.3 10.6 0.038 0.532 CTD 41 0.1 5.42 0.01 1.01 0.3 10.8 0.045 0.536 0.36 1.33 CTD 42 0.12 5.47 0.01 1.01 0.5 11 0.048 0.551 0.36 1.33 CTD 43 0.12 5.44 0.01 1.01 0.5 11 0.034 0.529 0.36 1.31 CTD 44 0.12 5.47 0.01 1.01 0.4 10.9 0.04 0.536 0.37 1.32 CTD 45 0.12 5.45 0.01 1.01 0.3 10.9 0.034 0.536 0.38 1.32 CTD 46 0.11 5.46 0.01 1.02 0.6 11.1 0.041 0.535 0.36 1.33 CTD 48 0.11 5.47 0.01 1.01 0.6 11 0.045 0.546 0.39 1.34 CTD 50 0.11 5.49 0.02 1.02 0.7 11.1 0.038 0.53 0.37 1.34 CTD 52 0.12 5.46 0.02 1.01 0.4 10.8 0.04 0.531 0.38 1.35 CTD 54 0.12 5.44 0.02 1.02 0.5 10.9 0.048 0.541 0.36 1.33 CTD 56 0.11 5.47 0.02 1.02 0.6 11.1 0.039 0.534 0.37 1.35 CTD 58 0.12 5.48 0.02 1.03 0.5 11 0.036 0.526 0.36 1.33 CTD 59 0.11 5.48 0.02 1.02 0.6 11.2 0.037 0.53 0.37 1.34 CTD 68 0.13 5.48 0.02 1.03 1 11.5 0.036 0.537 0.37 1.33 CTD 70 0.11 5.51 0.02 1.03 0.6 11.1 0.035 0.533 0.39 1.36 CTD 73 0.1 5.49 0.01 1.01 0.6 11.1 0.039 0.534 0.38 1.34 CTD 74 0.1 5.51 0.02 1.02 0.6 11 0.056 0.547 0.36 1.32 CTD 77 0.12 5.52 0.02 1.02 0.6 11.l 0.041 0.537 0.37 1.33 CTD 78 0.12 5.52 0.03 1.02 0.6 11.1 0.043 0.536 0.37 1.33 CTD 80 0.12 5.54 0.01 1.01 0.5 11 0.04 0.536 0.36 1.32 CTD 82 0.12 5.47 0.02 1.01 0.5 10.9 0.043 0.538 0.36 1.32 CTD 85 0.12 5.42 0.02 1.02 0.5 11 0.05 0.538 0.39 1.35 CTD 87 0.14 5.5 0.02 1.03 0.4 10.9 0.052 0.545 0.36 1.31 CTD 89 0.14 5.48 0.02 1.03 0.5 10.9 0.042 0.533 0.37 1.34 CTD 90 0.14 5.48 0.01 1.02 0.6 11.1 0.046 0.547 0.38 1.39 CTD 92 0.12 5.46 0.02 1.02 0.5 11 0.038 0.533 0.38 1.34 CTD 94 0.1 5.48 0.02 1.02 0.7 11.2 0.042 0.542 0.37 1.33 CTD 96 0.13 5.49 0.02 1.02 0.5 11 0.052 0.542 0.4 1.37 CTD 97 0.11 5.45 0.02 1.02 0.7 11.1 0.039 0.528 0.37 1.33 CTD 98 0.1 5.45 0.02 1.02 0.6 11 0.044 0.531 0.4 1.36 CTD 99 0.12 5.46 0.01 1.01 0.4 10.7 0.039 0.53 0.39 1.35 CTD 100 0.11 5.49 0.02 1.02 0.7 11.1 0.041 0.536 0.39 1.36 CTD 101 0.11 0.01 0.6 0.037 0.39 CTD 102 0.16 5.49 0.02 1.02 0.5 11 0.048 0.548 0.39 1.33 CTD 103 0.12 0.02 0.6 0.045 0.41 CTD 104 0.12 5.5 0.02 1.02 0.6 11.1 0.042 0.542 0.39 1.34 CTD 105 0.12 5.49 0.02 1 0.6 11 0.041 0.533 0.39 1.36 9 References Armishaw, Paul, "Estimating measurement uncertainty in an afternoon. A case study in the practical application of measurement uncertainty." Accred Qual Assur, 8, pp. 21 8-224 (2003). Armstrong, F.A.J., Stearns, C.A., and Strickland, J.D.H., "The measurement of upwelling and subsequent biological processes by means of the Technicon Autoanalyzer and associated equipment," Deep-Sea Research, 14, pp.3 81-389 (1967). Hood, E.M. (2010). "Introduction to the collection of expert reports and guidelines." The GO­SHIP Repeat Hydrography Manual: A Collection of Expert Reports and Guidelines. IOCCP Report No 14, ICPO Publication Series No. 134, Version 1, 2010. Hydes, D., Aoyarma, M., Aminot, A., Bakker, K., Becker, S., Coverly, S., Daniel, A.G., Dickson, O., Grosso, R., Kerouel, R., van Ooijen, J., Sato, K., Tanhua, T., Woodward, E.M.S., and Zhang, J.Z. (2010). "Determination of dissolved nutrients (N, P, Si) in seawater with high precision and inter-comparability using gas-segmented continuous flow analysers." The GO-SHIP Repeat Hydrography Manual: A Collection of Expert Reports and Guidelines. IOCCP Report No 14, ICPO Publication Series No. 134, Version 1, 2010. Kerouel, Roger and Alain Aminot, "Fluorometric determination of ammonia in sea and estuarine waters by direct segmented flow analysis". Journal of Marine Chemistry 57 (1997) pp. 265-275. Murphy, J. And Riley, J.P., "A Modified Single Solution Method for the Determination of Phosphate in Natural Waters", Anal. Chim. Acta, 27, p.30, (1962) Wood, E.D., F.A.J. Armstrong, and F.A. Richards. (1967) "Determination of nitrate in seawater by cadmium-copper reduction to nitrite." Journal of the Marine Biological Association of U.K. 47: pp. 23-31. APPENDIX 3 – CFC LAB REPORT 2018 SR3 Chlorofluorocarbon (CFC), Sulfur Hexafluoride (SF6), and Nitrous Oxide (N2O)* Measurements * Note that N2O measurements are a Level 3 measurement. The concentrations were measured on the same water samples collected for the Level 1 CFC/SF6 measurements. The N2O analysis is still under development. Please contact the PI for any use of these data PI: Mark J. Warner, University of Washington (warner@u.washington.edu) Samplers and Analysts: Mark J. Warner, University of Washington Daniel Anderson, University of Washington Samples for the analysis of dissolved CFC-11, CFC-12, SF6, and N2O were collected from approximately 1720 of the Niskin water samples during the expedition. When taken, water samples for CFC analysis were the first samples drawn from the 12-liter bottles. Care was taken to co-ordinate the sampling of CFCs with other samples to minimize the time between the initial opening of each bottle and the completion of sample drawing. In most cases, dissolved oxygen and dissolved inorganic carbon were collected within several minutes of the initial opening of each bottle. To minimize contact with air, the CFC samples were collected from the Niskin bottle petcock into 250-cc ground glass syringes through plastic 3-way stopcocks. The syringes were stored in large ice chest in the laboratory at 3.5° - 6°C until 30-45 minutes before analysis to reduce the degassing and bubble formation in the sample. At that time, they were transferred to a water bath at approximately 29°C in order to increase the stripping efficiency during analysis. Concentrations of CFC-11, CFC-12, SF6, and N2O in air samples, seawater and gas standards were measured by shipboard electron capture gas chromatography (EC-GC). This system from the University of Washington was located in a portable laboratory on the heli-deck. Samples were introduced into the GC-EC via a purge and trap system. Approximately 200- ml water samples were purged with nitrogen and the compounds of interest were trapped on a Porapak Q/Carboxen 1000/Molecular Sieve 5A trap cooled by an immersion bath to - 60°C. During the purging of the sample (6 minutes at 220 ml min-1 flow), the gas stream was stripped of any water vapor via a Nafion trap in line with an ascarite/magnesium perchlorate dessicant tube prior to transfer to the trap. The trap was isolated and heated by direct resistance to 175°C. The desorbed contents of the trap were back-flushed and transferred onto the analytical pre-columns. The first precolumn was a 40-cm length of 1/8-in tubing packed with 80/100 mesh Porasil B. This precolumn was used to separate the CFC-11 from the other gases. The second pre-column was 13 cm of 1/8-in tubing packed with 80/100 mesh molecular sieve 5A. This pre-column separated the N2O from CFC-12 and SF6. Three analytical columns in three gas chromatographs with electron capture detectors were used in the analysis. CFC-11 was separated from other compounds by a long column consisting of 36 cm of Porasil B and 150 cm of Carbograph 1AC maintained at 90°C. CFC-12 and SF6 were analyzed using a column consisting of 2.33 m of molecular sieve 5A and 1.5 m of Carbograph 1AC maintained at 80°C. The analytical column for N2O was 30 cm of molecular sieve 5A in a 120°C oven. The carrier gas for this column was instrumental grade P-5 gas (95% Ar/5% CH4) that was directed onto the second precolumn and into the third column for the N2O analyses. All three detectors were run at 300°C. The analytical system was calibrated frequently using a standard gas of known gas 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, precolumns, main chromatographic columns and EC detectors were similar to those used for analyzing water samples. Three sizes of gas sample loops were used. Multiple injections of these loop volumes could be made to allow the system to be calibrated over a relatively wide range of concentrations. Air samples and system blanks (injections of loops of CFC-free gas) were injected and analyzed in a similar manner. The typical analysis time for samples was 750 sec. For atmospheric sampling, an ~100 meter length of 3/8-in OD Dekaron tubing was run from the portable laboratory to the bow of the ship. A flow of air was drawn through this line to 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 flow (100 ml min-1) of the compressed air to be directed to the gas sample valves of the CFC/SF6/N2O analytical system, while the bulk flow of the air (>7 l min-1) was vented through the back-pressure regulator. Air samples were generally analyzed when the relative wind direction was within 50 degrees of the bow of the ship to reduce the possibility of shipboard contamination. The pump was run for approximately 30 minutes prior to analysis to insure that the air inlet lines and pump were thoroughly flushed. The average atmospheric concentrations determined during the cruise (from a sets of 4 or 5 measurements analyzed when possible) were 241.7 +/- 8.7 parts per trillion (ppt) for CFC-11 (n=21), 518.6 +/- 10.9 ppt for CFC-12 (N=21), 9.3 +/- 0.5 ppt for SF6 (N=20), and 336.2 +/- 5.5 parts per billion for N2O (N=5). Note that a larger aliquot was required for higher precision N2O analysis, and this higher aliquot resulted in SF6 peak areas outside the range of the calibration curve used for seawater samples. Concentrations of the CFCs in air, seawater samples and gas standards are reported relative to the SIO98 calibration scale (Prinn et al., 2000). Concentrations in air and standard gas are reported in units of mole fraction in dry gas, and are typically in the parts per trillion (ppt) range for CFCs and SF6 and parts per billion (ppb) for N2O. Dissolved CFC concentrations are given in units of picomoles per kilogram seawater (pmol kg-1), SF6 in femtomoles per kilogram seawater (fmol kg-1), and N2O in nanomoles per kilogram seawater (nmol kg-1). CFC concentrations in air and seawater samples were determined by fitting their chromatographic peak areas to multi-point calibration curves, generated by injecting multiple sample loops of gas from a working standard (UW WRS 32399) into the analytical instrument. Full-range calibration curves were run at the beginning and end of the cruise, as well as during long transits/weather delays when possible. Single injections of a fixed volume of standard gas at one atmosphere were run much more frequently (at intervals of 2 hours) to monitor short-term changes in detector sensitivity. The SF6 peak was often on a small bump on the baseline, resulting in a large dependence of the peak area on the choice of endpoints for integration. Estimated accuracy is +/- 3%. Estimated limit of detection is 1 fmol kg-1 for CFC- 11, 2 fmol kg-1 for CFC-12, 0.05 fmol kg-1 for SF6, and 0.5 nmol kg-1 for N2O. The efficiency of the purging process was evaluated at every other station by re-stripping water samples and comparing the residual concentrations to initial values. These re-strip values were less than 1% for CFC-11 and essentially zero for CFC-12 and SF6. For N2O, the re-strip values were complicated by the apparent production of N2O within the re- stripped sample within the sparging chamber for a subset of the samples. See the discussion below. Based on the re-strips of numerous samples from the deep ocean, the mean values were approximately 4%. On this expedition, based on the analysis of 45 duplicate samples, we estimate precisions (1 standard deviation) of 0.3% or 0.002 pmol kg-1 (whichever is greater) for dissolved CFC-11, 0.8% or 0.004 pmol kg-1 for CFC-12 measurements, 0.036 fmol kg-1 or 4.1% for SF6, and 0.18 nmol kg-1 or 1.2% for N2O. Analytical Difficulties The major analytical challenge for this voyage was the sensitivity of the electron capture detector used for the measurement of SF6 and CFC-12 to changes in atmospheric pressure. The peak area of an injection of one large sample loop of the increased by approximately 4% per decrease of 1 mb in atmospheric pressure. In addition the baseline shifted upwards and was very sensitive to the motion of the ship. At atmospheric pressures below 970 mb, the broad plateau on which the SF6 peak eluted became a broad peak with the SF6 peak on the downslope. In rough seas, it was difficult to separate the smaller SF6 peaks from the broader peaks associated with the ship roll. For most of the analyses during these periods, any peak within a time window (74 to 80 sec) was identified as SF6 with endpoints manually chosen. In most of these instances, the reported low-level SF6 concentrations are flagged as questionable (flag 3). One CTD (#32) was not sampled due to analytical difficulties with this same ECD. Unknown contamination caused the detector voltage to be pegged at its maximum response. After 6 hours or so, it returned to normal. Prinn, R.G., Weiss, R.F., Fraser, P.J., Simmonds, P.G., Cunnold, D.M., Alyea, F.N., O'Doherty, S., Salameh, P., Miller, B.R., Huang, J., Wang, R.H.J., Hartley, D.E., Harth, C., Steele, L.P., Sturrock, G., Midgley, P.M., McCulloch, A., 2000. A history of chemically and radiatively important gases in air deduced from ALE/GAGE/AGAGE. Journal of Geophysical Research, 105, 17,751-17,792 REFERENCES Rosenberg, M., Fukamachi, Y., Rintoul, S., Church, J., Curran, C., Helmond, I., Miller, K., McLaughlan, D., Berry, K., Johnston, N. and Richman, J., unpublished. Kerguelen Deep Western Boundary Current Experiment and CLIVAR I9 transect, marine science cruises AU0304 and AU0403 - oceanographic field measurements and analysis. ACE Cooperative Research Centre, unpublished report. 78 pp. Rosenberg, M. and Rintoul, S., unpublished-1. Aurora Australis marine science cruise AU1121 – oceanographic field measurements and analysis. ACE Cooperative Research Centre, September 2011, unpublished report. 45 pp. Rosenberg, M. and Rintoul, S., unpublished-2. Aurora Australis marine science cruise AU1203 – oceanographic field measurements and analysis. ACE Cooperative Research Centre, November 2012, unpublished report. 30 pp. Rosenberg, M. and Rintoul, S., unpublished-3. Aurora Australis marine science cruise AU1402, Totten and Mertz CTDs and moorings – oceanographic field measurements and analysis. ACE Cooperative Research Centre, May 2016, unpublished report. 65 pp. ACKNOWLEDGEMENTS Thanks to all scientific personnel who participated in the cruise, to the oceanography and hydrochemistry team for a great job collecting and analysing the data, to all MNF support staff on the cruise, and to the crew of the RV Investigator. Funding support comes from the Australian Government Department of the Environment and CSIRO through the National Environment Science Program and the Centre for Southern Hemisphere Oceans Research. Additional support comes from the Australian Government Business Cooperative Research Centres Programme through the Antarctic Climate and Ecosystems Cooperative Research Centre (ACECRC). Acknowledgement also for long term support goes to the Australian Antarctic Division and Australia’s Integrated Marine Observing System (IMOS), and to the Marine National Facility (MNF) for ongoing support. CCHDO Data Processing Notes Data History • File Online Carolina Berys in1801.pdf (download) #93736 Date: 2018-10-03 Current Status: unprocessed • File Online Carolina Berys in1801.sea (download) #d4203 Date: 2018-10-03 Current Status: unprocessed • File Online Carolina Berys in1801.sum (download) #dc7de Date: 2018-10-03 Current Status: unprocessed • File Online Carolina Berys in2018_v01_CTD.zip (download) #ca1d9 Date: 2018-10-03 Current Status: unprocessed • File Online Carolina Berys README_in1801_ctd_exchangeformat (download) #296d7 Date: 2018-10-03 Current Status: unprocessed • File Online Carolina Berys 096U20180111_woceexchange_version01oct2018.zip (download) #b74e7 Date: 2018-10-03 Current Status: unprocessed • File Submission Carolina for Mark Rosenberg 096U20180111_woceexchange_version01oct2018.zip (download) #b74e7 Date: 2018-10-03 Current Status: unprocessed Notes 096U20180111_woceexchange_version01oct2018.zip contains data and cruise report for RV Investigator cruise 096U20180111 (aliases in2018_v01, in1801) includes CTD data and bottle data with CFC update. • File Submission Carolina for Mark Rosenberg README_in1801_ctd_exchangeformat (download) #296d7 Date: 2018-10-03 Current Status: unprocessed Notes 096U20180111_woceexchange_version01oct2018.zip contains data and cruise report for RV Investigator cruise 096U20180111 (aliases in2018_v01, in1801) includes CTD data and bottle data with CFC update. • File Submission Carolina for Mark Rosenberg in2018_v01_CTD.zip (download) #ca1d9 Date: 2018-10-03 Current Status: unprocessed Notes 096U20180111_woceexchange_version01oct2018.zip contains data and cruise report for RV Investigator cruise 096U20180111 (aliases in2018_v01, in1801) includes CTD data and bottle data with CFC update. • File Submission Carolina for Mark Rosenberg in1801.sum (download) #dc7de Date: 2018-10-03 Current Status: unprocessed Notes 096U20180111_woceexchange_version01oct2018.zip contains data and cruise report for RV Investigator cruise 096U20180111 (aliases in2018_v01, in1801) includes CTD data and bottle data with CFC update. • File Submission Carolina for Mark Rosenberg in1801.sea (download) #d4203 Date: 2018-10-03 Current Status: unprocessed Notes 096U20180111_woceexchange_version01oct2018.zip contains data and cruise report for RV Investigator cruise 096U20180111 (aliases in2018_v01, in1801) includes CTD data and bottle data with CFC update. • File Submission Carolina for Mark Rosenberg in1801.pdf (download) #93736 Date: 2018-10-03 Current Status: unprocessed Notes 096U20180111_woceexchange_version01oct2018.zip contains data and cruise report for RV Investigator cruise 096U20180111 (aliases in2018_v01, in1801) includes CTD data and bottle data with CFC update.