CRUISE REPORT: P15S (Updated MAY 2017) Highlights Cruise Summary Information Section Designation P15S Expedition designation (ExpoCodes) 096U20160426 Chief Scientists Bernadette Sloyan (leg 1), Susan Wijffles (leg 2) Dates 2016 APR 26 - 2016 JUN 22 Ship R/V Investigator Ports of call Hobart - Wellington (NZ) - Lautoka (Fiji) 45° 29' 49"S Geographic Boundaries 149°25'41"E 168°36'57"W 66° 19' 55"S Stations 140 Floats and drifters deployed Argo: 25, Deep Argo: 2, bio-geochemical: 13, shear and BGC: 3 Moorings deployed or recovered 0 Contact Information: Bernadette Sloyan Susan Wijffles Bernadette.Sloyan@cisro.au Susan.Wijffels@cisro.au RV Investigator Voyage Summary Voyage #: IN2016_V03 Voyage title: Monitoring Ocean Change and Variability along 170°W from the ice edge to the equator Mobilisation: Hobart, Tuesday 26 April, 2016 Depart Leg 1: Hobart, 2000 Tuesday 26 April, 2016 Arrive Leg 1: Wellington (NZ): 1100 Thursday 26 May Depart Leg 2: Wellington (NZ): 1230, Friday 27 May, 2016 Arrive Leg 2: Lautoka (Fiji), 0800 Wednesday, 30 June, 2016 Demobilisation: Hobart, Thursday July 14th, Friday July 15th & Monday July 18th, 2016 Voyage Manager Leg 1: Don McKenzie Contact details: Don.Mckenzie@csiro.au Voyage Manager Leg 2: Stephen Thomas Contact details: Stephen.Thomas@csiro.au Chief Scientist Leg 1: Bernadette Sloyan Affiliation: CSIRO Oceans Contact details: Bernadette.Sloyan@csiro.au and Atmosphere Chief Scientist Leg 2: Susan Wijffels Affiliation: CSIRO Oceans Contact details: Susan.Wijffels@csiro.au and Atmosphere Principal Bernadette Sloyan, Susan Wijffels, Bronte Tilbrook, Lev Investigators: Bodrossy, Bec Cowley Project name: As above Affiliation: CSIRO Oceans Contact details: Susan.Wijffels@csiro.au and Atmosphere Bronte.tilbrook@csiro.au Lev.Bodrossy@csiro.au Rebecca.Cowley@csiro.au Principal Mark Warner, John Bullister Investigators: Project name: As above Contact details: warner@u.washington.edu Affiliation: U. Washington, Seattle, WA USA NOAA-PMEL Supplementary Project Principal Alex Forrest, University of Tasmania Investigator: Project name: Working from the other side: facing the challenges of under-ice for autonomous navigation in Antarctica Affiliation: AMC, Contact details: Email: Alex.Forrest@amc.edu.au University of Tasmania Scientific objectives Sloyan, Wijffels, Cowley, Tilbrook, Bullister, Warner, Bodrossy: The full suite of key ocean parameters and the deep ocean heat and carbon reservoirs remain poorly measured. This proposal will complete full-depth, high-precision hydrographic, carbon, and tracer measurements, along 170°W from the sea-ice edge to the equator, to monitor and detect ocean variability and change including changes in the carbonate chemistry associated with acidification. The line comprises the line P15S that is part of the international GO-SHIP repeat global survey network (www.go- ship.org). These data, together with other observational data and numerical models, will allow for the detection and attribution of ocean change and variability and to assess the impact of the ocean on climate variability. This hydrographic section will monitor ocean change and variability by: 1. Directly measuring the full suite of ocean water properties (temperature, salinity, velocity, nutrients, tracers and ocean mixing) at high vertical and spatial resolution throughout the entire water column and in the deep boundary currents, contributing to the international GO-SHIP program. 2. Providing high precision biogeochemical measurements to monitor changes in ocean carbon storage and oxygen concentrations, contributing to the IOCCP international program to monitor the global carbon budget. 3. Directly measure ocean mixing to improve our knowledge of the ocean Meridional Overturning Circulation. 4. Provide high precision baseline data to calibrate the Argo array, XBT program, and other autonomous observations (ocean gliders, moorings and satellites) in the vicinity of the section. 5. Deploy Argo floats for the core mission and contributions to the international SOCCOM project. 6. Obtain side-by-side CTD/XBT data for the assessment of bias errors in XBT measurements. Voyage objectives Sloyan, Wijffels, Cowley, Tilbrook, Warner, Bullister, Bodrossy: The primary voyage objective is to obtain a repeat occupation of the 155 full-depth CTD and Niskin casts that comprise the GO-SHIP P15S section, with chemistry performed on water collected at 36 bottle levels. We measured temperature, salinity, pressure, oxygen, fluorometry, shear and micro-scale temperature continuously, and the major nutrients, oxygen, salinity, CFC and carbon components discretely via chemical analysis on board. Small amounts of material will be filtered and stored for genomic analyses back on land. CSIRO has completed this line twice before and international groups have completed similar work along lines further east. The work plan and timings are based on these past voyages. Argo float deployments will also be carried out – usually when just leaving a CTD station (SOCCOM floats) or during transit (we may slow the ship speed slightly). These will be over the ship’s stern (preferred). Results 2016 occupation of the P15S Hydrographic section: Overall delivery against the original plan was around 90%. Of the 155 stations originally planned, before leaving port, the plan was scaled back to 150 stations due to emerging information about the time required for the Wellington port call and a recommended reduction in the planned transit speeds from 12 to 11 knots. However, two extra ship days were provided later to compensate for time lost due to winch/wire issues. Ultimately of the original 155, we achieved occupation of 140 stations. Ten stations were abandoned on Leg 1, most due to wire or termination damage, one to weather and one to sea ice. One station was abandoned on Leg 2 due to a winch brake failure, ongoing winch alarm and wrap laying issues. Besides the CTD sensor traces, most casts provided Niskin bottle water samples for on board analyses. A few stations did not collect samples due to electrical damage to the CTD cable and subsequent loss of communication to the rosette. The heave compensation system (only used during Leg 2) on the CTD winches appears to be a key factor which enabled the completion of the section without further wire damage. It also has a profound and beneficial impact on the raw sensor streams, almost entirely removing package flow contamination in these data. The other key event was the near-loss of the entire frame, instruments and our main CTD wire due to a winch break failure at station 83. The safe recovery of both the wire and instrument package by the ship’s crew was nothing short of a miracle. The winch was rebuilt, the cable trimmed, spooled out and de- torqued, and the system was put back into service. This was voyage saving, as we later learned that our spare CTD (#22) had an unrepairable leak and there were no other spare CTD buses on board. CTD traces: The performance of the CTD system was mixed, but the issues are largely recoverable through post-calibration. While the sensors were generally stable throughout the voyage, large and uncharacteristic offsets were found between the sensor behaviour at sea (compared to excellent bottle salts) and in the calibration laboratory. This issue remains unexplained. Two secondary C-cells were somehow damaged and not working within specifications. Despite this, due to the sensor stability, having dual sensor lines, and the high quality of the bottle salts and through assistance from SeaBird, the final calibrated data will be excellent. See Appendix 1 for details on C-cell troubleshooting. Table 2 has the full list of CTD stations occupied. Optics: On leg 1 (stations 1-50), and in support of SOCCOM (see below), a University of Maine Wetlabs FLBBRTD (SN3698) was installed onto the 9plus analogue channels, measuring the optical parameters fluorescence, backscatter, Photosynthetically Active Radiance (PAR) and light transmission. This was removed in Wellington. From stations 56-140, the MNF’s Chelsea Aquatracker was fitted onto the frame, returning fluorescence, backscatter, and light transmission. Hydrochemical Data: Laboratory results for the major nutrients, oxygen and salinity, from the CSIRO hydrochemistry team are excellent and will meet GO-SHIP standards. This is the best deep section data set this team has ever delivered and it is an outstanding effort. The team kept up with the intense throughput associated with processing 36 bottle samples per cast. The good instrumentation, standards used and very stable laboratory temperatures were also vital ingredients, along with the teams’ dedication and thorough preparation. Anthropogenic trace gases: The measurements of the chlorofluorocarbon-11 (CFC-11), CFC-12 and sulphur hexafluoride (SF6) by the University of Washington/NOAA-PMEL team are of high quality -2187 samples were collected in coordination with the carbon chemistry team. See Appendix 2 for details and highlights. Carbon chemistry: A total of 2625 water samples were analysed for total dissolved inorganic carbon from a subset of the Niskin water samples, with an additional 269 duplicate samples analysed. Also, 2628 seawater samples were analysed for total alkalinity, plus 224 duplicate samples. The data are deemed of very high quality. See Appendix 3 for details and highlights from the carbon team. Helium Data: Seawater was collected from some of the Niskin bottles at 20 stations to produce 219 duplicate 10-inch long sealed (crimped) copper tubes for future analysis of helium isotopes onshore. Originally we had planned to sample 22 stations, however the sea ice edge did not permit sampling as far as 68°S. At CTD station 2 the helium crimping equipment froze. We relocated the crimper to the dry- clean laboratory and helium sampling was completed out of the normal water sampling order. See Appendix 9 for an overview of the helium sampling. Velocity Shear: Data was collected via a two unit Lowered Acoustic Doppler Current profiler system on nearly all casts. On some casts, data download delays meant we had to abandon those data in order to avoid a schedule slip. The data are also somewhat compromised by two factors: • Heading on the master (150kHz) instrument was bad • One beam on this instrument also failed. However, we believe these data will be still very useful after processing for mixing and flow studies. See Appendix 10 for further details. Temperature microstructure: On nearly all casts, fast (100Hz) temperature and package motion were measured via Chi-pods. This data can be used to determine ocean mixing and dissipation rates. Typically, 2 instruments sampled the waters at the leading edge of the frame (above and below). Data were downloaded every second day or as needed. See Appendix 4 for more detail. Underway velocity: Both RDI Ocean Surveyors (150kHz and 75kHz) acoustic Doppler profilers (ADCPs) were run continuously for the voyage. The raw data looks good, and will likely underpin an excellent final velocity data set. The OS150 alignment error used on acquisition was wrong and the correct value is currently unknown since the instrument was refit in October 2015. This requires a new bottom tracking data set to be collected for calibration. There is a heading error in the processing for the Leg 1 data that also remains unresolved. The acquisition system appeared to drop navigation data intermittently, possibly due to buffer limits. We believe these can all be recovered in post processing. Both ringing and bubble contamination afflict the upper bins, but their impact was partially reduced by extending the drop keel to its medium setting. eXpendable BathyThermograph side-by-side data: At several groups of station, two teams would drop eXpendable BathyThermograph (XBT) probes during the upper 1000db of the downcast. The purpose is to diagnose and quantify depth and temperature biases in XBT types and ages to help improve their use for climate studies. Several probe types and temperature regimes were covered. In total 295 probes were deployed. See Appendix 5 for details. Nitrogen processes, budgets, plankton and bacterial phylogeny: The data arising from this study will be a major source of new information on N2 fixation rates and the controls of the N-cycle contributing to regional primary productivity in the different water masses along the P15 GO-SHIP line. They will fill in a major knowledge gap in regards to N and C cycling in the world open oceans. Most of these data require substation shore-based analyses. Samples that were taken for: • Picoplankton analysis, using flowcytometry back on land • Chlorophyll a and phytoplankton pigment analysis, using HPLC back on land • DNA analyses using targeted functional gene expression analyses and high- throughput sequencing back on land • Primary productivity, following isotopic tracer incorporation into the particulated matter, using stable isotopes 13C, aboard using incubation bins • Dissolved inorganic nitrogen uptake measurements, using standard 15N protocols, aboard using incubation bins • N2-fixation rates, using 15N gas as an injected tracer to measure fixation rates, aboard using incubation bins • Nitrification rates See Appendix 6 for details. Profiling Float deployments: The Argo community joined together to take full advantage of the relatively rare chance to deploy profiling floats into the far Southern Ocean with a shipped-based high quality GO-SHIP deployment profile with full chemistry for calibration. The aft laboratory was literally filled with floats of various types when it left Hobart. In total we deployed 43 profilers – 25 floats for the core Argo mission, 2 prototype deep Argo floats, 13 bio-geochemical floats for the Southern Ocean Carbon and Climate Observations and Modeling (SOCCOM) experiment. In addition, 3 non- Argo shear and BGC floats were deployed for the University of Tasmania. Floats were deployed on leaving a completed station or during transit. At each SOCCOM float deployment CTD, samples were collected for pH sample for depths to 2000m, up to 24 per cast plus 2 duplicates at any of those depths (0.8 litres each). High Pressure Liquid Chromatograph samples at surface and chlorophyll max, plus a duplicate at one of those depths (1-2 litres each). Particulate Organic Carbon sample at surface and chlorophyll max, plus a duplicate at one of those depths (2-3 litres each). These samples were sent back to the US for shore-based analysis. The details of the float deployments can be found in Table 1. Deep Argo CTD testing: Two prototype SBE-61 internally recording CTDs were attached to the frame above the SBE 9plus intakes. The SBE-61 is being developed for use in the deep Argo program and is still being tested and refined. The SBE’s were on for all 140 CTD casts, and survived the sea floor impact on station 83. The data will be returned for analysis by SeaBird Electronics, Seattle. Inertial Navigation System test (U. Tasmania piggy back project): The PHINS (PHotonic Inertial Navigation System) is a device capable of measuring all navigational parameters associated with the motion of a vehicle (e.g. heading, speed, position, and attitude), and is to be used in Autonomous Underwater Vehicle navigation and control. This cruise provided the perfect opportunity to test the behaviour of the PHINS technology at a range of different latitudes, with the aim of quantifying the effect of latitude on the accuracy of heading and position. To this end, the PHINS was operated continuously, with a repeating 12 hour testing regime, for the duration of the voyage. See Appendix 7 for details. Atmospheric Chemistry and Aerosols: During the voyage, instrumentation was run continuously to investigate the chemical composition, size distribution, optical properties and cloud nucleating properties of marine aerosol over the southern hemisphere. These parameters are important in the quantification of regional contributions of aerosols to radiative forcing, and will help to improve meteorological and climate change models. With a few exceptions, the instrumentation has operated with only minor issues and a wealth of data has been successfully collected. See Appendix 8 Graduate student training: In addition to the science objectives, we were able to offer a seagoing observational experience to several graduate students in marine science from Australia and New Zealand. As well as assisting with the CTD and water sampling, the students undertook small projects in data analysis, and helped trouble shoot the systems on the ship. We believe this was a terrific and successful learning experience for these students, in the challenges of observational science and physical oceanography. VOYAGE NARRATIVE Leg 1- Narrative by Bernadette Sloyan Tuesday 26 April – Tuesday 3 May 2016 We departed Hobart on Tuesday 26 April at 2000 and began our transit to our first plan CTD stations of the P15S hydrographic section (170W, 68S). On the transit we stopped to completed a test CTD station (149 25.704’E, 45 29.813’S) and all CTD volunteers were shown how to run the CTD console and instructed on water sampling method for carbon, oxygen, helium, nutrients and salt. The CTD watches were established and everyone settled into their respective watches. We provided a link to the Master of the sea ice images that were being update daily by Benoit Legrassy (CSIRO). The Master found these images very useful for navigation during the last few days of the transit, determining the position of the northern edge of the sea-ice and likely location of our most southern station. The weather during the transit was relatively calm and we averaged 11-12 knots. On the transit 12 Argo floats were deployed (see Table 1). Wednesday 4 May – Sunday 8 May 2016 As Investigator approached the ice edge the outside air temperature decreased to sub-zero temperatures. We consulted with Steve Rintoul, Nathan Bindoff and Mark Rosenberg regarding strategies to mitigate freezing of CTD sensors and Niskin bottles. Following their advice, we will dried the conductivity sensors prior to deployment and opened the CTD door at the last possible moment. We started CTD operation on CTD Winch 2 (outboard) and using CTD 20. We arrived at our first CTD (CTD 002) location (169 59.97 W, 66 20.08 S) at 8pm. Air temperature was -17.0C and decreasing. Condition were calm with less than 10 knots of wind. The CTD was deployed smoothly and the station completed successfully. The CTD upon removal from the water snapped froze – frozen sensor, tubing, and spigots. In the CTD room pipes (freshwater and salt) and the Helium crimping equipment froze during the duration of the door being open. We had to use a hair dryer to defrost the niskin spigots. Once the pipes and taps defrosted water leaked from cracks and all water valves to the CTD room were isolated. The CTD water samplers were very cold by the end of sampling. No damage was done to the CTD sensors, Niskins, or rosette. The current configuration of the CTD room is not suitable for sub-zero CTD operations. A heater needs to added to ensure we raise the room above 0°C. After CTD 002, we continued south in anticipation of a CTD station further south. During the transit the wind increased to 40 knots and spray froze when hitting the ships superstructure. Sea-ice was seen on the surface. At 5am Thursday morning we decided with sea-ice in the area and strong winds it was unlikely we would be able to complete a CTD station further south. Therefore, we turned north and CTD 002 became our most southern CTD station. CTD stations, 003, 004, 005 and 006 were completed without incident, although CTD 005 was undertaken in a confused sea. We completed our first mechanical re- termination at the end of station 005. On Saturday (7 May) as we prepared to deploy CTD 007 the CTD winch wire jumped the pulley and was jammed between the winch cheeks. The wire required an electrical re- termination. We moved to CTD Winch 1 in an attempt to continue CTD operations. At 350 m the CTD deck box sounded an alarm indicating loss of communication with the CTD. The deck box was turned off and the rosette was returned to the deck. Upon recovery the wire was tested and found to be damaged. We now need to re-terminate both CTD wires. With both CTD wires requiring re-termination we were unable to undertake CTDs for 24 hours. Given the delay we abandoned CTD 007 and made a slow transit to CTD 008. During the transit, we tested the deck box using the spare CTD; It tested okay. The fuses were examined and they had not blown. Water was found in both cables and over 500m was cut from each cable. On Sunday as we prepared the CTD (CTD 008) ready for deployment the deck unit failed and was turned off. On inspection the transformer on the deck unit had failed and CTD instrument (CTD 20) was now faulty. The problem was sourced to an incorrect fuse in the unit which was corrected. Working on CTD winch 2 and the spare CTD (CTD 22) we completed CTD 008 and 009. CTD 010 was deployed but at 2000 m the deck box alarmed and blew a fuse. The broken fuse was replaced but blew immediately. The CTD/rosette package was recovered. Upon recovery we found that the electrical termination failed. We now have to re- terminate CTD winch 2. For CTD 011 we moved to the CTD winch 1 and completed the abandoned station 10. No LADCP data were taken as the connecting cable was broken. The MNF electronic technicians repaired the CTD 20 unit. We now have 2 working CTD units. At the end of most of these stations either an Argo or SOCCOM float was deployed. Monday 9 May – Sunday 15 May 2016 CTD 012 and 013 were completed. On CTD 014 at 3300 dbar on the up-cast we lost communication to CTD. The station was aborted and we hauled the CTD/rosette back to the surface. Another broken electrical termination. Only bottom water samples were collected. We now have another 24-hour delay as both CTD winch wires require an electrical re- termination. By Wednesday we were back in the water and completed CTD 015. On CTD 016 we again lost communication to the CTD package at 7 dbar on the downcast. We abandoned the station. We switched to CTD winch 2 (outboard) and deployed the wire with a 35 Kg weight. The electrical termination had failed on return. Now have two winch cables that need re- termination. We moved to cold terminations. These take 2-3 hours to be completed. CTD 017 was further delayed due to weather (12 hours). The station was eventually completed. Niskin bottles 2-7 failed to close. Signal to close was sent but no reply received. Alarm sounded as CTD/rosette was returned to deck when a cable distortion went over a sieve. Electrical termination had failed on deck. For CTD 018 we moved to CTD winch 2 (cold mould) and completed the station, however the bottles failed to fire; No bottle samples were collected. A CTD cable was changed and the carousel tested, bottle non- firing issue was fixed. Moving to cold mould electrical termination increased the success rate of CTD stations. During Saturday we completed CTD stations 019 through to 022. We had further issues at CTD 023. We had two attempts at starting the station. On the first the CTD deck unit alarmed just as the rosette entered the water. The rosette was recovered and all electrical connections were tested; these were all working. We then tested all connections by spraying water on the CTD rosette with tension on the wire. Everything seemed fine. We then re-deployed the package and it again failed on entry to the water, just as the mechanical termination entered the water. We recovered the CTD, went to breakfast to decide what to do next. It was decided to move the distorted wire past the mechanical termination and coil this excess wire within the rosette frame. Thus the new mechanical termination was on an undamaged section of wire. We also found that we had lost a nut that holds the package to the wire, on inspection a few other bolts were hanging on by one thread. The crew then checked and tightened all nuts and bolts on the rosette frame. We re- deployed the CTD with the damaged wire past the mechanical termination. The CTD deck box did not alarm and we proceeded with the stations. The wire had no kinks on return, but the deck box did alarm as we came back on board. The cable tested positive, so a new mechanical termination was completed with more damaged wire coiled inside the CTD frame. Continuing to take these mitigation steps – moving wire through the mechanical termination and re- terminating using cold mould - we were able to complete CTD 023 -025. We lost approximately 93 hours due to wire issues. Monday 16 May – Sunday 22 May 2016 This was our most successful week, with the mitigation steps, we averaged 4 CTD stations a day. We completed 18 CTD stations – CTD 026 - 043. We added to our mitigation steps, rotating the CTD anti-clockwise, some times 3-4 times, at the end of a station before landing the rosette on the deck. This action was implemented given that LACDP initial processing showed that the CTD was rotating during the cast. With the CTD situation somewhat under control, we had a chance to begin to look at the data. The nutrient data was compared to the previous occupations of this section. The LADCP was processed using the CTD and SADCP data. This showed that there was a significant difference between the headings of the downward and upward ADCPs. Using software developed for ADCP processing (moorings) we determined that the lower ADCP unit heading was noisy and “wanders” significantly during a cast. We have implemented a LADCP processing that uses only the up-ward ADCP heading data. Saturday and Sunday saw our first significant weather delays. Our planned CTD station at 45 56.41 S, 171 49.84 W was not attempted as the wind was 35-40 knots and we are running out of time. We decide to move to the next station. We expect the front to slide southeast and have improved weather conditions at the next station. We continued to transit to 45 33.52 S, 172 16.71. We arrived at this location at midnight and the wind was still 45-50 knots. We decided to heave-to and wait out the weather. At 5am the wind was still averaging 40 knots. We had a look at the weather forecast and the strong winds were predicted to continue for the next 6-10 hours. We decided to move to the next station at 45 10.57 S, 172 43.92 W. We arrived at the station location and waited 1.5 hours for the wind to decrease. We started CTD 044 at 12:30. The station was completed and the wind speed had decreased to 15 knots. After completion of station 044 we decided to back-track south to pick up the CTD station at 45 33.52 S, 172 16.71 W. We examined the GRIB charts and decided that although the wind would increase as we moved south there was the chance of completing a station at the base of the Chatham Plateau. 1.5 hours into the transit the wind had increased to a mean of 35 knots and gusts over 40 knots. It was decided that we would be unable to complete a station further south. Thus we turned around and headed north. Unfortunately, we have missed stations at the based of the Chatham Plateau. Station 045 was completed successfully. Processing of CTD 040 LADCP data showed that the 150 kHz downward unit had a broken beam – beam 4. We have now implemented a 3-beam solution method Monday 23 May – Tuesday 24 May At CTD 046, the deck unit alarm sounded on deployment. The CTD was brought back on board. The cabling was checked and everything tested positive. The CTD was redeployed, alarm sounded again. The alarm is the bottom depth alarm. The property traces looked fine. It was decided to continue the station and move to CTD 20 at the next station. Large wire kinks were found on recovery of the CTD. We decided move to CTD winch 1 and re-terminate the wire (CTD winch 2). At CTD 047, now using CTD 20, the pumps switched off at approximately 1200 dbar on the down-cast. Given the time constraints, we decided to continue the station. Pumps came on at approximately 1600 dbar, however the pump again turned off on the upcast. There were large kinks in the wire. A new CTD cable fixed the pump issue, however we required another cold mould re-termination. Deployment of CTD 048 was delayed due to the short distance between stations and having to fault find the issues of pumps turning off and on, and re-terminate the wire. We were further delayed due to CAP computing issues. These delays required constant re-planning of CTD stations. The delays resulted in the dropping of three planned station on the Chatham Rise (shallower than 1200 m) and two station on the northern slope of the Plateau. We hope leg 2, that has been provided with an extra 24 hours, will be able to complete the stations on the northern slope. CTD 049 and 050 were successfully completed. Our final CTD station (050) was completed at 0830 on Tuesday morning. We then began our transit to Wellington. In total we lost a total of 10 planned CTD stations on leg 1, of which two were due to the northward extent of sea-ice. Investigator arrived in Wellington at 10am on May 27. Handovers began around midday and went until late afternoon. SOCCOM samples were removed from the vessel and shipped to Scripps for analysis. Leg 2- Narrative by Susan Wijffels Friday May 27 We left around 1230pm with a largely new science party and new marine crew. All of our 63 day’ers returned after a night ashore. Every one settled in, we ran the safety induction, muster and held a brief science/life-aboard briefing. Most started to move into watches. Saturday May 28 We made quick headway downwind and swell towards our first station, making up some time. We trained the watches on water sampling techniques and the underway systems. We also had many discussions on managing or mitigating against the wire damage experienced on leg. These centred around: 1. Preventing zero tension events that might lead to a snap and high-load sequence – this means only lowering slowly in the upper few 100ms on the downcast. We discussed this with the bosun (Graham) and winch drivers and need to manage these low tension events in big sea states. 2. Measuring the rotation of the package via a newly installed Motion Reference Unit (MRU) and attempting to compensate the observed rotation on retrieval by spinning the package. 3. In cases where the ship is rolling on station, reduce the CTD-boom extension to reduce the swell effect on the tensions 4. Trying heave compensation during a down cast to see if that helps reduce tension shocks. Sunday May 29 CTD 51 was started around 4am and proceeded smoothly in a fairly mild sea state. The acquisition went smoothly. Sampling took a while as the watches are still being trained, and many were down with sea sickness. CTD 52, 53 and 54 went relatively smoothly- though we noticed a few snap and load events in the building sea state. Many volunteers are out of action due to seas sickness and the DAP and SIT team, Bernie Heaney and I are assisting the watches. Monday May 30 CTD 55 resulted in some kinks forming just above the frame. These were pulled through the mechanical termination and stowed inside the frame to avoid an electrical re-termination. We are firing the near surface bottle on the fly to reduce exposure to the surface waves. We realized the Boss Flourometer had been offloaded in New Zealand. We worked on finding the MNF flourometer to prepare it to be added to the frame. CTD 56 After discussion and with the strong support of the ship’s bosun, we decided to employ heave compensation on the downcast and lowered the speed to 50m/min. This will reduce exposure to a snap/load event during the downcast where drag is opposing gravity. Upcast was slowed to 50m/min until 2500db and then increased to 60m/min. Heave compensation was not used on upcast due to the danger of a bad wrap at the lay turnarounds at the drum ends. CTD station 57 we used HC at 60m/min, but with slow uphaul speeds out of HC. A SOCCOM float was deployed in dirty conditions over the aft port corner. MNF’s Chelsea Aquatracker was fitted to the 9plus on channel 6. CTD 58 revealed new kinks developing. As the station was delayed as a squall came through we pulled the wire through the mechanical termination again. The cast proceeded fine but again with slower wire speeds, which is driving an unsustainable schedule slip. Tuesday May 31 CTD 59 Tried increasing downcast wire speeds with HC on, and successfully used HC during the bottom approach. Upcast speeds were kept to 50m/min until 2500db and then increased to 60m/min. CTD 60 Used HC during the upcast but with a switch off during the drum end wraps. The deck team worked this well, diligently working with the CTD watch to monitor the wraps on the drum. CTD61 – Successful and operated as above. SOCCOM float deployed. Wednesday June 1 CTD 62 completed as above. During CTD 63 after firing eight bottles, the deckbox fuse blew at 2900db and we lost communication with the 9plus. We retrieved the CTD and frame without communication. When the frame came aboard and the wire de-tensioned, many spools sprung loose on the drum indicating the cable was under high torque, which agreed with the MRU readings showing the package was continuously rotating clockwise (3-10) times per upcast. Subsequent diagnosis on the wire shows that it has a short 4km from the termination. This essentially makes this winch/wire unusable for the rest of our voyage. I sent out a call to international colleagues to ask for advice on managing wire damage. The response was excellent from our GO-SHIP collaborators. Suggestions included minimizing snap/shock load events, putting on a vane to reduce rotation and thus increased torqueing of the wire, and streaming out the wire with a swivel and weight to de-torque the cable. The mechanical termination was moved to CTD Winch 1. The system tests all looked OK. CTD 64. As we spooled out this new cable we came across many messy wraps and gaps on the drum near the end plates. During the upcast this required careful spooling to ensure the cable lays went on properly, reducing the effective wire speeds considerably. HC was used on both the up and down casts (but switched off when the cable lay is at the drum ends). SIT team and ship’s engineers start work on manufacturing a vane from material we sourced from NIWA in New Zealand. Thursday June 2 CTD 65 - 67. Went smoothly except for stops for minor wrap adjustments – we are now in HC and doing up and down casts at 60m/min. Both CTD watch and deck crew are monitoring the winch drum. Frame continues to rotate. Friday June 3 CTD 68 – completed without incident though the frame continues to rotate. A vane constructed by SIT staff and the ship's engineers was fitted to the package. As a test we deployed down to 500db and back up, to confirm that it worked as hoped. On the full cast the vane very effectively prevented any rotation of the frame. CTD 70 – 71 were completed. Several CAP crashes occurred and there were several incidents of having to spool back out and in again on the upcasts to prevent a bad lay on the drum. Saturday June 4 CTD 72-74 – we attempted to upgrade the software on Winch 1 to the same version as Winch 2, but this has failed. There is a continuing need to stop and adjust spooling during these casts, costing between 5-20 minutes per cast. Sunday June 5 CTDs 75-78 completed. Around three spool adjustments per cast with both deck team and CTD watch monitoring the cable wraps carefully. Monday June 6 CTDs 79-81 completed as above. Schedule slowly sliding behind. Tuesday June 7 CTD 82 was completed as above. CTD 83 proceeded smoothly. At 1103am, just after firing the second bottle on, the winch brake failed completely and the cable started to spool out violently at over 200m/min. In a few minutes our CTD frame was on the sea floor. By the time the Chief Engineer had managed to manually screw down the break band at least a further 1000m of cable was also payed out. The ship’s crew then put in a mammoth effort over the next 36 hours to retrieve the cable and rosette. Tuesday June 8 Ongoing activities to prepare for the retrieval of the frame. This included stoppering off the cable with 3 Chicago clamps, keeping the ship hovering over the package, stripping and rebuilding the CTD winch break, testing its efficacy and then checking the winch gearbox, motor and controls. Once the winch was tested and ready, tension was transferred back to the winch drum, and uphaul began slowly at 10- 20m/min. There were some moments with large tension spikes just before we lofted the wire off a rough bottom, and then the tension returned to what we would normally expect for the frame on uphaul. Once we were certain the frame had been lifted off the sea floor, we powered on the deckbox, and the CTD started sending data as usual. This turned out to be remarkable given the wire damage. A slow agonizing retrieval near 20-30m/min ensued, with the frame rotating very rapidly. A few hundred meters above the termination, there were knots in the conducting cable (which took hours to unsnarl and feed through the blocks) and the wire was wrapped around the package on retrieval. The frame was back on deck around 410am Once on deck we could see the top guard rail of the frame was snapped, but amazingly no Niskins were smashed. Even the upper LADCP, which was pushed over, remained functional. As far as we can tell nearly all our sensors had no calibration shift. The ships engineers and deck crew rebuilt and tested the winch break, checked the system and readied it for use. If this had failed we would have had to move to the 24 bottle frame and coring boom out of the shelter deck. Just in case, this backup system was set up in the shelter deck area. The kinked and knotted cable was cut away and then we spooled out the cable with a small weight and swivel to help de-torque it. This took another 11.5 hours to complete, with the uphaul very slow due to frequent winch alarms constantly shutting down power and interrupting the operation. An entire 1.5 hours was lost trying to diagnose the source of these somewhat random winch alarms. Rather than continue to lose time, once the wire was fully on board, we moved the ship 15nm, which merged two stations and resulted a 45nm spacing. The transfer of the newly terminated cable to the CTD and frame, and the set up for the next station by the science team was fast. The LADCP was mounted on a bracket from the 24 bottle frame, and as a result it blocked lanyards from two Niskins, so these were left off. Tuesday June 9 CTD 85 was a merger of two stations resulting in 45’ separation at this part of the section. The rebuilt winch seemed to work reasonably well, though many stops and rewinds were needed. The upward looking LADCP was remounted on its old frame which had been repaired by the ship’s engineers. CTDs 86-87 proceeded well, with 2-3 spooling adjustments. Upcast speeds are slowed to keep tensions below 2.1-2.2T at depth but were sped up to 70m/min above ~3000db to make up time. This seems to work well. A request to the MNF for additional ship time to help compensate for the time lost to date due to the winch break failure was successful with the granting of an additional 24 hours to this leg. Wednesday June 10 – Saturday June 11 CTD 88-95 proceeded smoothly with 2-3 spooling adjustments. The secondary conductivity sensor continued to develop an anomalous salty bias in the upper 1000m (both compared to the bottle salts and the primary channel). Swapped in SBE C4 SN 4718 and checked the line plumbing. A deep SOLO was deployed gently in its box after station 88. Sunday June 12 CTDs 94-95 were completed. The new C cell did not fix the anomalous behaviour of the secondary channel. SIT fitted a new pump to that line. We continue to require close attention to cable lays on the drum by both the deck crew and the CTD watch. Each station has several stops to adjust the spool or to backwind to correct a bad lay. Random winch alarms also slowed down the stations. We realigned the flow path on both 9plus channels to go from deep to shallow. Monday June 13 - Hump Day CTDs 96-100 proceeded as above. Further delays occurred due to the CTD door opening. A Hump Day meeting was held. We could see the lights of Nuie from the bridge. Tuesday June 14 We continue to search for the causes of the bad conductivity in the secondary channel. After CTD 101, we pulled the 9plus forward to give greater clearance of the rosette frame struts. This did not solve it in the data from CTD 102. Wednesday June 15 CTD 103. We decided to try the other 9plus (CTD #22 SN 1324) to ensure we had a useable secondary C trace. However at 300db the oxygen values corrupted and then the deckbox alarmed. Power was shut down and the frame was retrieved. On inspection it was found that the 9plus had leaked. We had to switch back to CTD #22 (SN 552). The aborted cast data was parked and a new station 103 was completed. It is likely that we have no spare 9plus on board at this point. CTDs 104-105 completed. The old square vane was put back on as the new version was not preventing rotation as well. Thursday June 16 CTD 106-111 completed as normal (2-3 spooling adjustments). As we are passing across a deep ridge we have close station spacing. The station turnarounds are fast and this is tough on the chemistry laboratories. After CTD 110 we changed out the oxygen sensor (SN 3195).on the secondary line, based on a suggestion by Dave Murphy at SeaBird. Friday June 17 CTDs 112-114 completed. Before 113, Ben Baldwin suggested trying yet another C cell in the secondary line. This fixed the problem! We had, in fact, two bad C-cells, one after the other! It is a relief to have a backup channel as there is more sea snot and other fouling turning up on the frame and in the bottles. Saturday June 18 – Sunday June 24 CTDs 115 – 141 were completed without incident in hot steamy conditions. The deck crew became very efficient at minimizing spooling stops while still closely monitoring the cable and winch drum, and the deployments and retrievals were honed down to an efficient operation between the deck, bridge and science crews. Faster upcast speeds above ~3500db also helped us bank time. In this way we were able to occupy nearly all of the planned stations. A great achievement given the challenges we faced at the start and the near loss of our primary cable and instrument package. Summary Despite the challenges we were able to overcome most problems and complete the bulk of our planned work. The quality of the data collected is very high, particularly from the chemistry teams who have delivered an excellent and very high resolution (due to the 36 bottle sampling) data set. We are confident that this occupation of P15S has uncovered clear and ongoing changes to the deep ocean heat and carbon content, and chemistry. The novel genomic and production sampling coordinated by Eric Raes will likely deliver some ground-breaking insights. The mixing information taken via the shear measured by the LADCP, sADCP and fine and microscale properties via the chi-pods and CTD will also be very insightful and unprecedented along this line. Voyage Track (see pdf) Marsden Squares (see pdf) Move a red “x” into squares in which data was collected Moorings, bottom mounted gear and drifting systems Table 1: Float details in order of deployment. All deployments have code: D06 Institutions/PIs are as follows: SIO = Scripps Institution of Oceanography -PI – Dean Roemmich SOCCOM = Southern Ocean Carbon and Climate Observation and Modelling experiment – PI Lynne Talley UTAS – University of Tasmania, PI - Helen Phillips and Pete Strutton CSIRO PI – Susan Wijffels. Deploy Order Hull Date/time Longitude Latitude Type Owner No. ------------ ----- --------------- ------------ ----------- --------- ------ 1 8390 27/4/2016 22:04 151 27.29' E 47 57.20' S Solo II SIO 2 8447 28/4/2016 04:33 152 21.20' E 49 59.90' S Solo II SIO 3 7741 29/4/2016 12:50 156 33.97' E 54 0.03' S APEX CSIRO 4 7738 30/4/2016 04:04 159 28.82' E 56 14.40' S APEX CSIRO 5 7742 1/5/2016 01:50 164 59.00' E 59 14.90' S APEX CSIRO 6 8352 1/5/2016 07:09 166 16.19' E 60 0.06' S Solo II SIO 7 8448 1/5/2016 17:37 169 10.20' E 61 31.00' S Solo II SIO 8 7743 1/5/2016 21:14 170 14.04' E 62 00.07' S APEX CSIRO 9 8454 2/5/2016 04:48 172 33.76' E 63 0.36' S Solo II SIO 10 8455 3/5/2016 06:47 178 30.22' W 64 45.00' S Solo II SIO 11 8456 4/5/2016 01:30 172 29.70' W 65 47.20' S Solo II SIO 12 7740 4/5/2016 5:47 170 43.41' W 66 11.79' S APEX CSIRO 13 8457 4/5/2016 17:20 169 58.60' W 66 39.30' S Solo II SIO 14 F0568 5/5/2016 06:25 170 03.95' W 65 39.84' S NAVIS SOCCOM 15 7739 4/5/2016 21:23 169 49.30' W 66 20.50' S APEX CSIRO 16 F0570 4/5/2016 12:10 170 0.10' W 66 20.51' S NAVIS SOCCOM 17 8462 5/5/2016 06:20 170 03.95' W 65 39.84' S Solo II SIO 18 8463 6/5/2016 12:56 169 58.50' W 63 59.70' S Solo II SIO 19 – CTD 6 F0565 6/5/2016 07:42 170 04.30' W 64 0.00' S NAVIS SOCCOM 20 – CTD 9 8464 8/5/2016 09:22 169 59.82' W 62 29.71' S Solo II SIO 21 – CTD 11 9761 8/5/2016 18:35 169 59.30' W 61 59.90' S APEX SOCCOM 22 – CTD 15 F0571 11/5/2016 15:37 170 01.10' W 59 59.70' S NAVIS SOCCOM 23 8460 10/5/2016 02:46 169 59.20' W 60 30.40' S Solo II SIO 24 – CTD 19 9265 13/5/2016 16:10 170 0.50' W 57 59.80' S APEX SOCCOM 25 – CTD 25 F0566 15/5/2016 15:18 170 0.70' W 55 0.70' S NAVIS SOCCOM 26 – CTD 27 7718 16/5/2016 07:10 169 56.04' W 53 59.15' S APEX UTAS 27 – CTD 29 7719 16/5/2016 21:31 170 0.92' W 52 59.92' S APEX UTAS 28 – CTD 29 7789 16/5/2016 21:27 170 0.87' W 53 00.06' S APEX UTAS 29 – CTD 31 9660 17/5/2016 11:57 170 04.20' W 57 59.70' S APEX SOCCOM 30 – CTD 30 7612 17/5/2016 04:51 169 59.30' W 52 29.70' S APEX CSIRO 31 – CTD 35 9632 18/5/2016 16:27 169 59.50' W 50 0.50' S APEX SOCCOM 32 8453 18/5/2016 06:32 170 0.00' W 49 0.00' S Solo II SIO 33 – CTD 39 9634 19/5/2016 20:11 169 59.30' W 47 59.16' S APEX SOCCOM 34 – CTD 40 7611 20/5/2016 03:56 169 58.90' W 47 29.03' S APEX CSIRO 35 – CTD 42 8465 20/5/2016 18:14 170 54.60' W 46 42.80' S Solo II SIO 36 - CTD 43 9762 21/5/2016 05:23 171 22.20' W 46 19.80' S APEX SOCCOM 37 – CTD 44 7610 22/5/2016 04:11 172 43.90' W 45 10.50' S APEX CSIRO 38 – CTD 57 9630 30/5/2016 09:17 172 41.70' W 39 58.00' S APEX SOCCOM 39 – CTD 59 F0634 31/5/2016 00:43 172 07.55' W 39 04.13' S NAVIS CSIRO 40 – CTD 61 9752 31/5/2016 15:03 171 30.98' W 38 11.09' S APEX SOCCOM 41 – CTD 88 6012 9/6/2016 22:46 170 0.13' W 24 57.53' S DEEP SOLO SIO 42 – CTD 92 6013 11/6/2016 05:16 169 99.38' W 22 98.93' S DEEP SOLO SIO 43 – CTD 120 F0632 18/6/2016 18:29 169 37.59' W 9 55.35' S NAVIS CSIRO Summary of Measurements and samples taken DATA PI NO UNITS TYPE Item see page above see see Enter No. above above code(s) from DESCRIPTION list on last page ---- ---------------- ----- -------- ------- ----------------------------- Sloyan/Wijffels 140 CTD Full depth continuous profiles of temperature, conductivity, pressure, oxygen, flourescence, PAR, light transmission, scattering, temperature microstructure, velocity, and additional prototype measurements of temperature, pressure and conductivity. Sloyan/Wijffels 140 Niskin With the above, discrete water casts samples were capture by 36 Niskin bottles per cast, and analysed by onboard laboratories for: nitrate, nitrite, phosphate, oxygen, silicate, and salinity. Tilbrook 140 Niskin From a subset of the Niskins above, alkalinity, total dissolved inorganic carbon. Raes/Bodrossy 140 Niskin From a subset of the Niskins above, microbial material was filtered and stored for later genomic analysis Warner/Bullister 140 Niskin From a subset of the Niskins above, concentrations of CFC-11, CFC-12 and SF-6. Cowley/Wijffels 295 XBT At some CTD stations, XBTs were drops dropped simultaneous with the downcast from 0-1000db. Sloyan/Downes 20 Niskins From a subset of the Niskins between 66S and 42.73S Alroe/Brown underway Atmospheric Chemistry and Aerosols Table 2. List of all CTDs completed. Stn Start Time End Time Longitude Latitude Depth (m) --- ------------------------ ------------------------ ---------- -------- --------- 1 2016-04-27T04:00:32.472Z 2016-04-27T06:59:57.909Z 149.428 -45.497 4299 2 2016-05-04T08:44:01.018Z 2016-05-04T11:46:03.271Z 189.992 -66.332 3277 3 2016-05-05T03:20:41.153Z 2016-05-05T06:00:56.633Z 189.968 -65.662 3297 4 2016-05-05T13:20:24.907Z 2016-05-05T16:12:14.822Z 189.984 -64.995 2836 5 2016-05-05T21:45:09.215Z 2016-05-06T00:44:24.863Z -170.003 -64.502 2348 6 2016-05-06T05:01:56.231Z 2016-05-06T07:28:53.065Z 189.958 -63.990 2807 8 2016-05-08T01:41:57.338Z 2016-05-08T03:16:23.764Z 189.968 -63.001 3046 9 2016-05-08T06:50:03.329Z 2016-05-08T09:11:46.453Z 190.008 -62.499 2539 10 2016-05-08T12:21:19.393Z 189.998 -62.001 3302 11 2016-05-08T15:35:30.046Z 2016-05-08T18:19:30.052Z -170.004 -62.003 3360 12 2016-05-08T21:46:21.480Z 2016-05-09T00:50:36.208Z 189.998 -61.491 3470 13 2016-05-09T16:31:07.920Z 2016-05-09T20:32:56.941Z 189.988 -61.001 4483 14 2016-05-09T23:35:04.451Z 190.002 -60.500 3951 15 2016-05-11T11:51:23.283Z 2016-05-11T15:25:39.232Z 189.996 -60.000 3905 16 2016-05-11T18:40:15.773Z -169.997 -59.498 4672 17 2016-05-12T20:00:04.319Z 2016-05-13T00:57:54.416Z 190.002 -58.994 4763 18 2016-05-13T04:41:15.570Z 2016-05-13T08:56:24.213Z 189.986 -58.491 5190 19 2016-05-13T12:19:34.718Z 2016-05-13T16:02:55.979Z -170.010 -58.001 4432 20 2016-05-13T19:10:57.839Z 2016-05-13T23:12:03.895Z 189.994 -57.503 5019 21 2016-05-14T02:14:19.014Z 2016-05-14T06:32:38.209Z 190.003 -57.002 5078 22 2016-05-14T09:26:16.442Z 2016-05-14T13:52:34.294Z 189.991 -56.498 5090 23 2016-05-14T21:22:12.759Z 2016-05-15T01:56:39.672Z -170.008 -56.002 5121 24 2016-05-15T04:41:21.185Z 2016-05-15T08:21:22.581Z 189.989 -55.514 4833 25 2016-05-15T11:08:33.772Z 2016-05-15T15:04:08.054Z -170.002 -54.996 4843 26 2016-05-15T20:00:12.895Z 2016-05-15T23:57:17.125Z 189.997 -54.500 4831 27 2016-05-16T02:49:06.749Z 2016-05-16T06:58:44.984Z -169.985 -53.996 5142 28 2016-05-16T09:54:08.128Z 2016-05-16T13:49:43.812Z 190.009 -53.501 5226 29 2016-05-16T16:37:36.199Z 2016-05-16T21:18:15.385Z 189.989 -53.004 5220 30 2016-05-17T00:16:45.970Z 2016-05-17T04:29:21.431Z 189.990 -52.505 5161 31 2016-05-17T07:55:27.336Z 2016-05-17T11:47:36.463Z 189.922 -52.002 4913 32 2016-05-17T14:36:45.966Z 2016-05-17T18:37:59.133Z 189.984 -51.492 4732 33 2016-05-17T21:41:11.848Z 2016-05-18T01:43:26.543Z 189.990 -51.002 5248 34 2016-05-18T04:20:50.075Z 2016-05-18T08:27:37.658Z 190.004 -50.497 5052 35 2016-05-18T11:37:36.343Z 2016-05-18T16:13:53.136Z 190.007 -50.006 5384 36 2016-05-18T19:15:06.047Z 2016-05-18T23:30:41.690Z 189.983 -49.504 5220 37 2016-05-19T02:15:29.121Z 2016-05-19T06:14:07.361Z 189.996 -48.995 5262 38 2016-05-19T09:15:42.998Z 2016-05-19T13:13:36.267Z 190.000 -48.502 5298 39 2016-05-19T15:59:05.698Z 2016-05-19T19:58:50.793Z 190.007 -47.995 5310 40 2016-05-19T23:38:42.257Z 2016-05-20T03:49:04.376Z 190.009 -47.503 5379 41 2016-05-20T06:49:55.735Z 2016-05-20T10:51:27.177Z -170.466 -47.109 5412 42 2016-05-20T13:48:55.354Z 2016-05-20T18:06:13.182Z 189.089 -46.719 5296 43 2016-05-21T01:16:15.147Z 2016-05-21T05:18:16.866Z 188.624 -46.326 5100 44 2016-05-22T00:21:11.875Z 2016-05-22T04:06:09.426Z -172.736 -45.176 4665 45 2016-05-22T10:03:02.223Z 2016-05-22T13:20:54.416Z -173.141 -44.835 3830 46 2016-05-22T16:39:56.631Z 2016-05-22T19:39:03.940Z 186.498 -44.525 3414 47 2016-05-22T23:35:42.231Z 2016-05-23T02:40:24.000Z -173.746 -44.328 3102 48 2016-05-23T06:20:59.593Z 2016-05-23T08:21:23.577Z 186.063 -44.156 1892 49 2016-05-23T15:42:28.390Z 2016-05-23T17:01:48.390Z 185.215 -42.931 1057 50 2016-05-23T18:19:40.160Z 2016-05-23T19:55:49.608Z 185.347 -42.746 1584 51 2016-05-28T16:14:20.306Z 2016-05-28T18:54:54.994Z -174.410 -42.400 2666 52 2016-05-28T21:29:48.241Z 2016-05-29T00:04:10.766Z -174.250 -42.167 2866 53 2016-05-29T03:10:55.467Z 2016-05-29T06:24:11.017Z 186.052 -41.717 3116 54 2016-05-29T09:20:12.256Z 2016-05-29T12:48:15.813Z 186.363 -41.273 3292 55 2016-05-29T16:03:03.069Z 2016-05-29T19:21:51.563Z 186.668 -40.832 4178 56 2016-05-29T22:03:34.309Z 2016-05-30T02:04:33.488Z 186.976 -40.392 4592 57 2016-05-30T04:47:48.414Z 2016-05-30T09:01:22.620Z 187.294 -39.958 4739 58 2016-05-30T12:14:08.948Z 2016-05-30T16:12:59.901Z -172.414 -39.511 4776 59 2016-05-30T20:33:42.659Z 2016-05-31T00:29:43.153Z 187.883 -39.068 4861 60 2016-05-31T03:40:12.877Z 2016-05-31T08:05:21.954Z -171.808 -38.628 4929 61 2016-05-31T10:54:53.015Z 2016-05-31T14:55:29.261Z 188.499 -38.187 4945 62 2016-05-31T17:39:55.439Z 2016-05-31T21:49:35.251Z -171.201 -37.757 5028 63 2016-06-01T00:46:26.310Z 189.107 -37.307 5146 64 2016-06-01T07:45:39.848Z 2016-06-01T12:21:23.997Z 189.394 -36.871 5303 65 2016-06-01T15:00:17.591Z 2016-06-01T18:57:40.511Z 189.706 -36.450 5087 66 2016-06-01T21:52:55.429Z 2016-06-02T02:10:17.334Z 189.998 -36.002 5084 67 2016-06-02T07:11:03.580Z 2016-06-02T08:09:51.319Z 189.993 -35.680 4372 68 2016-06-02T10:05:44.979Z 2016-06-02T14:11:33.883Z 190.000 -35.337 4909 69 2016-06-02T17:14:37.276Z 2016-06-02T21:02:31.630Z -169.995 -35.014 5264 70 2016-06-02T23:56:59.914Z 2016-06-03T04:17:59.232Z -170.006 -34.505 5505 71 2016-06-03T06:55:55.109Z 2016-06-03T11:30:53.771Z 190.001 -34.012 5547 72 2016-06-03T14:09:08.789Z 2016-06-03T18:18:02.498Z 190.000 -33.501 5446 73 2016-06-03T21:12:13.104Z 2016-06-04T01:32:03.632Z 189.994 -33.000 5591 74 2016-06-04T04:25:07.081Z 2016-06-04T09:44:26.841Z 190.003 -32.500 5572 75 2016-06-04T12:27:50.130Z 2016-06-04T16:51:53.619Z 190.005 -32.002 5700 76 2016-06-04T19:44:17.163Z 2016-06-04T23:48:47.511Z 190.006 -31.499 5553 77 2016-06-05T02:23:03.598Z 2016-06-05T06:52:03.414Z 190.002 -31.023 5630 78 2016-06-05T09:36:11.341Z 2016-06-05T13:56:01.685Z 190.004 -30.512 5556 79 2016-06-05T16:40:46.912Z 2016-06-05T21:25:47.606Z -169.993 -29.999 5437 80 2016-06-05T23:53:43.091Z 2016-06-06T04:03:12.410Z 190.000 -29.501 5226 81 2016-06-06T06:53:23.015Z 2016-06-06T11:36:55.821Z -169.995 -29.006 5605 82 2016-06-06T14:09:24.425Z 2016-06-06T18:28:26.073Z 190.001 -28.503 5454 83 2016-06-07T15:26:50.239Z 2016-06-07T15:53:02.758Z -169.991 -27.984 5264 84 2016-06-08T10:24:16.518Z 2016-06-08T15:05:51.923Z 190.002 -27.272 5464 85 2016-06-08T19:10:59.700Z 2016-06-09T00:17:28.530Z 190.004 -26.495 5637 86 2016-06-09T02:51:15.437Z 2016-06-09T07:54:44.048Z 190.007 -26.000 5607 87 2016-06-09T10:31:19.445Z 2016-06-09T15:11:53.560Z 190.002 -25.509 5836 88 2016-06-09T18:06:23.701Z 2016-06-09T22:29:28.525Z 189.998 -24.999 5653 89 2016-06-10T01:42:23.191Z 2016-06-10T06:08:34.689Z 189.999 -24.501 5670 90 2016-06-10T09:20:24.195Z 2016-06-10T13:53:06.924Z 189.999 -24.000 5689 91 2016-06-10T16:52:43.422Z 2016-06-10T21:20:17.826Z 190.004 -23.505 5676 92 2016-06-11T00:26:01.170Z 2016-06-11T04:56:47.183Z 190.004 -22.999 5701 93 2016-06-11T08:02:25.191Z 2016-06-11T12:32:10.517Z 190.000 -22.501 5663 94 2016-06-11T15:30:50.404Z 2016-06-11T20:06:09.433Z 190.000 -22.002 5636 95 2016-06-11T22:53:18.177Z 2016-06-12T03:03:14.292Z 190.001 -21.503 5430 96 2016-06-12T05:52:54.391Z 2016-06-12T10:06:28.855Z 190.001 -20.998 5482 97 2016-06-12T12:47:03.016Z 2016-06-12T17:32:12.377Z 190.001 -20.503 5675 98 2016-06-12T20:14:10.806Z 2016-06-13T00:23:47.764Z -170.002 -20.000 5341 99 2016-06-13T03:03:07.613Z 2016-06-13T06:49:42.210Z 189.997 -19.498 4915 100 2016-06-13T09:33:26.523Z 2016-06-13T12:14:50.468Z 189.942 -19.004 2989 101 2016-06-13T15:03:29.146Z 2016-06-13T18:54:55.035Z 189.998 -18.503 5269 102 2016-06-13T21:39:46.446Z 2016-06-14T01:15:19.931Z 190.000 -18.001 4919 103 2016-06-14T06:52:34.183Z 2016-06-14T10:30:37.926Z 189.999 -17.499 5037 104 2016-06-14T13:19:40.044Z 2016-06-14T16:51:38.553Z 189.998 -17.003 5005 105 2016-06-14T19:49:13.424Z 2016-06-14T23:24:11.140Z -170.000 -16.504 5140 106 2016-06-15T02:10:16.869Z 2016-06-15T06:06:31.818Z 189.999 -16.003 5150 107 2016-06-15T08:54:05.975Z 2016-06-15T12:53:20.966Z 189.999 -15.498 5095 108 2016-06-15T15:32:26.391Z 2016-06-15T18:56:06.305Z 190.000 -15.005 4826 109 2016-06-15T20:52:44.028Z 2016-06-15T23:30:52.379Z 190.001 -14.666 3330 110 2016-06-16T01:40:00.371Z 2016-06-16T04:49:52.408Z 190.002 -14.282 3546 111 2016-06-16T06:43:49.711Z 2016-06-16T09:24:24.872Z -169.999 -13.972 2972 112 2016-06-16T11:14:01.550Z 2016-06-16T14:26:37.400Z -169.999 -13.819 4338 113 2016-06-16T16:18:09.474Z 2016-06-16T19:47:25.972Z 189.998 -13.504 4888 114 2016-06-16T22:54:35.623Z 2016-06-17T02:30:24.514Z 190.001 -13.000 4980 115 2016-06-17T05:22:04.447Z 2016-06-17T09:01:31.046Z -169.999 -12.499 5012 116 2016-06-17T11:45:19.226Z 2016-06-17T15:35:37.121Z 189.997 -11.998 5097 117 2016-06-17T18:25:04.949Z 2016-06-17T21:58:04.975Z -169.999 -11.496 5069 118 2016-06-18T00:37:17.771Z 2016-06-18T04:30:02.323Z 190.000 -11.001 5135 119 2016-06-18T07:22:02.899Z 2016-06-18T10:47:57.099Z 190.001 -10.500 4878 120 2016-06-18T14:33:07.577Z 2016-06-18T18:21:06.416Z 190.371 -9.925 5227 121 2016-06-18T22:41:57.912Z 2016-06-19T02:48:28.206Z 191.002 -9.499 5357 122 2016-06-19T05:43:59.835Z 2016-06-19T09:22:06.274Z 191.125 -8.997 4891 123 2016-06-19T12:09:30.173Z 2016-06-19T16:06:03.387Z 191.251 -8.495 5182 124 2016-06-19T18:58:14.874Z 2016-06-19T22:39:57.802Z 191.384 -8.001 5212 125 2016-06-20T01:21:14.743Z 2016-06-20T05:22:17.796Z 191.249 -7.501 5287 126 2016-06-20T08:06:41.515Z 2016-06-20T12:15:06.408Z 191.249 -7.000 5676 127 2016-06-20T14:56:28.342Z 2016-06-20T18:58:25.358Z 191.251 -6.502 5553 128 2016-06-20T21:39:59.661Z 2016-06-21T01:50:54.802Z 191.249 -6.000 5679 129 2016-06-21T04:34:11.165Z 2016-06-21T08:39:59.859Z 191.250 -5.502 5476 130 2016-06-21T11:17:38.778Z 2016-06-21T15:18:39.517Z -168.750 -5.000 5583 131 2016-06-21T17:50:18.275Z 2016-06-21T21:47:59.558Z 191.250 -4.501 5555 132 2016-06-22T00:21:47.029Z 2016-06-22T04:27:36.064Z 191.249 -4.001 5178 133 2016-06-22T07:06:59.058Z 2016-06-22T10:53:32.647Z 191.250 -3.502 5023 134 2016-06-22T13:38:31.916Z 2016-06-22T17:25:35.631Z 191.249 -3.000 5388 135 2016-06-22T20:10:50.573Z 2016-06-22T23:53:22.984Z 191.250 -2.499 5346 136 2016-06-23T02:35:31.797Z 2016-06-23T05:19:52.127Z 191.250 -2.001 3413 137 2016-06-23T08:09:26.337Z 2016-06-23T12:30:51.322Z 191.251 -1.501 5926 138 2016-06-23T15:14:59.409Z 2016-06-23T19:24:07.539Z 191.250 -1.001 5803 139 2016-06-23T22:08:54.069Z 2016-06-24T02:01:32.511Z 191.250 -0.501 5513 140 2016-06-24T04:55:31.999Z 2016-06-24T09:09:54.961Z 191.250 -0.002 5628 Personnel List Leg 1 Name Organisation Role --- ---------------------- ------------ -------------------------- 1. Don McKenzie CSIRO MNF Voyage Manager 2. Lloyd Fletcher Doctor Aspen Medical 3. Bernadette Sloyan CSIRO Chief Scientist 4. Kate Berry CSIRO Carbon Team 5. Abe Passmore CSIRO Carbon Team 6. Christine Rees CSIRO MNF Hydrochemist 7. Erik Van Ooijen CSIRO Carbon Team 8. Eric Raes U. WA Bacteria/Genomics 9. Craig Neill CSIRO Carbon Team 10. Kelly Brown CSIRO Hydrochemist 11. John Church CSIRO CTD Watch Leader 12. Ian McRobert CSIRO MNF Electronics 13. Rod Palmer CSIRO MNF Electronics 14. Bonnie Chang U. WA CFC 15. Dave Wisegarver NOAA PMEL CFC 16. Stephen Tibben CSIRO MNF Hydrochemist 17. Anoosh Sarraf CSIRO MNF Data Processing 18. Steven Van Graas CSIRO MNF Data Processing 19. Matt Boyd CSIRO MNF GSM 20. Peter Hughes CSIRO MNF Hydrochemist 21. Taha Cowen U. Tasmania CTD watch 22. Madi Rosevear U. Tasmania CTD watch 23. Tobias Aldridge U. Tasmania CTD watch/iXblue PHINS INS 24. Hayden Martin ANU Carbon Team 25. Paul Sandery U. Tasmania CTD watch 26. Rodrigo Gurdec JCU CTD watch 27. Nicole Hellessey U. Tasmania Bacteria/Genomics 28. Swan Sow CSIRO Bacteria/Genomics 29. Nic Pittman U. Tasmania CTD watch 30. Joel Alroe QUT Atmospherics Leg 2 Name Organisation Role --- ---------------------- ------------ -------------------------- 1. Steve Thomas CSIRO MNF Voyage Manager 2. Susan Wijffels CSIRO Chief Scientist 3. Ben Baldwinson CSIRO MNF Electronics 4. Will Ponsonby CSIRO MNF Electronics 5. Hugh Barker CSIRO MNF Data Processing 6. Stew Wilde CSIRO MNF Data Processing 7. Bernie Heaney CSIRO MNF GSM 8. Ann Thresher CSIRO CTD Watch Leader 9. Mark Rosenberg U. Tasmania CTD Watch Leader 10. Esmee Van Wijk CSIRO CTD watch 11. Yue Hau Li U. Tasmania CTD watch 12. Asha Vijayeta Monash U. CTD watch 13. Maija Kaipio U. Auckland CTD watch 14. Edward King CSIRO CTD watch 15. Mainak Mondal ANU CTD watch 16. Luwei Yang U. Tasmania CTD watch 17. Tobias Aldridge U. Tasmania CTD watch/iXblue PHINS INS 18. Christine Rees CSIRO MNF Hydrochemist 19. Cassie Schwanger CSIRO Hydrochemist 20. Kelly Brown CSIRO Hydrochemist 21. Stephen Tibben CSIRO MNF Hydrochemist 22. Bronte Tilbrook CSIRO Carbon Team/co-PI 23. Kate Berry CSIRO Carbon Team 24. Abe Passmore CSIRO Carbon Team 25. Erik Van Ooijen CSIRO Carbon Team 26. Craig Neill CSIRO Carbon Team 27. Hayden Martin ANU Carbon Team 28. Jessica Ericson U. Tasmania Carbon Team 29. Charles Maxson U. Auckland Carbon Team 30. Eric Raes U. WA Bacteria/Genomics 31. Gaby Paniagua Cabarrus U. Tasmania Bacteria/Genomics 32. Bernhard Tschitschko UNSW Bacteria/Genomics 33. Reece Brown QUT Atmospherics 34. Bonnie Chang U. WA, USA CFC 35. Rolf Sonnerup U. WA, USA CFC Marine Crew Leg 1 Name Role ------------------ ----------------------- Mike Watson Master Roderick Quinn Chief Mate Brendan Eakin Second Mate Thomas Watson Third Mate Gennadiy Gervasiev Chief Engineer Sam Benson First Engineer Ian McDonald Second Engineer Damian Wright Third Engineer John Curran Electrical Engineer Alan Martin Chief Caterer Emma Lade Caterer Rebecca Lee Chief Cook Matt Gardiner Cook Jonathan Lumb Chief Integrated Rating Dean Hingston Integrated Rating Darren Capon Integrated Rating Murray Lord Integrated Rating Matthew McNeill Integrated Rating Kel Lewis Integrated Rating Ryan Drennan Integrated Rating Leg 2 Name Role ------------------ ----------------------- John Highton Master Gurmukh Nagra Chief Mate Adrian Koolhof Second Mate James Hokin Third Mate Chris Minness Chief Engineer Mark Elliot First Engineer Michael Sinclair Second Engineer Ryan Agnew Third Engineer Shan Kromkamp Electrical Engineer Cassy Rowse Chief Caterer Emma Lade Caterer Keith Shepherd Chief Cook Matt Gardiner Cook Graham McDougall Chief Integrated Rating Chris Dorling Integrated Rating Matt McNeill Integrated Rating Paul Langford Integrated Rating Peter Taylor Integrated Rating Dennis Bassi Integrated Rating Rod Langham Integrated Rating Acknowledgements We thank the Masters and crew of the Investigator, and the MNF electronic and computing support teams. Their willingness to help work through some of the major issues we encountered was essential to our success. Don McKenzie and Steve Thomas, our Voyage Managers, were a joy to work with. Their thorough knowledge of the vessel and equipment was invaluable, their calm personalities and strong support for our goals and care for our team made our jobs very easy and kept all safe and happy. We thank the MNF management team for their support in organizing the large team, and for making extra time available to help reach our goals. We thank Mark Rayner and the CSIRO hydrochemistry team for their outstanding preparation for this challenging voyage. Mike Jackson was invaluable in assisting us upgrade the laboratories HVAC for the challenges of the tropics. This voyage is the last one to be supported by the Australian Climate Change Science Program (Department of Environment). We thank our international GO-SHIP colleagues (Brian King, Greg Johnson, Toste Tanhua, Kats Katsumata, Jim Swift) for sending their advice on winches, wire torsion, tension and cable management to help us improve operation of the new systems on Investigator. We also thank Norge Larson and David Murphy from Seabird Electronics for their prompt and helpful advice with troubleshooting our conductivity cell issues. Lastly, we are grateful to our Leg 2 Bosun, Graham McDougall, and Chief Engineer, Chris Minness, for their outstanding work in assisting with the winch brake failure incident and restoring a workable system to us. This enabled the successful completion of our work and their actions were truly voyage saving. Signature Your name Bernadette Sloyan Susan Wijffels Title Chief Scientist (Leg 1) Chief Scientist (Leg 2) Signature(s) Date 14 July 2016 List of additional figures and documents Appendix 1 CTD Calibrations Issues Appendix 2 Anthropogenic Trace Gases Appendix 3 Total Dissolved Inorganic Carbon and Total Alkalinity Appendix 4 Temperature Microstructure Appendix 5 XBT Calibration Projects Appendix 6 Nitrogen processes, budgets, plankton and bacterial phylogeny Appendix 7 Inertial Navigation System tests Appendix 8 Atmospheric Chemistry and Aerosols Appendix 9 Helium isotopes Appendix 10 Lowered ADCP Issues Appendix 1 CTD calibration issues S.E. Wijffels, June 2016 Issue 1 – Large Conductivity Offsets Uncalibrated CTD – bottle conductivity differences are large ~ 0.01 - 0.02, for both channels and both CTDs. Stations 1-47 were done with sensors calibrated in March 2016. Note, after station 7, due to damage, the CTD was changed from # 20 to #22 but sensors from 20 were moved to 22 and operated out to station 46. Then we changed back to CTD 20 but with sensors with much older calibrations. This is a large and surprising conductivity offset error - out of tolerance for both the instrument (SBE C4 and T3 and 9plus) and the calibration laboratories (SeaBird and CSIRO). Steps taken to track this down at sea include: 1) Checking all SNs and calibration coefficients used on acquisition (multiple times)– while we found some errors, none explained this problem 2) Checking bottle salts against historical P15S occupations. These agreed to within tolerance (0.001) where they should, in the well mixed and ancient North Pacific Deep Waters. 3) Analysed all past CTD calibrations on CTD data from Investigator. These all showed similar sized offsets, with cells remaining stable between calibrations and across buses. Most disturbingly, the primary set used on our stations 1-46 had a lower offset (salty by 0.01) before it went through the CSIRO calibration lab in March (now salty by 0.025). In fact, for all Investigator data, a clear pattern emerged showing that all CSIRO calibrations resulted in a salty offset (0.01-0.025) compared to at sea bottle salts, while all SBE calibrations were fresh (0.007-0.01). This pattern remains regardless of the 9plus bus used. See below. 4) Tested the raw hex data recorded by the CAP acquisition system against the SBE SeaSoft processing suite, and demonstrated that the resulting data are identical to within numerical precision. Thus we do not believe it to be due to CAP. 5) Engaged Norge Larsen and Dave Murphy at SBE, who kindly sent suggestions on what to test. At the end of process, they are equally mystified. We suggest that the MNF work with the CSIRO calibration laboratory to try to understand where these offsets arise. Issue 2 - Pressure dependent error in our secondary C-cells. We found two types of depth dependence of CTD-bottle salt offsets in our data. Most T/C cell combinations give an offset that is downward increasing (or upward decreasing). This error is relatively small and in spec (~0.002). More concerning, the T/C secondary channel on CTD 20 had an offset that swings salty towards the surface. This persisted even when the C cell was changed! This behaviour could be seen on acquisition. Below are example of the offsets, with the bottom right showing the large swing to salty on the secondary channels. (see pdf) After discussions by email with Norge Larson, the linear shift with pressure is well known as explained here from Norge: “The linear pressure effect in salinity is a common feature of the SBE-4 conductivity cell. There is a pressure correction coefficient on the conductivity calibration sheet (CPCOR) which is the theoretical compression coefficient for pure borosilicate glass. In reality the conductivity cell exhibits a composite compression coefficient due to its hard epoxy coating. This expresses itself as a residual linear pressure effect of typical magnitude (0.7 - 1) * (+0.001 psu / 1000 dbar). The physical mechanism is well studied and is properly corrected by adjusting the value of CPCOR to a smaller magnitude number (coefficient remains a negative value).” This advice has been used in the calibration model we will use to adjust the data to the bottle salts. The strong swing to salty values was not explained. However, after swapping out the secondary thermistor, oxygen sensor, checking the flow lines, moving the CTD to change the flow dynamics, we finally swapped in a THIRD C-cell. This last change fixed the problem. The two damaged cells (SBE 4C SNs 2312 and 2235) will be sent back to SeaBird for careful diagnosis. Norge was skeptical it could be a crack in the ceramic of the cell. An example on this cell error can be seen in the secondary-primary differences below. This pattern was seen on acquisition. Issue 3 – Calibration Model to apply to the Conductivity Data The depth-dependent calibration changes noted above will not be removed by the current cell constant and offset used by CAPpro. Thus we need to include more terms. I tested 4 calibration models – a 7 term model used by Scripps ODF (constant plus quadratic in T,C and P), a fit where the SBE coefficients CTcorr and CPcorr are varied as well as the cell constant and offset (SBE model), and the current one used in CAPpro (conductivity offset and slope). These models, were run across burst samples from both the primary and secondary channels for all sensor combinations, and the residuals compared. The upshot is that a SBE model that keeps CTcorr at the nominal value and allows CPcorr to be varied is the most physically sensible (based on advice from SBE) and fits as much of the variance as the more complex ODF model. The resulting residuals are largely unstructured, except for small time drifts and shifts (due to cell rinses or cleans). The bad C-cells in the secondary channels for stations 51-113 did not yield well to calibration (as expected) and this data should not be used. Figure 1.1 Residuals in primary CTD-bottle conductivities for stations 1-46. Red is the ODF model, blue is the current model used in CAPpro (offset by 1e-3 S/m) and green is the SBE –P model (offset by 2e-3). Below (offset by -1e-3) are the variance accounted for by the non-standard model terms. The SBE model does as well as the more complex ODF model. Figure 1.2: As for Figure 1.1, but for the second set of primary sensors used in stations 47-140. Sensor combinations and calibration dates: blue shows changes made Sensor/ 1-46 47-50 51-87 88-93 94-110 111-113 114 - Station (Leg1) (Leg2) -------- ----- ----- ----- ----- ------ ------- ------ T1 4722 6022 6022 6022 6022 6022 6022 CSIRO SBE SBE SBE SBE SBE SBE 3/16 7/15 7/15 7/15 7/15 7/15 7/15 C1 3868 44425 4425 4425 4425 4425 4425 CSIRO SSBE SBE SBE SBE SBE SBE 3/16 77/15 7/15 7/15 7/15 7/15 7/15 Pump 1 2492 8344 8344 8344 8344 8344 8344 T2 4522 6024 6024 6024 4718 4718 4718 CSIRO SBE SBE SBE CSIRO CSIRO CSIRO 3/16 7/15 7/15 7/15 10/15 10/15 10/15 C2 4426 2312 2312 2235 2235 2235 4426 SBE bad bad bad bad bad SBE 7/15 7/15 Pump 2 2494 8345 8345 8345 5105 5105 5105 DO1 3154 1794 1794 1794 1794 1794 1794 DO2 3198 3199 3199 3199 3199 3198 3198 9plus 552 552 552 552 552 552 552 (1-7) 1243 (8-46) Analysis of past voyage conductivity offsets Based on raw scan files and bottle salts IN2016_V02 Voyage title: SOTS: Southern Ocean Time Series automated moorings for climate and carbon cycle studies southwest of Tasmania Mobilisation: Hobart, Friday-Monday, 11-14 March 2016 Depart: Monday 14th March 1000 Return: Hobart, 0930 Saturday 16 April 2016 Table 1: Lowered CTD configuration CTD Configuration UNIT MODEL SERIAL NUMBER ----------------------------- -------- ------------------------------ CTD#20 SBE9+ V2 552 Primary Temperature SBE 3T 4722 Primary Conductivity SBE4C 3868 Secondary Temperature SBE3T 4522 Secondary Conductivity SBE4C Castl 3168 | casts2-39 2235 | Cast 40 4426 Primary Pump SBE5 2492 Secondary Pump SBE5 2494 Primary Oxygen (AO) SBE43 castl-1794 | From cast2-3154 Secondary Oxygen (Al) SBE43 casts 1-39 3159 | Cast 40-3198 PAR (A2) QCP2300 70111 Altimeter (A3) PA500 5301 Transmissometer (A4) C-Star CST-1421DR Spare (A5) Wetlabs ECO-Chlorophyll (A6) FLBBNTU 3698 (User supplied) Wetlabs ECO - Scattering (A7) FLBBNTU 3698 (User supplied) LADCP Downward looking WHM150 16710 LADCP Upward looking WHM300 16673 Same CTD and sensors as on our voyage and large S offsets are the same. Last cast changed to same C sensor as our voyage 1-46 and offsets agree. This suggests it is not the bus but is due to the calibrations. Bottle/CTD offsets on voyages leading up to V03: IN2016_V01 Voyage title: HEOBI: Heard Earth-Ocean- Biosphere Interactions Mobilisation: Fremantle, 6th-7th January 2016 Depart: Fremantle, 1430 Friday 8th January 2016 Return: Hobart, 0800 Saturday 27th February 2016 Table 1: CTD configuration CTD Configuration The CTD configuration used throughout the voyage is shown in Table 1 UNIT MODEL SERIAL NUMBER ---------------------------- ------------ ---------------------------- CTD#20 V2 SBE9+ 552 Primary Temperature SBE 3T 4722 Primary Conductivity SBE4C 3868 Secondary Temperature SBE3T 4522 Secondary Conductivity SBE4C 3168/2312 (cast 19 onwards) Primary Pump SBE5 2492 Secondary Pump SBE5 2494 (AO) Primary Oxygen SBE43 1794 (Al) Secondary Oxygen SBE43 3159 (A2) PAR Biospherical 70111 (A3) Altimeter PA500 5301 (A4) Transmissometer C-Star CST-1421DR (A5) ORP ORP4CTD ORP4CTD-09/ORP4CTD-03 (A6) Fluorometer-Chlorophyll FLBBRTD 3698 (User supplied) (A7) Fluorometer-Scattering FLBBRTD 3698 (User supplied) Appendix 2 Anthropogenic Trace Gases Rolf Sonnerup, U. Washington, USA Introduction Oceanic distributions of the anthropogenic trace gases, chlorofluorocarbon-11 (CFC- 11), CFC-12 and sulfur hexafluoride (SF6) reveal pathways and time-scales for waters to move from the surface mixed layer into the interior ocean. The 1990s World Ocean Circulation Experiment (WOCE) global survey provided a snapshot of the oceanic uptake of CFCs into the thermoclines of the subtropical gyres, and into intermediate, deep, and abyssal waters. These tracers provide critical measures of how quickly the ocean interacts with the atmosphere, and its anthropogenic changes. This project was part of the international CLIVAR Repeat Hydrography CO2/Tracer Program (RH) effort to measure CFC and SF6 on all of the CLIVAR RH (now GO-SHIP) lines. An important finding of the RH program thus far has been warming of bottom waters throughout the world ocean over the past 20 years. The P15S section is vital to the RH program goals because it crosses the deep western boundary current (DWBC) of the Southwest Pacific, an important abyssal pathway for anthropogenic change, in four separate locations. In 1996 and 2009, P15S measurements sampled the leading edge of the CFCs’ arrival in the abyssal Pacific as far north as 9ºS, in the Samoan Passage. The tracer observations provide an opportunity to use the CFCs to estimate the more difficult to quantify anthropogenic CO2 and heat burdens in the abyssal Southwest Pacific. Measurements 2187 samples were collected and analyzed following Bullister and Wisegarver, 2008. Findings In comparison with the most recent occupation of the P15 line for tracers (2009), we found • Decreases CFCs in the upper 500m reflecting the recent (since 1994) decline in atmospheric CFC levels • At low latitudes (north of 35°S) deeper penetration of CFCs by ~ 200m • Significant increases in the abyss, reflecting the arrival of and increases in the anthropogenic influence on the abyssal Southwest Pacific. For example CFC-12 increased o from 0.075 to 0.12 and 0.075 to 0.14 pmol kg-1 at DWBC crossings to the North and South of Chatham rise o from 0.019 to 0.030 pmol kg-1 in the DWBC’s transit through the Samoan Passage (9°S) The abyssal CFC plume (defined as detectable values in excess of 0.005 pmol kg-1) had shoaled from 4000m in 1996 to 3400m in 2009 to 3000 m in 2016 at 30°S. Farther to the North, the abyssal plume had not shoaled significantly since 2009. Both CFCs were easily detectable at the seafloor over the full extent of the section from 66°S to the equator. The mid-depth (1000-3000m) location where CFC-free waters are found had not moved significantly since 2009. However, as a consequence of the shoaling abyssal plume, and deepening penetration through the thermocline, the total volume of CFC free waters in this region was decreasing. In the locations where CFC12 was not detectable (North of 35S, 1500-35000m typically) we detected a bottle blank on order (preliminarily) of 0.005 pmol kg-1 for CFC-11. The reported CFC-11 values were not corrected for this possible offset. Bottle blanks of zero for SF6, CFC-12, and CCl4 were estimated from niskin samples in this region. Appendix 3 Total Dissolved Inorganic Carbon and Total Alkalinity PI: Dr Bronte Tilbrook, CSIRO Oceans and Atmosphere, and Antarctic Climate and Ecosystems Co- operative Research Centre, Hobart, Tasmania Samples were analysed for total dissolved inorganic carbon dioxide and total alkalinity following techniques developed for measurements in ocean waters on WOCE/CLIVAR sections. Certified reference materials from the Scripps Institution of Oceanography are analysed to determine the accuracy and precision of the measurements. Detailed analytical procedures are provided in Dickson et al (2007). Water sampling Stations sampled for total dissolved inorganic carbon and total alkalinity are shown in Figure 1 and listed in Table 1. For each sample, water was siphoned from a 10L Niskin bottle into 250 ml glass bottles using silicone tubing. The bottles were rinsed three times with water from the Niskin bottle and the seawater sample was then overflowed by about one half of the bottle volume. Each bottle had about a 5ml head space, and 100 microlitres of a saturated solution of mercuric chloride was added prior to sealing the samples using air-tight screw caps. Samples were sealed within one minute of collection. An additional 100 samples were collected using the same method from the ships underway seawater line while the ship was in transit to and from the P15S section. Samples were analysed onboard within 1- 3 days of collection. Figure 1: Carbon water sampling sites (blue dots) for section P15S with some CTD station numbers shown. Total dissolved inorganic carbon: Total dissolved carbon dioxide (TCO2) was analysed using a SOMMA system and 5011 UIC coulometer (Johnson et al., 1993 and Dickson et al.,2007). The SOMMA loads seawater from a sample bottle into a calibrated pipette (21.8ml) that is thermostated to 20°C. The sample in the pipette is dispensed into a stripping chamber to which 1 ml of a 10% (v/v) solution of phosphoric acid has been added. High purity nitrogen carrier gas (>99.995%) is bubbled through the water to extract the CO2 from the sample. The CO2 in the carrier gas stream flows into the cathode compartment of a coulometer cell where it is quantitatively trapped in an ethanolamine solution. The absorbed CO2 reacts to form hydroxyethylcarbamic acid, causing a change in the colour of the cell solution due to the presence of a thymolphthalein pH indicator in the solution. Base is generated at the cell cathode, until the solution colour returns to its starting point. About 36 samples are analysed before a new coulometer cell and solution are required. This provides enough capacity for a whole station with duplicates, and certified reference material. The efficiency of the coulometric method is determined by injecting known amounts of pure CO2 (>99.99%) at the beginning of each new cell. After the calibration of the SOMMA is complete, test seawater samples are analysed followed by certified reference material from the Scripps Institution of Oceanography. The SOMMA system also loads sample into a Seabird conductivity cell, which is used along with a temperature to determine the salinity of the sample. Concentrations are in units of micromol kg-1. For legs 1 and 2, a total of 2625 water samples were analysed for TCO2 (Figure 2), with an additional 269 duplicate samples analysed from shallow, mid-depth and deep samples to cover the range of TCO2 values through the water column. Certified Reference Material from Scripps Institution of Oceanography (Batch 363) was analysed at the beginning and end of the coulometer cells. Over a typical cell, the measurements of reference material drifted by 1-2 micromol kg-1. The average offset for each cell was used to correct the final TCO2 values of the samples. The initial analysis of duplicate samples gave an average absolute difference of 1.71 +- 1.24 micromol kg-1 (s.d., n=269) indicating a precision of better than 2 micromol kg-1. Total alkalinity: Automated open-cell potentiometric titrations were used to measure total alkalinity (TA) (Dickson et al, 2007). Two systems were operated side by side, with Tiamo software used to control the titrations. Each titration was performed on a 100ml seawater sample measured using an Metrohm Dosino 800 burette and a 5ml burette on a Metrohm Titrando 904 was used to deliver acid titrant. The delivery volumes for the Titrando and Dosino burettes were calibrated in the laboratory prior to cruise. Metrohm combination pH electrodes were used to track the progress of the titrations. Refrigerated water baths were used to keep the acid titrant and sample at a constant temperature of 20.5C for each analysis. For a titration, the sample is first acidified to a pH of about 3.6 using 0.1N HCl titrant, which contains 0.6 mol Kg-1 sodium chloride to match the ionic strength of seawater. After the initial addition of acid, the acidified seawater is stirred for 10 minutes to remove dissolved CO2 from the sample. Smaller aliquots of titrant are then added and acid volume and electrode millivolt readings is recorded by the Tiamo software until a pH of about 2.9 is reached. A non-linear fitting routine similar to Johansson and Wedborg (1982) and Dickson et al. (2007) was used to calculate TA. The routine used was compared to a calculated result for data published in Dickson et al (2007) and both methods agree within 0.01%. The performance of the titration systems was monitored using certified seawater reference material from the Scripps Institution of Oceanography (Batch 363), and by using duplicate water samples collected from the CTD casts. The duplicate water samples were collected from surface, mid-depth and deep water samples to cover the range of total alkalinity values for the water column. There was about a 6 micromol kg-1 offset between the measured and certified reference material values for TA due to the acid titrant having a slightly different concentration than originally assigned. Evaporation of acid titrant was also a source of a small drift, and the titrant was regularly replaced with new titrant that prepared prior to the cruise and stored in sealed borosilicate glass bottles. The average offset between the measured and certified reference material values were used to correct the TA for samples from each station. For the section, 2628 seawater samples were analysed (Figure 3), plus 224 duplicate samples. The analysis of duplicate samples for both titration systems showed average absolute differences of 0.90 +- 0.90 micromol kg-1 (s.d., n=119) and 0.97 +- 1.17 mircomol kg-1 (s.d. n=106), indicating a precision of better than +-1 micromol kg-1. Figure 2: Preliminary total dissolved inorganic carbon (micromole kg-1) measurements along the P15S section, Apr-Jun 2016. Figure 3: Preliminary total alkalinity (micromole kg-1) measurements along the P15S section, Apr-Jun 2016. Table 1: Station/CTD numbers (STNNBR), locations and numbers of TCO2 and TA samples. STN DATE TIME DEPTH SAMPLE NBR yyyymmdd hhmm LATITUDE LONGITUDE db NUMBER --- -------- ---- -------- --------- ----- ------ 2 20160504 0844 -66.332 -170.008 3277 36 3 20160505 0320 -65.662 -170.032 3297 32 4 20160505 1320 -64.995 -170.016 2836 31 5 20160505 2145 -64.502 -170.004 2348 2 6 20160506 0501 -63.990 -170.042 2807 31 8 20160508 0141 -63.001 -170.032 3046 33 9 20160508 0650 -62.499 -169.992 2539 2 11 20160508 1535 -62.003 -170.004 3360 33 12 20160508 2149 -61.492 -169.997 3470 2 13 20160509 1631 -61.005 -170.004 4483 33 14 20160509 2335 -60.502 -169.991 3951 5 15 20160511 1151 -60.000 -170.005 3905 35 17 20160512 2000 -58.994 -169.998 4763 30 19 20160513 1219 -58.001 -170.010 4432 34 20 20160513 1911 -57.504 -170.006 5019 36 21 20160514 1414 -57.002 -169.998 5078 33 22 20160514 0926 -56.498 -170.009 5090 2 23 20160514 2122 -56.002 -169.008 5121 36 24 20160515 0441 -55.514 -170.011 4833 2 25 20160515 1108 -54.996 -170.002 4843 30 26 20160515 2000 -54.500 -170.003 4831 10 27 20160516 0249 -53.996 -169.985 5142 30 28 20160516 0954 -53.501 -169.991 5226 10 29 20160516 1637 -53.004 -170.011 5220 30 30 20160517 0016 -52.505 -170.010 5161 10 31 20160517 0755 -52.002 -170.078 4913 30 32 20160517 1436 -51.492 -170.016 4732 10 33 20160517 2141 -51.002 -170.010 5248 32 34 20160518 0420 -51.497 -169.996 5052 10 35 20160518 1137 -50.006 -169.993 5384 33 36 20160518 1915 -49.504 -170.017 5220 10 37 20160519 0215 -48.995 -170.004 5262 30 38 20160519 0915 -48.502 -170.000 5298 10 39 20160519 1559 -47.995 -169.993 5310 32 40 20160519 2338 -47.503 -169.989 5379 10 41 20160520 0649 -47.109 -170.466 5412 32 42 20160520 1348 -46.719 -170.911 5296 10 43 20160521 0116 -46.326 -171.376 5100 32 44 20160522 0021 -45.176 -172.736 4665 32 45 20160522 1003 -44.835 -173.141 3830 31 46 20160522 1639 -44.525 -173.502 3414 28 47 20160522 2335 -44.328 -173.746 3102 15 48 20160523 0620 -44.156 -173.938 1892 26 49 20160523 1542 -42.931 -174.785 1057 16 50 20160523 1819 -42.746 -174.653 1584 23 STN DATE TIME DEPTH SAMPLE NBR yyyymmdd hhmm LATITUDE LONGITUDE db NUMBER --- -------- ---- -------- --------- ----- ------ 51 20160528 1614 -42.400 -174.410 2666 21 52 20160528 2129 -42.167 -174.250 2866 11 53 20160529 0310 -41.717 -173.949 3116 24 54 20160529 0920 -41.273 -173.637 3292 8 55 20160529 1603 -40.832 -173.332 4178 29 56 20160529 2203 -40.392 -173.024 4592 9 57 20160530 0447 -39.958 -173.706 4739 30 58 20160530 1214 -39.511 -172.414 4776 8 59 20160530 2033 -39.068 -172.117 4861 30 60 20160531 0340 -38.628 -171.808 4929 8 61 20160531 1054 -38.187 -171.501 4945 32 62 20160531 1739 -37.757 -171.201 5028 8 63 20160531 0046 -37.307 -170.893 5146 8 64 20160601 0745 -36.871 -170.606 5303 30 65 20160601 1500 -36.450 -170.294 5087 9 66 20160601 2152 -36.002 -170.002 5084 31 67 20160602 0711 -35.680 -170.007 4372 8 68 20160602 1005 -35.337 -170.000 4909 30 69 20160602 1714 -35.014 -169.995 5264 8 70 20160602 2356 -34.505 -170.006 5505 29 71 20160603 0655 -34.012 -169.999 5547 4 72 20160603 1409 -33.501 -170.000 5446 28 73 20160603 2112 -33.000 -170.006 5591 4 74 20160604 0425 -32.500 -169.997 5572 28 75 20160604 1227 -32.002 -169.995 5700 4 76 20160604 1944 -31.499 -169.994 5553 28 77 20160605 0223 -31.023 -169.998 5630 4 78 20160605 0936 -30.512 -169.996 5556 32 79 20160605 1640 -29.999 -169.993 5437 4 80 20160605 2353 -29.501 -170.000 5226 29 81 20160606 0653 -29.006 -169.995 5605 4 82 20160606 1409 -28.503 -169.999 5454 28 83 20160607 1526 -27.984 -169.991 5264 2 84 20160608 1024 -27.272 -169.998 5464 30 85 20160608 1910 -26.495 -169.996 5637 8 86 20160609 0251 -26.000 -169.993 5607 30 87 20160609 1031 -25.509 -169.998 5836 5 88 20160609 1806 -24.999 -170.002 5653 30 89 20160610 0142 -24.501 -170.001 5670 7 90 20160610 0920 -24.000 -170.001 5689 30 91 20160610 1652 -23.505 -169.996 5676 8 92 20160611 0026 -22.999 -169.996 5701 29 93 20160611 0802 -22.501 -170.000 5663 7 94 20160611 1530 -22.002 -170.000 5636 32 95 20160611 2253 -21.503 -169.999 5430 7 96 20160612 0552 -20.998 -169.999 5482 30 97 20160612 1247 -20.503 -169.999 5675 8 98 20160612 2014 -20.000 -170.002 5341 30 99 20160613 0303 -19.498 -170.003 4915 7 100 20160613 0933 -19.004 -170.058 2989 24 101 20160613 1503 -18.503 -170.002 5269 12 STN DATE TIME DEPTH SAMPLE NBR yyyymmdd hhmm LATITUDE LONGITUDE db NUMBER --- -------- ---- -------- --------- ----- ------ 102 20160613 2139 -18.001 -170.000 4919 30 103 20160614 0652 -17.499 -170.001 5037 9 104 20160614 1319 -17.003 -170.002 5005 30 105 20160614 1949 -16.504 -170.000 5226 8 106 20160615 0210 -16.003 -170.001 5150 28 107 20160615 0854 -15.498 -170.001 5095 7 108 20160615 1532 -15.005 -170.000 4826 30 109 20160615 2052 -14.666 -169.999 3330 7 110 20160616 0140 -14.282 -169.998 3546 23 111 20160616 0643 -13.972 -169.999 2972 6 112 20160616 1114 -13.819 -169.999 4338 23 113 20160616 1618 -13.504 -170.002 4888 7 114 20160616 2254 -13.000 -169.999 4980 29 115 20160616 0522 -12.499 -169.999 5012 7 116 20160617 1145 -11.998 -170.003 5097 25 117 20160617 1825 -11.496 -169.999 5069 7 118 20160618 0037 -11.001 -170.000 5135 24 119 20160618 0722 -10.500 -169.999 4878 7 120 20160618 1433 -9.925 -169.629 5227 24 121 20160618 2241 -9.499 -168.998 5357 18 122 20160619 0543 -8.997 -168.875 4891 19 123 20160619 1209 -8.495 -168.749 5182 18 124 20160619 1858 -8.001 -168.616 5212 24 125 20160620 0121 -7.501 -168.751 5287 20 126 20160620 0806 -7.000 -168.751 5676 23 127 20160620 1456 -6.502 -168.749 5553 8 128 20160620 2139 -6.000 -168.751 5679 29 129 20160621 0434 -5.502 -168.750 5476 8 130 20160621 1117 -5.000 -168.750 5583 28 131 20160621 1750 -4.501 -168.750 5555 8 132 20160622 0021 -4.001 -168.751 5178 28 133 20160622 0706 -3.502 -168.750 5023 8 134 20160622 1338 -3.000 -168.751 5388 30 135 20160622 2010 -2.499 -168.750 5346 8 136 20160623 0235 -2.001 -168.750 3413 24 137 20160623 0809 -1.501 -168.749 5926 12 138 20160623 1514 -1.001 -168.750 5803 28 139 20160623 2208 -0.501 -168.750 5512 8 140 20160624 0455 -0.002 -168.750 5628 29 Radiocarbon in total dissolved inorganic carbon: PIs: Dr Ann McNichol, Woods Hole Oceanographic Institution, Massachusetts, USA Dr Robert Key, Princeton University, New Jersey, USA A total of 600 samples were collected for analysis of 14C. Seawater samples were collected about every 4 to 8 CTD stations (Table 2) using a combination of shallow sampling (upper 2000m) and sampling through the entire water column. The samples were collected in cleaned one liter ground- glass stoppered, borosilicate glass bottles. Silicon tubing attached to Niskin bottle spigots was used to fill the bottles. Each bottle was first filled about 30% as a rinse, followed by filling and overflowing the bottle by about 50%. Samples were preserved by adding 100 microlitres of a saturated mercuric chloride solution. The ground glass necks of the sample bottles were dried and Apiezon grease applied to the stopper before sealing. Samples will be analysed using an accelerator mass spectrometer at Woods Hole Oceanographic Institution. Table 2: Station/CTD numbers (STNNBR), locations and numbers of radiocarbon samples. STNNBR DATE TIME LATITUDE LONGITUDE DEPTH 14C yyyymmdd hhmm db samples ------ -------- ---- -------- --------- ----- ------- 3 20160505 0320 -65.662 -170.032 3297 32 6 20160506 0501 -63.990 -170.042 2807 32 13 20160509 1631 -61.005 -170.004 4483 32 21 20160514 1414 -57.002 -169.998 5078 32 29 20160516 1637 -53.004 -170.011 5220 32 35 20160518 1137 -50.006 -169.993 5384 32 41 20160520 0649 -47.109 -170.466 5412 32 45 20160522 1003 -44.835 -173.141 3830 31 51 20160528 1614 -42.400 -174.410 2666 16 55 20160529 1603 -40.832 -173.332 4178 16 61 20160531 1054 -38.187 -171.501 4945 32 66 20160601 2152 -36.002 -170.002 5084 16 72 20160603 1409 -33.501 -170.000 5446 16 78 20160605 0936 -30.512 -169.996 5556 32 86 20160609 0251 -26.000 -169.993 5607 16 94 20160611 1530 -22.002 -170.000 5636 32 100 20160613 0933 -19.004 -170.058 2989 16 106 20160615 0210 -16.003 -170.001 5150 16 112 20160616 1114 -13.819 -169.999 4338 23 118 20160618 0037 -11.001 -170.000 5135 16 121 20160618 2241 -9.499 -168.998 5357 18 124 20160619 1858 -8.001 -168.616 5212 23 130 20160621 1117 -5.000 -168.750 5583 16 134 20160622 1338 -3.000 -168.751 5388 16 140 20160624 0455 -0.002 -168.750 5628 25 pH and total alkalinity PI: Professor Andrew Dickson, Scripps Institution of Oceanography Samples for calibration of sensors on SOCCOM floats were collected from Niskin bottles in the upper 2000m of the water column. Floats were deployed as the ship was leaving the CTD station and just after completion of the CTD cast. The water samples were collected in pre-cleaned glass-stoppered borosilicate bottles, the same as for radiocarbon samples. Each bottle was first filled about 30% as a rinse, followed by filling and overflowing the bottle by about 50%. Samples were preserved by adding 100 microlitres of a saturated mercuric chloride solution. Apiezon grease was applied to the ground glass stoppers and the bottles sealed. Samples will be analysed at Scripps Institution of Oceanography using spectrophotometry (pH) and open cell potentiometric titration (total alkalinity), as described in Dickson et al (2007). Table 3: Station/CTD numbers (STNNBR), locations and numbers of samples for pH and TA analyses. STNNBR DATE TIME LATITUDE LONGITUDE DEPTH NUMBER yyyymmdd hhmm db SAMPLES ------ -------- ---- -------- --------- ----- ------- 3 20160505 0320 -65.662 -170.032 3297 28 6 20160506 0501 -63.990 -170.042 2807 29 11 20160508 1535 -62.003 -170.004 3360 27 15 20160511 1151 -60.000 -170.005 3905 27 19 20160513 1219 -58.001 -170.010 4432 23 25 20160515 1108 -54.996 -170.002 4843 24 31 20160517 0755 -52.002 -170.078 4913 24 35 20160518 1137 -50.006 -169.993 5384 24 39 20160519 1559 -47.995 -169.993 5310 24 43 20160521 0116 -46.326 -171.376 5100 23 57 20160530 0447 -39.958 -173.706 4739 25 61 20160531 1054 -38.187 -171.501 4945 24 Dissolved Calcium and Magnesium PI: Professor Stephen Eggins, Australian National University, Canberra, ACT Duplicate samples were collected from 10 depths (approx. 20, 50, 100, 150, 200, 300, 500, 750, 1000 and 2000m) at each of the stations listed in Table 3. Seawater was collected into 30m plastic luer-lok syringes. The syringes were rinsed three times with sample, filled, and a 0.22 micron PES membrane filter attached to the syringe. The filter was flushed with about 10ml of seawater and 5ml polypropylene vials were rinsed three times with filtered water. The vials were then filled and capped and stored at room temperature in sealed plastic bags and returned to Australia for analysis by isotope dilution using a multi collector inductively couple plasma mass spectrometer. Table 4: Station/CTD numbers (STNNBR), locations and numbers of of calcium and magnesium water column samples. STNNBR DATE TIME LATITUDE LONGITUDE DEPTH NUMBER yyyymmdd hhmm db SAMPLES ------ -------- ---- -------- --------- ----- ------- 5 20160505 2145 -64.502 -170.004 2348 10 12 20160508 2149 -61.492 -169.997 3470 10 17 20160512 2000 -58.994 -169.998 4763 10 23 20160514 2122 -56.002 -169.008 5121 10 30 20160517 0016 -52.505 -170.010 5161 10 37 20160519 0215 -48.995 -170.004 5262 10 40 20160519 2338 -47.503 -169.989 5379 10 43 20160521 0116 -46.326 -171.376 5100 10 45 20160522 1003 -44.835 -173.141 3830 10 53 20160529 0310 -41.717 -173.949 3116 10 59 20160530 2033 -39.068 -172.117 4861 10 64 20160601 0745 -36.871 -170.606 5303 10 72 20160603 1409 -33.501 -170.000 5446 10 78 20160605 0936 -30.512 -169.996 5556 10 82 20160606 1409 -28.503 -169.999 5454 10 86 20160609 0251 -26.000 -169.993 5607 10 92 20160611 0026 -22.999 -169.996 5701 10 98 20160612 2014 -20.000 -170.002 5341 10 104 20160614 1319 -17.003 -170.002 5005 10 110 20160616 0140 -14.282 -169.998 3546 10 116 20160617 1145 -11.998 -170.003 5097 10 122 20160619 0543 -8.997 -168.875 4891 9 128 20160620 2139 -6.000 -168.751 5679 10 134 20160622 1338 -3.000 -168.751 5388 10 140 20160624 0455 -0.002 -168.750 5628 9 References Dickson, A.G., Sabine, C.L and Christian, J.R. (Eds) (2007). Guide to Best Practices for Ocean CO2 Measurements. PICES Special Publication 3. Johansson, O. and Wedborg, M. (1982) Oceanologica Acta, 5, pp 209–210. Johnson, K.M., Wills, K.D., Butler, D.B., Johnson, W.K., and Wong, C.S. (1993). Coulometric total carbon dioxide analysis for marine studies: Maximizing the performance of an automated continuous gas extraction system and coulometric detector. Marine Chemistry, 44, pp 167–189. APPENDIX 4 TEMPERATURE MICROSTRUCTURE PI Jonathon Nash, U. Oregon Report by Esmee Van Wijk, CSIRO Chipods are instruments that measure high frequency temperature and instrument motion at 100 Hz. The data is used to estimate mixing rates; the dissipation rate of small-scale temperature variance and the turbulent diffusivity of heat. There were 4 instrument packages installed on the 36 bottle rosette; 2 upward looking and 2 downward looking chipods. These were configured so that the upward thermistors were raised above the rosette frame near the outer rim, and on a stalk to ensure a clear view of the water passing over the package. The downward thermistors are more subject to contamination by deflection of the fluid around the instrument as they are located above the bottom limit of the rosette frame but with as clear a view of the water column as possible. The instruments are powered by 2 Lithium D-cell batteries, are internally recording and are pressure rated to 6000db. Even though the chipods record all data internally onto memory cards, the data was downloaded every two days. It would take 25-40 mins to download each instrument (if everything was working perfectly) and there was only just enough time to do this in the time we needed to turn around the rosette and get it back into the water. It required one person to download the chipods, which was a significant diversion of time away from the core work of the sampling team. It was also necessary to then back up the data from the mixing computer onto a hard drive and then onto the server. Generating check plots to make sure that the instruments were working correctly took additional time. All of this was only possible because we had one extra volunteer from another program who was able to assist with the CTD sampling. For future cruises, the chipod team should send their own technician or ensure that these are internally recording with no downloading required as this extra work had not been considered when planning the staffing for this voyage. Problems: 1. Often the downloading would hang on a particular file and the mini host logger would not respond. You would then need to work out which file was causing the problem and then download all of the other files around this one individually. No matter how many times you would try to download the affected file, it would continually crash. 2. Occasionally one of the instruments would get stuck in a loop where it would run strange characters across the data screen. The only way to fix this would be to disconnect the USB cable and the sensor cable (difficult with a rosette that is being sampled and with the pressure case right inside the internals the only way this be done was by taking bottles off the CTD after sampling had been completed, which then delayed the CTD for the next station. 3. Once when having the above problem I was not able to communicate with the instrument after three separate tries of disconnecting and reconnecting. I left this instrument and downloaded the others and then disconnected and reconnected once again and it worked on the fourth time. This kind of troubleshooting can take up a lot of extra time. 4. I needed to replace four thermistors during Leg 2 of the voyage, plus two pressure cases and loggers, as well as a sensor cable due. 5. After cast 83 where the CTD hit bottom, the two upward thermistors were sheared off and the upward stalk had collapsed. I replaced the thermistors and re-attached the upward stalk to the frame - this was not exactly at the same height as it had been before. 6. Something to emphasise (and that would have been handy to know from the start) is that if you are having problems it is worth forcing the instrument to start logging by typing in the ‘sl’ (start logging) command, waiting for a few seconds and then hitting the space bar to see if bytes are being written to file. If this is the last thing you do before disconnecting the USB it would often work. APPENDIX 5 XBT CALIBRATION PROJECTS Ann Thresher and Rebecca Cowley XBTs measure upper ocean temperatures using a thermistor, and a calculated depth based on an assumed fall rate and time. It has been shown that this fall rate has changed over the history of the XBT resulting in a bias of the data in the archives. In order to compute the real fall rate for XBTs of various vintages, it is necessary to drop them coincident with a CTD. An approximation of the correct fall rate is then calculated using the upper ocean thermal structure, matching features and generating new fall-rate coefficients. CSIRO has led this effort with Rebecca Cowley conducting these experiments whenever possible in order to completely characterize these changes through time. XBTs of various ages were loaded onto Investigator with the aim of dropping them with CTDs during IN2016-V03. Because of the latitude range covered, this also gives us information about fall rates in water of different temperatures (which is also suspected of affecting XBT speed). Two systems, the Ship’s and the CSIRO Wireless systems, were used to simultaneously drop XBTs as a CTD was deployed. The goal was to complete as many XBTs as possible before the CTD dropped below their maximum depth. In most cases, we managed to drop 4-6 XBTs per system before the CTD reached 700-800db, providing good data for the comparison. More were dropped if they were shorter range XBTs or failed early. During leg1, we dropped a total of 112 XBTs (62 on the CSIRO wireless system and 59 on the ship’s system). During leg 2, we dropped a total of 88 XBTS using the Ship’s system and 86 using the CSIRO Wireless system. A few of these were dropped for training purposes and will not be useful for analysis. For the entire voyage, 32 CTDs were used at latitudes ranging from 66o S to 6o 30 S. The table below shows the CTD stations vs XBT deployments. Problems encountered were, for the most part, minor. Some boxes of XBTs had more failures (early wire break, no traces) than others. T-5 XBTs (rated to 1800db) were found to be useless and so were abandoned though we may try to collect some data when over shallower water. Given that these were manufactured in 1990, their failure is not surprising. The wireless system sometimes had communication problems with the computer and both the box and the computer had to be rebooted several times during the tests. The Ship system had no issues, though it appeared to renumber at least one drop. Some XBTs were misidentified early in the trip and these can hopefully be corrected. Others were dropped from the wrong system and so the serial numbers, batch dates, etc will need to be adjusted. All notes are in the log sheets. All data and the summary log sheets can be found on the science drive in the XBT folder. Latitude CTD # Ship System CSIRO Wireless System -------------- ---------- ---------------- ------------------------ 43°32’S to NA. 12 – T5 for hit T5 for hit 43°41’S 26/04/2016 bottom testing 12 – bottom testing 55°30’S to NA. 12 – T5 for hit 12 – T5 for hit 55°36’S 29/04/2016 bottom testing bottom testing 66°30’S 2 3 – DB 4 – DB 62°30’S 9 4 – DB 4 – DB 62°S 10 3 – DB 3 – DB 62°S 11 3 – DB 3 – DB 61°30’S 12 3 – DB 1 – DB 60°S 15 3 – DB 2 – DB 59°S 17 3 – DB 3 – DB 58°30’S 18 3 – DB 3 – DB 58°S 19 3 – DB 3 – DB 57°S 21 3 – DB 3 – DB 56°30’S 22 3 – DB 3 – DB 55°30’S 24 4 – DB 3 – DB ---------------------------------------------------------------------- Totals Leg 1: 12 62 59 36°S 66 3 – T-5 – 3 – T-5 – training/testing training/testing 35°40’S 67 3 – DB 3 – DB mis-id’d as T-5s 35°20’S 68 4 – DB 4 – DB 35°S 69 4 – DB 4 – DB 34°30’S 70 4 – DB 4 – DB 34°S 71 4 – DB 4 – DB 13°30’S 113 4 – T-4 4 – T-4 13°S 114 4 – T-4 4 – T-4 12°30’S 115 6 – T-4 5 – T-4 12°S 116 5 – T-4 5 – T-4 11°30’S 117 5 – T-4 serial 5 – T-4 serial #s switched #s switched with wireless with ship 11°S 118 5 – T-4 5 – T-4 10°30’S 119 6 – T-4 5 – T-4 Bad box 9°55’S 120 7 – T-4 7 – T-4 9°S 122 4 – DB batch 4 – DB batch date wrong date wrong 8°30’S 123 4 – DB 4 – DB 8°S 124 4 – DB 4 – DB 7°30’S 125 4 – DB 4 – DB 7°S 126 4 – DB 4 – DB 6°30’S 127 4 – DB 4 – DB ---------------------------------------------------------------------- Totals Leg 2: 20 88 86 ====================================================================== Overall totals 32 150 145 APPENDIX 6 NITROGEN PROCESSES, BUDGETS, PLANKTON AND BACTERIAL PHYLOGENY ALONG THE P15 GO-SHIP LINE: FROM THE ICE EDGE UP TO THE EQUATOR. by Eric Raes, U.W.A Introduction The supply of biologically-available nitrogen (N) can be a bottleneck in the efficiency of the biological oceanic carbon pump. Reactive nitrogen (Nr) in the open ocean regulates primary productivity and a cascade of associated carbon-nitrogen coupled transformations mediated by both eukaryotic and prokaryotic microorganisms (Ward et al., 2013). An understanding of potential alterations at the base of the food chain particulary reductions in planktonic biomass is essential, as a decline (Boyce et al., 2010) or communty shift (Montes-Hugo et al., 2009) in primary productivity will impact ecosystem services, such as O2 production, carbon sequestration, biogeochemical cycling and fisheries (Lehodey et al., 2010, Hollowed et al., 2013, Séférian et al., 2014). Rationale While we are getting better insights in the microbial community and their taxonomy, uptake and rate measurements of N and C are still very sparse throughout the world oceans and are a high priority to accurately quantify C, N cycles and the associated primary productivity. Our research is motivated by the need to further enhance our fundamental knowledge of the N-cycle and the different biogeochemical and physical parameters that control primary productivity. Aims The main aim of this study was to contribute knowledge of important fluxes of key elements (nitrogen and carbon) in this largely unstudied region (from a biological oceanography point of view). In order to tackle this aim we investigated the relationships between dissolved inorganic nutrients, phytoplankton pigment composition, microbial community structures, dinitrogen fixation rates, NO3- and NH4+ assimilation rates, and nitrification rates along the p15 GO-SHIP line from 66˚S to 0˚S. Specifically our objectives were: 1. To test whether N2 fixation is a process facilitating planktonic CO2 fixation along the whole p15 line. 2. To unravel the biogeochemical components of the N-cycle that control primary productivity and N regeneration. 3. To link primary productivity and N transformation processes to functional phylogenetic groups of marine protists and microbes (archaea and bacteria) involved in the C and N cycle through targeted molecular approaches which elucidate community structure and activity (functional gene expression). Outcomes and benefits The data arising from this study will be a major source of new information on N2 fixation rates and the controls of the N-cycle contributing to regional primary productivity in the different water masses along the p15 GO-SHIP line. A basic understanding of the biological and physical oceanographic parameters that control primary productivity in the world’s oceans is crucial to maintain clear conservation strategies of the natural marine ecology (Burrows et al., 2011). These data will provide new insights that will hopefully allow us to better understand, predict and manage the impacts of human induced climate changes. Methods Samples were taken for • Picoplankton analysis, using flowcytometry back on land a. collaborations with University of Technology Sydney (UTS) and Macquarie University • Chlorophyll a and phytoplankton pigment analysis, using HPLC back on land a. collaborations with CSIRO, University of Tasmania (UTAS) and Alfred Wegner Institute (AWI) • DNA analyses using targeted functional gene expression analyses and high- throughput sequencing back on land a. collaborations with CSIRO and AWI • Primary productivity, following isotopic tracer incorporation into the particulated matter, using stable isotopes 13C, aboard using incubation bins a. collaborations with AWI • Dissolved inorganic nitrogen uptake measurements, using standard 15N protocols, aboard using incubation bins a. collaborations with AWI • N2-fixation rates, using 15N gas as an injected tracer to measure fixation rates, aboard using incubation bins a. collaborations with Southern Cross University and AWI • Nitrification rates a. collaborations with AWI Note: a. We have collected the first dissolved inorganic nitrogen assimilation and fixation rates along the entire p15 Line. These data will fill in a major knowledge gap in regards to N and C cycling in the world open oceans. b. We have collected the first high resolution (every half a degree and depth stratified) data set for DNA analysis stretching from the ice edge up to the equator. c. All these samples will be analysed back on land so unfortunately we don’t have any preliminary results. IN2016_V03 Genomics team: Nicole Hellessey, Swan Sow, Gaby Paniagua Cabarrus, Bernhard Tschitschko and Eric Raes References: Boyce, D. G., Lewis, M. R. & Worm, B. 2010. Global phytoplankton decline over the past century. Nature, 466, 591-596. Burrows, M. T., Schoeman, D. S., Buckley, L. B., Moore, P., Poloczanska, E. S., Brander, K. M., Brown, C., Bruno, J. F., Duarte, C. M., Halpern, B. S., Holding, J., Kappel, C. V., Kiessling, W., O’Connor, M. I., Pandolfi, J. M., Parmesan, C., Schwing, F. B., Sydeman, W. J. & Richardson, A. J. 2011. The Pace of Shifting Climate in Marine and Terrestrial Ecosystems. Science, 334, 652-655. Hollowed, A. B., Barange, M., Beamish, R. J., Brander, K., Cochrane, K., Drinkwater, K., Foreman, M. G., Hare, J. A., Holt, J. & Ito, S.-i. 2013. Projected impacts of climate change on marine fish and fisheries. ICES Journal of Marine Science: Journal du Conseil, 70, 1023-1037. Lehodey, P., Senina, I., Sibert, J., Bopp, L., Calmettes, B., Hampton, J. & Murtugudde, R. 2010. Preliminary forecasts of Pacific bigeye tuna population trends under the A2 IPCC scenario. Progress in Oceanography, 86, 302-315. Montes-Hugo, M., Doney, S. C., Ducklow, H. W., Fraser, W., Martinson, D., Stammerjohn, S. E. & Schofield, O. 2009. Recent changes in phytoplankton communities associated with rapid regional climate change along the western Antarctic Peninsula. Science, 323, 1470-1473. Séférian, R., Bopp, L., Gehlen, M., Swingedouw, D., Mignot, J., Guilyardi, E. & Servonnat, J. 2014. Multiyear predictability of tropical marine productivity. Proceedings of the National Academy of Sciences, 201315855. Ward, B., Voss, M., Bange, H. W., Dippner, J. W., Middelburg, J. J. & Montoya, J. P. 2013. The marine nitrogen cycle: recent discoveries, uncertainties. APPENDIX 7 INERTIAL NAVIGATION SYSTEM TESTS By Tobias Aldridge Device Description: The PHINS (PHotonic Inertial Navigation System) is a device capable of measuring all navigational parameters associated with the motion of a vehicle (e.g. heading, speed, position, and attitude). Designed to be used for applications such as AUV navigation, the PHINS can accept many forms of navigational aiding (e.g. GPS, acoustic, pressure, etc.); however, the unit is also capable of operating in the absence of external aids. The challenge is that the navigational accuracy of PHINS units degrades the longer they operate without said aiding. As the navigational accuracy depends heavily on the initial alignment, which in turn is a function of the forcing around the z-axis, the rate of degradation will also increase as a function of latitude. What measurements, and where? This cruise provided the perfect opportunity to test the behaviour of the PHINS technology at a range of different latitudes, with the aim of quantifying the effect of latitude on the accuracy of heading and position. To this end, the PHINS was operated continuously, with a repeating 12 hour testing regime, for the duration of the voyage. This testing regime included 2 hours of operation with GPS aiding for the calibration phase of the testing, and then 10 hours operation with no aiding, to measure the quality of the positioning. Preliminary findings: A very clear trend of increasing heading accuracy was found with a decreasing latitude, shown in Figure 1. This was expected, as the ability of an INS device to align with North is reduced with increasing latitude. Figure 1: Preliminary results for PHINS standard deviation on heading. One data point per test. The device is considered aligned when the heading standard deviation is below 0.1 degrees In the general operations on board an AUV, the PHINS will be supplemented with a feed from the on board Doppler velocity log (DVL), tracking the velocity of motion over the sea floor. For this configuration, the primary cause of INS position degradation is the difference between PHINS estimated heading and true heading. This will result in a position error of 0.05 – 0.1% of distance travelled. For example, 200 – 400m off after a distance of 400km travelled. As this is a function of heading accuracy, the potential for position error will increase with increasing latitude. For a PHINS without any navigational aiding, the specified position accuracy is 0.6 nautical miles per hour error. It was expected that the position accuracy of the INS would improve with increasing latitude, as the heading uncertainty is reduced; however, preliminary results are showing no clear trend of improving position accuracy. These results are shown in Figure 2. Preliminary results are showing that the primary cause of position error for an unaided PHINS is an incorrect velocity estimation; this source of error is orders of magnitude higher than would be caused by heading uncertainty. Figure 2: Preliminary results for PHINS rate of position 'drift'. One data point per test. PHINS specification for unaided operation is 0.6 nm/hr How will these results be used? These results will inform both AUV deployments at high latitudes in general and future ARC SRI Gateway AUV deployments specifically. This is particularly true for deployments under Antarctic ice sheets, as it is often not possible to employ bottom tracking while exploring the underside of an ice sheet. APPENDIX 8 ATMOSPHERIC CHEMISTRY AND AEROSOLS By Reece Brown This voyage has seen the deployment of several pieces of aerosol instrumentation to investigate the chemical composition, size distribution, optical properties and cloud nucleating properties of marine aerosol over the southern hemisphere. These parameters are important in the quantification of regional contributions of aerosols to radiative forcing, and will help to improve meteorological and climate change models. With a few exceptions, the instrumentation has operated with only minor issues and a wealth of data has been successfully collected. Two mass spectrometer systems were used to investigate the chemical composition of aerosols. Particle composition was analysed through the use of an ACSM, which provides online, high resolution chemical analysis of particles. Early data analysis shows mass concentrations of sulphate, with lower levels of organics, chlorine and ammonium. These results are consistent with the sea spray generated aerosol which are expected to be the primary source of aerosols in the open ocean. There were some periods of very high organic mass concentrations due to non-optimum wind conditions causing the diesel exhaust to blow over the sampling inlet. However, this effect was kept to a minimum due to careful ship directions placement during CTD deployments. A PTRMS system was used to perform analysis on water soluble species including DMS, however further data analysis is required before this data will be understood. Offline PM1 filter and VOC collections systems were also employed to allow for further chemical analysis at a later date. Particle sizing measurements were performed utilizing two scanning mobility particle sizer (SMPS) systems, a NAIS, and an aerodynamic particle sizer (APS). The combination of equipment allowed for real time particle size measurements continuously from 0.5 nanometers up to 20 micrometres. The NAIS was also used to track potential particle formation events, however early analysis has not yielded any conclusive results. Particle concentrations were measured through a condensation particle counter (CPC) and were typically in the range of 200 – 300 particles per cubic centimetre of air when sampling clean ocean air. As a comparison a relatively clean city such as Brisbane will see concentrations ten times this value. Aerosol cloud condensation properties were measured through the use of a cloud condensation nuclei counter (CCNC) and a volatility hygroscopicity tandem differential mobility analyser (VHTDMA). The CCNC concentrations were generally only slightly lower than the CPC readings, indicating that the vast majority of particles measured are potential cloud condensation nuclei. This result is expected as sea salt is very hygroscopic and will readily form cloud droplets given suitable circumstances. The VHTDMA system analysed the volatility and hygroscopicity of particles, which are important parameters in determining if a particle can become a cloud condensation nuclei. The primary issues encountered during the first leg of IN2016_V03 were caused through sea spray entering into the inlet due to high sea swells. During leg two a similar issue was encountered due to the high humidity in the tropical regions causing condensation in the sampling lines. In both cases careful management of instrument setup and water traps, regular dryer maintenance, and clearing of condensation from the lines allowed for meaningful data to be collected despite these setbacks. APPENDIX 9 - HELIUM SAMPLING Stephanie Downes, Antarctic Climate and Ecosystems Co-operative Research Centre, Hobart, Tasmania John Lupton, NOAA/Pacific Marine Environmental Laboratory, Newport, OR, USA Helium is a passive tracer ideal for identifying hydrothermal activity and for tracing deep ocean circulation. However, helium has been sparsely sampled across Southern Ocean voyage transects and never before has it been sampled along the P15S line. On this voyage, 219 duplicate seawater samples were collected along 20 stations (Figure 1, Table 1). At each of the 20 stations, between 8 and 13 depths were sampled, paying particular attention to topographical features in the region to hopefully capture interesting hydrothermal activity close to mid-ocean ridges. Water sampling For each sample, a 24-inch copper tubing (5/8 inch in diameter) was filled with seawater drawn from the 10L Niskin bottles within two hours of the CTD arriving back on the ship. The copper tube was hermetically sealed (crimped) in three places using a hydraulic crimper to produce two 10-inch sealed duplicate samples. Directly after all samples for the station were crimped, the copper tubes were rinsed with fresh water, dried thoroughly, and stored in foam-lined cardboard boxes in fibreglass crates. Other than freezing of the crimper at the first few stations and a productive sea ice season eliminating the first proposed sampling station, all planned helium sampling stations and depths were accounted for. Analysis The helium isotopes will be processed and quality controlled onshore at the NOAA/Pacific Marine Environmental Laboratory (John Lupton). The samples will be processed to separate the dissolve gases from the water, followed by analysis of 3He concentrations, 4He concentrations and 3He/4He ratios using the extracted dissolved gases on a special mass spectrometer. Samples will be made publically available once onshore processing is completed. Figure 1: Helium stations (green) sampled. Also shown are major ocean currents (the Antarctic Circumpolar Current and Ross Gyre to the south), as well as previously inferred and identified hydrothermal activity (blue and yellow) within the vicinity of the P15S transect. Table 1. Station/CTD numbers (STNNBR), locations and numbers of He samples. STNNBR DATE TIME LATITUDE LONGITUDE DEPTH NUMBER yyyymmdd hhmm db SAMPLES ------ -------- ---- -------- --------- ----- ------- 2 20160504 0844 -66.332 -170.008 3277 10 5 20160505 2145 -64.502 -170.004 2348 9 9 20160508 0650 -62.499 -169.992 2539 10 12 20160508 2149 -61.492 -169.997 3470 10 14 20160509 2335 -60.502 -169.991 3951 11 19 20160513 1219 -58.001 -170.010 4432 11 20 20160513 1911 -57.504 -170.006 5019 12 21 20160514 1414 -57.002 -169.998 5078 12 22 20160514 0926 -56.498 -170.009 5090 12 24 20160515 0441 -55.514 -170.011 4833 13 26 20160515 2000 -54.500 -170.003 4831 13 29 20160516 1637 -53.004 -170.011 5220 13 33 20160517 2141 -51.002 -170.010 5248 13 37 20160519 0215 -48.995 -170.004 5262 13 41 20160520 0649 -47.109 -170.466 5412 13 46 20160522 1639 -44.525 -173.502 3414 10 47 20160522 2335 -44.328 -173.746 3102 8 48 20160523 0620 -44.156 -173.938 1892 8 49 20160523 1542 -42.931 -174.785 1057 16 50 20160523 1819 -42.746 -174.653 1584 8 APPENDIX 10 LOWERED ADCP ISSUES Bec Cowley and Bernadette Sloyan, 20 May, 2016 The slave (upward, 300 kHz) and master (downward, 150 kHz ) ADCPs on the CTD package were processed on-board. The processing software (LDEO LADCP) produced a warning error of a large offset in the heading between the upward and downward looking ADCP units. This error will result in incorrect velocity vectors when the data is processed. The raw data files were loaded into RDI propriety software to investigate further the heading error. The tilt, pitch and roll of the instruments was reviewed. During the review there was found to be a time offset between the instruments where one lagged the other in tilt. The time stamps were further investigated and an offset was found between the slave and master time stamps (Figure 1). Figure 1: Difference in time stamps (Slave-Master) for each deployment (numbered). We investigated applying a simple time offset to the raw data and re-processing, but this did not make any difference. A closer look at the heading values from the instruments gave a clear indication of the problem. The Master instrument has a poor heading record that is not consistent in its behaviour. A single example from Cast 7 is shown in figure 2. Figure 2: The upper panel shows the raw heading values for the master and slave, the lower panel the absolute difference between the two. The tilt, pitch and roll for the master look comparable to the slave, but with an offset (Figure 3 and 4). This is the case for most of the stations. We processed the LADCP from the previous section and found the same heading error. Thus we suspect the unit was faulty prior to our voyage. For this voyage we will process the LACDP data using only the slave heading data. Finally, during the voyage beam-4 of the downward looking unit failed. Figure 3. Master and slave pitch and roll from Station 7. Figure 4. Master and slave tilt from station 7. RV INVESTIGATOR HYDROCHEMISTRY DATA PROCESS REPORT Voyage: IN2016_v03 Leg 1/Leg2 Chief Scientist: Bernadette Sloyan/Susan Wijffels Voyage title: Monitoring Ocean Change and Variability along 170°W from the ice edge to the equator Report compiled by: Christine Rees, Peter Hughes, Stephen Tibben, Kelly Brown, Cassie Schwanger & Melissa Miller Contents 1 Itinerary 50 2 Key personnel list 50 3 Summary 51 3.1 Hydrochemistry 51 3.2 Rosette and CTD 51 3.3 Procedure Summary 51 4 Salinity Data Processing 52 4.1 Salinity Parameter Summary 52 4.2 CTD vs Hydro Salinities Plot 53 4.3 Missing or Suspect Salinity Data and Actions taken 53 5 Dissolved Oxygen Data Processing 54 5.1 Dissolved Oxygen Parameter Summary 54 5.2 CTD vs Hydro DO Plot 55 5.3 Dissolved Oxygen thiosulphate normality across voyage 55 5.4 Dissolved Oxygen blank concentration across voyage 55 5.5 Missing or Suspect Dissolved Oxygen Data and Actions taken 55 6 Nutrient Data Processing 56 6.1 Nutrient Parameter Summary 56 6.2 Nutrient calibration and data parameter summary 57 6.3 Accuracy - Reference Material for Nutrient in Seawater (RMNS) Plots 58 6.3.1 Silicate RMNS Plot 59 6.3.2 Phosphate RMNS Plot 59 6.3.3 Nitrate + Nitrite (NOx) RMNS Plot 59 6.3.4 Nitrite RMNS Plot 59 6.4 Analytical Precision 59 6.5 Sampling Precision 60 6.5.1 Silicate Duplicate Plot 60 6.5.2 Phosphate Duplicate Plot 60 6.5.3 Nitrate + Nitrite (NOx) Duplicate Plot 60 6.5.4 Nitrite Duplicate Plot 60 6.5.5 Redfield Ratio Plot (14.0) 60 6.6 Calibration and QC edited data 60 6.7 Investigation of Missing or Flagged Nutrient Data and Actions taken 61 6.8 Temperature & Humidity Change over Nutrient Analyses 63 7 Appendix 63 7.1 Salinity Reference Material 63 7.2 Hypro Flag Key for CSV & NetCDF file 63 7.3 GO-SHIP Specifications 64 7.4 RMNS Values for each CTD 64 7.5 Nutrient Methods 68 8 References 69 1 ITINERARY Depart Leg 1 Date Time Hobart 26 April 0800 Arrive Date Time Wellington (NZ) 26 May 1100 Depart Leg 2 Date Time Wellington (NZ) 27 May 1100 Arrive Date Time Lautoka (Fiji) 30 June 0800 2 KEY PERSONNEL LIST Name Role Organisation --------------------- ---------------------- ------------ Dr. Bernadette Sloyan Chief Scientist Leg 1 CSIRO Dr. Susan Wijffels Chief Scientist Leg 2 CSIRO Don McKenzie Voyage Manager Leg 1 CSIRO Stephen Thomas Voyage Manager Leg 2 CSIRO Peter Hughes Hydrochemist Leg 1 CSIRO Christine Rees Hydrochemist Leg 1 & 2 CSIRO Stephen Tibben Hydrochemist Leg 1 & 2 CSIRO Kelly Brown Hydrochemist Leg 1 & 2 CSIRO Melissa Miller Hydrochemist Leg 1 SCRIPPS Cassie Schwanger Hydrochemist Leg 2 CSIRO 3 SUMMARY All finalized data can be obtained from the CSIRO data centre. RMNS corrected nutrient data will be provided at a later date to the data centre. Dissolved Oxygen data has been corrected for Thiosulfate and blank concentration variation across the voyage (see section 5). Nutrient experimental samples for ammonium were frozen and measured during transit at the end of each voyage leg. 3.1 Hydrochemistry Analysis Sampled Salinity (Guildline Salinometer) 5740 Dissolved Oxygen (automated titration) 4690 CTD 94 UWY Nutrients (AA3) 4705 CTD 94 UWY 245 EXP (NH4) Note: CTD-samples collected from NISKIN bottles on CTD rosette, UWY-underway samples collected from underway seawater intake and EXP-experimental samples. 3.2 Rosette and CTD • 140 CTD stations were sampled with a 36 bottle rosette (12 L), Dep 1 was the test cast to train samplers. However, salinities were analysed from this deployment. • The following deployments failed either due to CTD malfunction or bottles not firing; deployment 7, 10, 14 (only 5 Niskin bottles closed), 16, 18, and 83. • See in2016_v03_HydrochemistryReport.pdf (voyage report) for more details on sample collection. 3.3 Procedure Summary The procedure for data processing is outline in Figure 1. Figure 1: The process above shows the data trail procedure from the initial data generated to output via HyPro for reporting. Nutrients: Data collected in Seal AACE 6.10 software HyPro: .csv & .CHD files (raw data) imported for peak analysis, calculationsand QC HyPro: waterfall and sensor plots compared for anamolies and outlier identification Salinity: Data collected in Osil software Excel file exported from Osil and deployment numbers added to Sample ID field HyPro: Excel file is imported for reporting; water- fall and sensor plots examined for outliers Dissolved Oxygen: Data is collected in SCRIPPS software Oxygen .LST files were directly imported into Hypro HyPro: .LST file is imported for reporting; water- fall and sensor plots examined for outliers 4 SALINITY DATA PROCESSING 4.1 Salinity Parameter Summary Details HyPro Version 4.12 Instrument Guildline Autosal Laboratory Salinometer 8400(B) – SN 71613 Software Osil Methods Hydrochemistry Operations Manual + Quick Reference Manual Accuracy ± 0.001 salinity units Analyst(s) Stephen Tibben Lab Temperature (±0.5°C) 21.0 -24.0°C during analysis. Bath Temperature 24°C Reference Material Osil IAPSO - Batch P157 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 7-8 hrs to reach 22°C before analysis. A duplicate sample from rosette position 2 was used to monitor the temperature of the samples to ensure temperature equilibration had occurred before analysis. Comments Principle investigators chose to use a smaller headspace within the salinity bottles (8 ml, compared with 25 ml recommended by Hydrochemistry team) from deployment 62 onwards. Experimental work during voyage showed no significant difference between salinity bottles with an 8 ml headspace compared to that of a 25 ml headspace. 4.2 CTD vs Hydro Salinities Plot (see pdf) 4.3 Missing or Suspect 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 Bottle Analysis Flag Reason for Flag or Action --- --------- ------ -------- ---- ----------------------------------- 1 26 C26 Salt 69 Sampling error? Training samplers/changed O-rings 1 5 C05 Salt 141 Niskin lid did not close, no sample 1 10 C10 Salt 69 Sampling error? Training 2 31 J32 Salt 69 Very high Niskin frozen 6 31 B31 Salt 69 Very high Niskin frozen 15 17 J17 Salt 133 Waterfall profile out 19 17, 23 Salt 141 Niskin bottles did not fire. 24 7 E07 Salt 141 Niskin bottles did not fire. 24 13 E13 Salt 69 Waterfall profile out 38 all all Salt 0 All samples had less than recommended headspace. 44 20 E21 Salt 141 Niskin Lanyard caught in lid bottle leaking. 47 36 Salt 141 Niskin fired in air. 49 2, 3, 6, Salt 141 Niskins not sampled 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 50 3, 7, 10, Salt 141 Niskins not sampled 12, 14, 16, 18, 20, 22, 24, 26, 29, 32 52 20 H20 Salt 133 Outlier – lanyard was caught on bottle so possible leak 53 17 Salt 141 Niskin end cap didn’t close 55 32 Salt 141 No data 67 25 K25 Salt 133 Waterfall profile out 72 10, 9 H10, H09 Salt 69 Waterfall profile out and also in error plot. 74 09 Salt 141 Niskin leaking did not sample 84 1, 2 Salt 141 Niskins not sampled 90 13 A13 Salt 0 Waterfall profile out 102 15,16,17 A15,A16, Salt 69 Waterfall profile out A17 RP15 was leaking 103 5 J05 Salt 133 Waterfall profile out, noted in sample log niskin rp 5 was warmer temperature than other bottles. 112 33-36 Salt 141 Niskins not sampled 113 10 Salt 141 Niskin not sampled 119 13 Salt 141 Niskin not sampled 124 10, 26 Salt 141 Niskin not sampled 134 11 Salt 141 Niskin not sampled 137 3 J03 Salt 0 Waterfall plot out 138 14 Salt 141 Niskin not sampled 139 14 C14 Salt 0 Waterfall plot out – niskin had just been majorly serviced 140 27 A27 Salt 133 Vertical profile plot out. Niskin Lanyard caught in lid - bottle leaking. Also bad for nutrients. 5 DISSOLVED OXYGEN DATA PROCESSING 5.1 Dissolved Oxygen Parameter Summary Details ---------------------------------------------------------------------------- HyPro Version 4.12 Instrument Automated Photometric Oxygen system Software SCRIPPS Methods SCRIPPS Accuracy 0.01 ml/L + 0.5% Analyst(s) Kelly Brown Lab Temperature (±1°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 ~18 hrs Comments Duplicate samples were collected randomly during every deployment to monitor sampling consistency. The duplicate sample was analysed as a test sample. There was some concern about the integrity of the tropical surface samples stored in the 21°C Hydrochemistry lab. An experiment was conducted to compare dissolved oxygen samples stored at 21°C and 30°C, no statistical difference was found between the dissolved oxygen concentrations. The samples continued to be stored in the hydrochemistry lab until analysis. An extra calculation for the final dissolved oxygen concentration was implemented during the voyage. This calculation smoothed the data due to the day-to-day variation in the thiosulphate titrant concentration and blank values. Kelly Brown performed the calculation according to the Oxygen Titration Manual SIO/STS version: Jun-2015 section 7.1 Thiosulfate Smoothing Procedure. Steve vanGraas wrote a script that pulled the corrected data into the existing LST files which was then be re-read by HyPro. 5.2 CTD vs Hydro DO Plot (see pdf) 5.3 Dissolved Oxygen thiosulphate normality across voyage(see pdf) 5.4 Dissolved Oxygen blank concentration across voyage(see pdf) 5.5 Missing or Suspect 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. CTD RP Bottle Analysis Flag Reason for Flag or Action --- ------ ------ -------- ---- -------------------------------------- 2 31 187 D.O. 69 High Niskin bottle froze uwy 017 647 D.O. 69 pCO2 system blowing air 4 11 252 D.O. 133 Incorrect volume possibly? Profile suspect 6 12 252 D.O. 133 Incorrect volume possibly? Profile suspect- flask pulled from box. 13 23 440 D.O. 141 Flask broke, lost sample, removed from file 15 17 430 D.O. 133 Profile is suspect, is also suspect for nuts, salt, cfc’s. 19 17, 23 D.O. 141 Bottles did not fire. 22 08 143 D.O. 141 Abort, titrator malfunc-tion, lost sample removed from file 30 20 407 D.O. 141 Abort, titrator malfunc-tion, lost sample removed from file 31 19 161 D.O. 141 Abort, titrator malfunc-tion, lost sample removed from file 32 21 261 D.O. 141 Abort, titrator malfunc-tion, lost sample removed from file 32 27 267 D.O. 141 Abort, titrator malfunc-tion, lost sample removed from file 38 11 147 D.O. 141 Flask smashed while sampling uwy 045 638 D.O. 69 NaOH/I bubble 39 01 232 D.O. 133 Draw Temp maybe incorrect, tempera- ture probe was malfunctioning. 39 03 235 D.O. 141 Also sample 03 Abort, titrator malfunction, lost sample. 41 04 136 D.O. 133 2 magnets in flask bad endpoint 42 04 200 D.O. 69 Profile suspect in waterfall plot. 44 20 D.O. 141 Niskin Lanyard caught in lid bottle leaking. 47 36 D.O. 141 Niskin fired in air. 53 36 653 D.O. 141 Abort, not enough NaOH/I in sample to titrate. 56 01 728 D.O. 133 black particles in flask 59 01 161 D.O. 141 Abort, titrator malfunction, lost sample removed from file 60 01 D.O. 141 Stopper put in bottle upside down 74 09 D.O. 141 Niskin leaking did not sample 100 11 322 D.O. 141 Abort, titrator malfunction, lost sample removed from file 103 05 566 D.O. 133 Waterfall profile out noted in sample log niskin rp 5 warmer temperature than other niskins. 110 04 582 D.O. 133 Waterfall profile out. 112 02 279 D.O. 141 Abort, titrator malfunction, lost sample removed from file 128 13 687 D.O. 141 Abort, titrator malfunction, lost sample removed from file 134 11 D.O. 141 NISKIN leaking not sampled for D.O. 136 14, 15 D.O. 141 NISKINS leaking not sampled for D.O. 138 14 D.O. 141 NISKIN leaking not sampled for D.O. 139 31 D.O. 141 NISKIN leaking not sampled for D.O. 140 19, 22, D.O. 141 NISKINS leaking not sampled for D.O. 27 6 NUTRIENT DATA PROCESSING 6.1 Nutrient Parameter Summary Details HyPro Version 4.12 Instrument AA3 Software Seal AACE 6.10 Methods AA3 Analysis Methods internal manual Nutrients analysed Silicate Phosphate Nitrate + Nitrite Ammonia Nitrite -------- --------- --------- -------- --------- Concentration range 140 3 42.0 1.4 2.0 µmol l-1 µmol l-1 µmol l-1 µmol l-1 µmol l-1 Method Detection Limit* 0.2 0.02 0.02 0.02 0.02 (MDL) µmol l-1 µmol l-1 µmol l-1 µmol l-1 µmol l-1 Matrix Corrections N N N N N Analyst(s) Peter Hughes, Melissa Miller, Christine Rees and Cassie Schwanger Lab Temperature (±1°C) Variable, 20.0 – 23.0°C Reference Material RMNS – CA, BV, BW Sampling Container type 10 mL polypropylene Sample Storage < 2 hrs at room temperature or ≤ 12 hrs @ 4°C Pre-processing of Samples None Comments Non-CTD related samples were analysed and processed with the prefix- uwy and exp. Exp samples were collected and frozen for ammonia analysis. Ammonia was measured at the end of Leg 1 and again at the end of Leg 2. Surface ammonia samples were collected from the CTD as well as a MDL that varied in depth. Underway samples were measured within a 24 hour period of sample collection. 6.2 Nutrient calibration and data parameter summary During the course of the voyage all run information was logged - LNSW batch, new cadmium column, new stock standard, daily standard information, fresh reagent information, instrumentation settings, pump tube changes and pump tube hours. This information along with calibration summary data and calibration plots for each analysis run are available in the following zip folder consisting of files containing; mdl, drift, baseline, carry-over, calibration & RMNS results: http://www.cmar.csiro.au/datacentre/process/data_files/Investigator_NF/in2016_v03/da ta/in2016_v03Hydro_nc.zip All NUT### file numbers with each ctd deployment analysed per analysis run can be viewed in the pdf file “AA3FileLog.pdf” in the above location. The latitude, longitude and time (UTC) that matches the UWY samples is located in file “IN2016 V03 UWY.pdf”. All runs have a corresponding AA3_Run_Analysis_sheet and AA3_Processing_Worksheet file to assist in characterizing data and note questionable peaks. This information is contained in the voyage documentation and available upon request. The raw data is imported into Hypro for peak determination. For each analysis run (indicated by a NUT###), HyPro fits the best calibration curve to the standards by performing several passes over each standard point. If the measured value is different from the calculated value it will allocate less weighting to the point in the calibration curve. HyPro will mark these points as suspect or bad within the calibration curve. Following standard procedures, the operator may choose to remove bad calibration points by placing a # in front of the peak start column within the data file (see section 6.6 for edited data). Below are the standard corrections and settings that Hypro applies to the raw data. Result Details Silicate Phosphate Nitrate + Nitrite Ammonia Nitrite -------------------- -------- --------- --------- --------- --------- Data Reported as µmol l-1 µmol l-1 µmol l-1 µmol l-1 µmol l-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 17/5/2015 off shore from Brisbane (-27.1S, 155.2E) using the clean instrument seawater supply inlet. Twenty five carboys were filtered through 1µM by Stephen Tibben and Kendall Sherrin on the 21st and 22nd of April 2016 and stored in the constant temperature room at 21°C. Medium of Baseline 18.2 Ω MQ Proportion of 1 duplicate for each CTD from NISKIN bottle 1 samples in duplicate? Comments Calibration and QC data that was edited or removed is located in the table in section 3.6.6. The reported data is not corrected to the RMNS. Per run RMNS data can be found in Appendix 5.4. 6.3 Accuracy - Reference Material for Nutrient in Seawater (RMNS) Plots The certified reference materials (CRM) for silicate, phosphate, nitrate and nitrite in seawater produced by KANSO – Japan was used in each nutrient analysis to ensure the accuracy of results. The RMNS was run 4 times after the calibration standards. No QC data is supplied for the experimental ammonia samples as there is not a CRM. Accuracy is determined by comparing the new standard batch with the old and tracking to ensure the concentration is within 1% accuracy between batches. The RMNS Lot CA (produced 22/02/2013) was measured 4 times in every CTD analysis. The RMNS Lot BV (produced 15/09/2011) was analysed every few days alongside the CA. The RMNS Lot BW was only measured once in 4 replicates during the voyage. RMNS results were converted from µ mol/kg to µ mol l-1 at 21°C in the following table. Table 1: RMNS CA, BV and BW concentrations (µM) at 21°C RMNS NO3 NOX NO2 PO4 SiO4 ---- ----- ----- ----- ---- ----- CA 20.13 20.20 0.065 1.44 37.46 BV 36.21 36.26 0.048 2.56 104.6 BW 25.18 25.25 0.069 1.58 61.45 The submitted nutrient results do NOT have RMNS corrections applied. During the voyage principal researchers corrected the data within each nutrient analysis using the CA RMNS. The following calculation was performed: RMNS Correction % error = (RMNS measured – RMNS Published)/RMNS Published Corrected Nutrient Concentration = Nutrient measured – (nutrient measured x error) Note: NOx data should be corrected as NO3 and NO2. 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), reference section 5.3, specifies using 1-3 % of full scale (depending on the nutrient) as acceptable limits of accuracy. The calculated RMNS values per CTD are reported in the table in section 5.4. 6.3.1 Silicate RMNS Plot 6.3.2 Phosphate RMNS Plot 6.3.3 Nitrate + Nitrite (NOx) RMNS Plot 6.3.4 Nitrite RMNS Plot 6.4 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 CRM over time (Armishaw 2003). Silicate Phosphate Nitrate + Nitrite Ammonia Nitrite (NOx) ---------------- -------- --------- ------------- ------- ------- Calculated MU* @ ±0.017 ±0.020 ±0.017 ±0.108 ±0.066¥ 1 µmol l-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 CRM. Method detection limits (MDL) achieved during the voyage were much lower than the nominal detection limits, indicating high analytical precision at lower concentrations. Results are µmol l-1. The precision of the RMNS is was also determined. MDL Silicate Phosphate Nitrate + Nitrite Ammonia Nitrite (NOx) ---------------- -------- --------- ------------- ------- ------- Nominal MDL* 0.20 0.02 0.02 0.02 0.02 Min 0.002 0.001 0.002 0.001 0.009 Max 0.227 0.015 0.032 0.011 0.009 Mean 0.057 0.004 0.007 0.003 0.009 Median 0.039 0.003 0.006 0.003 0.009 Precision of 0.050 0.003 0.005 0.002 NA MDL (stdev) *MDL is based on 3 times the standard deviation of Low Nutrient Seawater (LNSW) analysed in each nutrient run. Published RMNS 37.46 1.441 20.20 0.065 - (µmol l-1) w/uncertainty ± 0.22 ± 0.014 ± 0.16 ± 0.010 RMNS Min 36.03 1.413 19.96 0.062 - RMNS Max 38.51 1.488 20.54 0.087 - RMNS Mean 37.26 1.447 20.29 0.074 - RMNS Median 37.26 1.445 20.31 0.073 - RMNS Std Dev 0.43 0.017 0.12 0.005 - 6.5 Sampling Precision Duplicates samples were collected from NISKIN bottle 1 to measure the precision of nutrient sampling (this is not a measurement of analytical precision). The duplicate measurements are reported in the data as an average when the duplicates are flagged GOOD. The sampling precision is deemed good if difference between duplicate concentrations is below the MDL for silicate, phosphate and nitrite and within 0.05 µM for nitrate. 6.5.1 Silicate Duplicate Plot(see pdf) 6.5.2 Phosphate Duplicate Plot(see pdf) 6.5.3 Nitrate + Nitrite (NOx) Duplicate Plot(see pdf) 6.5.4 Nitrite Duplicate Plot 6.5.5 Redfield Ratio Plot (14.0)(see pdf) Plots consists of phosphate versus NOx, best fit ratio = 14.37. 6.6 Calibration and QC edited data CTD Peak Analysis Action --- --------------- -------- ------------------------------------------- 29 Cal 5 NO2 Cal 5 was removed from curve, no carry over corrections were applied 30 Cal 5 NO2 Cal 5 was removed from curve, no carry over corrections were applied 108 Recovery NOx No cadmium column recovery determined 113 Cal 2 NOx 2nd Cal 2 removed due to spike on the peak 122 Cal 2 SiO4 Removed – outlier on curve 123 Cal 2 SiO4 Removed – outlier on curve 128 Cal 2 NOx Removed – outlier on curve 128 Cal 4 SiO4 Removed – outlier on curve 129 Cal 1 NOx Removed – outlier on curve 134 Cal 3 SiO4 Removed – outlier on curve 135 Cal 3 SiO4 Removed – outlier on curve 136 Cal 3 SiO4 Removed – outlier on curve 139 Cal 1, 2, 3, 4, 5 SiO4 Removed – outlier on curve 140 Cal 1, 2, 3, 4 SiO4 Removed – outlier on curve 140 Cal 1 NOx Removed – outlier on curve 6.7 Investigation of Missing or Flagged Nutrient Data and Actions taken. The table below identifies all flagged data and data that was repeated. Data that falls below the detection limit, Flag 63, is not captured in this table. All GOOD data is flagged 0 in the .csv and .netcdf files. Refer to Appendix 7.2 for flag explanations. CTD RP Run Analysis Flag Reason for Flag or Action --- --------- ------- --------- ---- --------------------------------------------- 2 20 Nut017 NOx 65 Data good, hypro flag due to peak shape 3 11 Nut018 SiO4 65 Data good, hypro flag due to peak shape 4 03 Nut019 SiO4 65 Data good, hypro flag due to peak shape 9 07 Nut024 NOx 0 Outlier in waterfall profile for the first , analysis repeated and reported result from run nut025 11 04 Nut025 NOx 0 Outlier in waterfall profile, repeated in nut026, use result from nut026 11 28 Nut025 PO4 0 Outlier in waterfall profile, repeated in nut026, use result from nut026. 12 15 Nut026 NOx 0 Outlier in waterfall profile, repeated in nut027, use result from nut027. 15 17 Nut029 All Nuts 133 Does not follow water fall plot, flagged as bad. Niskin mistrip. 19 01 Nut032 NOx 0 Outlier in waterfall profile, repeated in nut033, use result from nut033 19 17,23 Nut032 All Nuts 141 Bottles did not fire, no samples collected 21 01,02 Nut034 Silicate 0 Odd Peak Shapes repeated in nut035 use results from nut035. 23 01 Nut036 NOx,NO2 0 2nd duplicate Flagged as Bad in HyPro – waterfall plot shows bad data. Duplicate >0.02. 24 21 Nut037 NOx 0 Suspect peak shape repeated in nut038 for final reported value. 27 22 Nut040 SiO4 65 Data good, hypro flag due to peak shape 41 11 All nuts 141 Emptied NISKIN before collecting nutrient samples. 48 01 Nut063 NOx 0 Difference between duplicates > 0.02µM (MDL), repeated in nut064 and use 2nd result. 49 2, 3, 6, Nut064 All Nuts 141 Niskins not sampled 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30 50 3, 7, 10, Nut064 All Nuts 141 Niskins not sampled 12, 14, 16, 18, 20, 22, 24, 26, 29, 32 EXP MLD Nut065 NH4 0 Suspect peak shape; repeated in nut066 for final 24 reported value. 52 20 Nut071 All Nuts 133 Outlier in waterfall profile, lanyard caught in top of NISKIN –lanyard pulled out. Repeated the analysis gave same result. 53 17 Nut072 All Nuts 141 Niskin end cap didn’t close 56 26 Nut075 NOx 0 Suspect peak shape; repeated in nut076 for final reported value 64 01 Nut083 NOx 0 Difference between duplicates > 0.02µM (MDL), repeated in nut084 and use 2nd result. 68 01 Nut087 NOx 0 Difference between duplicates > 0.02µM (MDL), repeated in nut088 use this 2nd result. 70 10 Nut089 All Nuts 133 Outlier in waterfall plot, noted that vent popped off NISKIN. 70 01 Nut089 SiO4 0 Difference between duplicates > 0.20µM (MDL), repeated in nut090 use this 2nd result. 79 all Nut098 NOx 0 Cd column blocked shifted peak windows and decreased NO3 conversion to NO2. Repeated samples in Nut099 for reported results. 81 03 Nut101 NOx 0 Blip on plateau, outlier in waterfall profile. Repeated in Nut102 for final result. 83 01, 02 Nut103 NOx 69 Bad duplicates >0.02, these NISKIN bottles were down at bottom of ocean floor. Crash Samples. 84 01, 02 Nut104 All Nuts 141 No samples collected 98 All Nut118 NOx 0 BAD calibration curve causing RMNS to be above 3%. Data removed from slk file and re- ran in nut120 for reported results. 103 5 Nut124 All Nuts 133 The depth profile show an anomaly in this RP sample and a bottle temperature note was recorded on the sampling sheet. Salt and oxygen data also show an anomaly. 106 All Nut127 NOx 0 RMNS low and results in profile much lower than previous runs. Repeated in nut 130. CTD RP Run Analysis Flag Reason for Flag or Action 111 All Nut132 NOx 0 Results in profile much lower than all other runs. Repeated in nut135. 112 33-36 Nut133 All Nuts 141 Air valves not closed on niskins, no samples collected 113 10 Nut134 All Nuts 141 Niskin leaked, no samples collected 117 10 Nut138 SiO4 0 Large air spike on top of peak, repeated in nut139 for reported final results. 119 all Nut140 NOx 0 RMNS 3% high, repeated run in nut142. 119 13 Nut142 All Nuts 141 No sample collected 121 30 Nut143 NOx 0 Bump in peak window –peak shape. Repeated in nut144 for reported result. 122 01 Nut144 NOx 69 Difference between duplicates 0.07µM (MDL = 0.02 µM), repeated in nut145 result not any better leave as is. 124 10, 26 Nut146 All Nuts 141 Niskins leaked, no samples collected 125 32 Nut149 NO2 129 The peak was off scale in AACE. Sample repeated with dilution 3mL sample + 6mL LNSW in run nut150 =(0.591-0.001)x3=1.77 µM updated csv file not netcdf 134 11 Nut157 All Nuts 141 Niskin leaked, no sample collected 138 14 Nut161 All Nuts 141 Niskin leaked, no sample collected 140 27 Nut163 All nuts 141 Lanyard caught in top cap-leaked. 6.8 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 “in2016_v03_hyd_voyagereport.docx” for room temperature graphs, nutrient samples were placed on XY3 auto sampler at the average room temperature of 21.5ºC. 7 Appendix 7.1 Salinity Reference Material Osil IAPSO Standard Seawater ---------------------------- K15 0.99985 Use by date 15/04/17 Batch P157 7.2 Hypro Flag Key for CSV & NetCDF file Flag Meaning 0 Data is 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 is bad – operator identified by # in slk file or by clicking on point. 129 Peak exceeds maximum A/D value. Data is bad. 134 Error flagged by software. Peak shape is bad - Median Absolute Deviation (MAD) analysis used. Standards, MDL’s and Duplicates deviate from the median, Calibration data falls outside 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. 7.3 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.1 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†, 2 and 0.2% precision, full-scale. PO4 Approximately 1-2% accuracy†, 2 and 0.4% precision, full scale. NO3 Approximately 1% accuracy†, 2 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. 1 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. 2 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. 7.4 RMNS Values for each CTD CTD SiO4 SiO4 PO4 PO4 NO2 NO2 NOx NOx mea- ex- mea- ex- mea- ex- mea- ex- sured pect- sured pect- sured pect- sured pect- ed ed ed ed ------- ----- ----- ---- ---- ----- ----- ----- ----- 2 37.9 37.5 1.48 1.44 0.082 0.065 20.37 20.20 3 38.5 37.5 1.48 1.44 0.081 0.065 20.31 20.20 3 106.1 104.7 2.62 2.56 0.066 0.048 36.53 36.26 4 38.2 37.5 1.48 1.44 0.080 0.065 20.31 20.20 4 105.7 104.7 2.61 2.56 0.063 0.048 36.48 36.26 5 38.1 37.5 1.47 1.44 0.074 0.065 20.41 20.20 6 38.1 37.5 1.48 1.44 0.085 0.065 20.50 20.20 8 38.2 37.5 1.46 1.44 0.074 0.065 20.41 20.20 9 38.1 37.5 1.47 1.44 0.074 0.065 20.39 20.20 11 38.1 37.5 1.46 1.44 0.072 0.065 20.45 20.20 11 105.1 104.7 2.58 2.56 0.055 0.048 36.55 36.26 12 38.0 37.5 1.46 1.44 0.078 0.065 20.47 20.20 12 105.1 104.7 2.58 2.56 0.059 0.048 36.42 36.26 13 37.7 37.5 1.48 1.44 0.076 0.065 20.40 20.20 14 37.6 37.5 1.47 1.44 0.084 0.065 20.43 20.20 15 37.7 37.5 1.47 1.44 0.072 0.065 20.38 20.20 17 37.5 37.5 1.46 1.44 0.074 0.065 20.42 20.20 19 37.6 37.5 1.46 1.44 0.076 0.065 20.54 20.20 20 37.6 37.5 1.47 1.44 0.067 0.065 20.29 20.20 21 37.4 37.5 1.46 1.44 0.075 0.065 20.31 20.20 21 104.3 104.7 2.57 2.56 0.055 0.048 36.30 36.26 22 37.4 37.5 1.46 1.44 0.076 0.065 20.29 20.20 23 37.7 37.5 1.48 1.44 0.073 0.065 20.28 20.20 24 37.8 37.5 1.48 1.44 0.072 0.065 20.36 20.20 25 37.8 37.5 1.47 1.44 0.075 0.065 20.35 20.20 26 37.8 37.5 1.47 1.44 0.075 0.065 20.35 20.20 27 37.4 37.5 1.46 1.44 0.078 0.065 20.38 20.20 28 37.4 37.5 1.47 1.44 0.076 0.065 20.28 20.20 29 37.6 37.5 1.46 1.44 0.075 0.065 20.40 20.20 30 37.5 37.5 1.47 1.44 0.076 0.065 20.44 20.20 31 37.5 37.5 1.47 1.44 0.070 0.065 20.37 20.20 32 37.6 37.5 1.45 1.44 0.066 0.065 20.38 20.20 CTD SiO4 SiO4 PO4 PO4 NO2 NO2 NOx NOx mea- ex- mea- ex- mea- ex- mea- ex- sured pect- sured pect- sured pect- sured pect- ed ed ed ed ------- ----- ----- ---- ---- ----- ----- ----- ----- 33 37.4 37.5 1.46 1.44 0.066 0.065 20.45 20.20 34 37.5 37.5 1.47 1.44 0.074 0.065 20.30 20.20 34 104.6 104.7 2.59 2.56 0.054 0.048 36.37 36.26 35 37.6 37.5 1.45 1.44 0.120 0.065 20.51 20.20 36 37.3 37.5 1.47 1.44 0.071 0.065 20.34 20.20 37 37.4 37.5 1.48 1.44 0.078 0.065 20.44 20.20 38 37.5 37.5 1.47 1.44 0.072 0.065 20.40 20.20 39 37.3 37.5 1.45 1.44 0.072 0.065 20.31 20.20 40 37.4 37.5 1.46 1.44 0.075 0.065 20.33 20.20 41 37.4 37.5 1.46 1.44 0.073 0.065 20.26 20.20 42 37.3 37.5 1.45 1.44 0.079 0.065 20.35 20.20 43 37.4 37.5 1.45 1.44 0.076 0.065 20.27 20.20 44 37.3 37.5 1.46 1.44 0.077 0.065 20.28 20.20 45 37.3 37.5 1.44 1.44 0.076 0.065 20.19 20.20 46 37.0 37.5 1.43 1.44 0.076 0.065 20.26 20.20 46 103.7 104.7 2.54 2.56 0.057 0.048 36.42 36.26 47 37.3 37.5 1.44 1.44 0.077 0.065 20.36 20.20 48 37.2 37.5 1.43 1.44 0.078 0.065 20.30 20.20 49 37.1 37.5 1.42 1.44 0.075 0.065 20.32 20.20 50 37.1 37.5 1.42 1.44 0.075 0.065 20.32 20.20 51 37.1 37.5 1.44 1.44 0.069 0.065 20.31 20.20 52 37.0 37.5 1.46 1.44 0.068 0.065 20.31 20.20 52 103.9 104.7 2.58 2.56 0.055 0.048 36.47 36.26 53 37.1 37.5 1.46 1.44 0.073 0.065 20.31 20.20 54 37.1 37.5 1.47 1.44 0.069 0.065 20.30 20.20 55 37.3 37.5 1.46 1.44 0.070 0.065 20.31 20.20 56 37.3 37.5 1.47 1.44 0.080 0.065 20.30 20.20 57 37.4 37.5 1.45 1.44 0.080 0.065 20.29 20.20 58 36.6 37.5 1.44 1.44 0.080 0.065 20.22 20.20 59 36.6 37.5 1.45 1.44 0.071 0.065 20.19 20.20 60 36.9 37.5 1.42 1.44 0.074 0.065 20.15 20.20 61 36.9 37.5 1.42 1.44 0.073 0.065 20.19 20.20 61 36.8 37.5 1.44 1.44 0.067 0.065 20.16 20.20 62 36.8 37.5 1.43 1.44 0.073 0.065 20.14 20.20 62 102.9 104.7 2.53 2.56 0.055 0.048 36.08 36.26 63 36.8 37.5 1.43 1.44 0.073 0.065 20.14 20.20 CTD SiO4 SiO4 PO4 PO4 NO2 NO2 NOx NOx mea- ex- mea- ex- mea- ex- mea- ex- sured pect- sured pect- sured pect- sured pect- ed ed ed ed ------- ----- ----- ---- ---- ----- ----- ----- ----- 64 36.6 37.5 1.43 1.44 0.076 0.065 20.12 20.20 65 36.6 37.5 1.45 1.44 0.071 0.065 20.11 20.20 66 36.8 37.5 1.44 1.44 0.069 0.065 20.12 20.20 67 36.8 37.5 1.45 1.44 0.071 0.065 20.12 20.20 68 36.6 37.5 1.44 1.44 0.070 0.065 20.09 20.20 69 36.6 37.5 1.43 1.44 0.070 0.065 20.09 20.20 70 36.6 37.5 1.44 1.44 0.066 0.065 20.03 20.20 70 102.7 104.7 2.55 2.56 0.051 0.048 36.00 36.26 71 36.7 37.5 1.45 1.44 0.072 0.065 20.19 20.20 72 36.6 37.5 1.46 1.44 0.072 0.065 20.18 20.20 73 36.7 37.5 1.45 1.44 0.070 0.065 20.21 20.20 74 36.7 37.5 1.44 1.44 0.072 0.065 20.27 20.20 75 36.7 37.5 1.43 1.44 0.062 0.065 20.30 20.20 76 36.7 37.5 1.44 1.44 0.072 0.065 20.25 20.20 77 36.7 37.5 1.46 1.44 0.073 0.065 20.24 20.20 78 36.9 37.5 1.44 1.44 0.071 0.065 20.16 20.20 79 37.2 37.5 1.45 1.44 0.079 0.065 20.14 20.20 80 37.2 37.5 1.46 1.44 0.080 0.065 20.18 20.20 80 103.7 104.7 2.56 2.56 0.064 0.048 36.09 36.26 81 37.9 37.5 1.43 1.44 0.076 0.065 20.07 20.20 82 37.4 37.5 1.44 1.44 0.072 0.065 20.13 20.20 83 38.0 37.5 1.43 1.44 0.074 0.065 20.14 20.20 84 37.4 37.5 1.42 1.44 0.072 0.065 20.07 20.20 85 37.1 37.5 1.44 1.44 0.007 0.065 20.20 20.20 85 103.9 104.7 2.54 2.56 0.053 0.048 36.04 36.26 86 37.2 37.5 1.45 1.44 0.073 0.065 19.96 20.20 87 37.2 37.5 1.44 1.44 0.076 0.065 20.18 20.20 88 37.0 37.5 1.44 1.44 0.078 0.065 20.22 20.20 89 37.3 37.5 1.43 1.44 0.068 0.065 20.20 20.20 90 37.4 37.5 1.45 1.44 0.069 0.065 20.22 20.20 91 37.1 37.5 1.44 1.44 0.070 0.065 20.23 20.20 92 37.2 37.5 1.45 1.44 0.076 0.065 20.28 20.20 93 37.0 37.5 1.43 1.44 0.072 0.065 20.09 20.20 94 36.8 37.5 1.43 1.44 0.071 0.065 20.01 20.20 95 36.9 37.5 1.42 1.44 0.075 0.065 20.11 20.20 96 36.9 37.5 1.44 1.44 0.076 0.065 20.15 20.20 CTD SiO4 SiO4 PO4 PO4 NO2 NO2 NOx NOx mea- ex- mea- ex- mea- ex- mea- ex- sured pect- sured pect- sured pect- sured pect- ed ed ed ed ------- ----- ----- ---- ---- ----- ----- ----- ----- 97 37.0 37.5 1.44 1.44 0.075 0.065 20.06 20.20 98 36.9 37.5 1.42 1.44 0.074 0.065 20.06 20.20 99 37.0 37.5 1.43 1.44 0.073 0.065 20.08 20.20 100 36.8 37.5 1.44 1.44 0.080 0.065 20.13 20.20 101 36.8 37.5 1.43 1.44 0.090 0.065 20.18 20.20 102 36.8 37.5 1.43 1.44 0.069 0.065 20.21 20.20 103 37.1 37.5 1.43 1.44 0.071 0.065 20.04 20.20 104 37.1 37.5 1.44 1.44 0.078 0.065 20.07 20.20 105 37.0 37.5 1.43 1.44 0.080 0.065 20.16 20.20 106 37.0 37.5 1.42 1.44 0.069 0.065 20.01 20.20 107 36.7 37.5 1.44 1.44 0.075 0.065 19.89 20.20 108 36.9 37.5 1.44 1.44 0.073 0.065 20.09 20.20 109 36.8 37.5 1.44 1.44 0.068 0.065 20.01 20.20 110 36.8 37.5 1.45 1.44 0.073 0.065 20.04 20.20 110 103.2 104.7 2.55 2.56 0.058 0.048 35.92 36.26 111 36.8 37.5 1.43 1.44 0.069 0.065 20.03 20.20 112 36.8 37.5 1.42 1.44 0.074 0.065 20.09 20.20 113 36.8 37.5 1.42 1.44 0.083 0.065 20.18 20.20 114 36.8 37.5 1.42 1.44 0.070 0.065 20.03 20.20 115 37.2 37.5 1.44 1.44 0.079 0.065 20.06 20.20 116 37.2 37.5 1.44 1.44 0.078 0.065 20.15 20.20 117 37.1 37.5 1.43 1.44 0.079 0.065 19.96 20.20 118 37.2 37.5 1.45 1.44 0.080 0.065 20.09 20.20 118 104.5 104.7 2.55 2.56 0.065 0.048 36.08 36.26 119 37.0 37.5 1.44 1.44 0.080 0.065 20.10 20.20 120 36.8 37.5 1.43 1.44 0.079 0.065 20.14 20.20 120 36.8 37.5 1.43 1.44 0.079 0.065 20.14 20.20 121 36.9 37.5 1.45 1.44 0.076 0.065 20.09 20.20 122 36.7 37.5 1.42 1.44 0.072 0.065 20.05 20.20 123 36.3 37.5 1.43 1.44 0.069 0.065 20.01 20.20 124, 125 37.4 37.5 1.44 1.44 0.072 0.065 20.04 20.20 126, 127 37.4 37.5 1.44 1.44 0.067 0.065 20.07 20.20 128 37.2 37.5 1.44 1.44 0.070 0.065 20.33 20.20 128 103.6 104.7 2.54 2.56 0.054 0.048 35.63 36.26 129 37.3 37.5 1.44 1.44 0.072 0.065 20.01 20.20 130 37.7 37.5 1.45 1.44 0.068 0.065 20.17 20.20 CTD SiO4 SiO4 PO4 PO4 NO2 NO2 NOx NOx mea- ex- mea- ex- mea- ex- mea- ex- sured pect- sured pect- sured pect- sured pect- ed ed ed ed ------- ----- ----- ---- ---- ----- ----- ----- ----- 131 37.7 37.5 1.44 1.44 0.065 0.065 20.13 20.20 132 37.6 37.5 1.45 1.44 0.070 0.065 20.16 20.20 133 37.8 37.5 1.45 1.44 0.069 0.065 20.39 20.20 134 37.8 37.5 1.43 1.44 0.068 0.065 20.04 20.20 134 37.8 37.5 1.43 1.44 0.068 0.065 20.04 20.20 135 37.4 37.5 1.42 1.44 0.067 0.065 20.04 20.20 136 37.7 37.5 1.43 1.44 0.072 0.065 20.10 20.20 137 37.2 37.5 1.43 1.44 0.069 0.065 20.09 20.20 138 37.3 37.5 1.43 1.44 0.068 0.065 20.01 20.20 139 37.8 37.5 1.44 1.44 0.071 0.065 20.00 20.20 139 104.2 104.7 2.54 2.56 0.055 0.048 36.01 36.26 140 37.3 37.5 1.42 1.44 0.070 0.065 20.02 20.20 uwy088- 37.8 37.5 1.41 1.44 0.057 0.065 20.00 20.20 090 uwy091- 37.1 37.5 1.42 1.44 0.057 0.065 20.13 20.20 094 7.5 Nutrient Methods CSIRO Oceans and Atmosphere Hydrochemistry nutrient analysis is performed with a segmented flow auto-analyser – Seal AA3 – to measure silicate, phosphate, nitrite, nitrate plus nitrite, and ammonia. Table 2: Calibration range and detection limits of nutrient analysis Details Instrument AA3 Software Seal AACE 6.10 Methods AA3 Analysis Methods internal manual Nutrient Silicate Phosphate Nitrate + Nitrite Ammonia Nitrite ------------ ------------- ------------- ------------- ------------- Concentration 140 µmol l-1 3 µmol l-1 42 µmol l-1 1.4 µmol l-1 2.0 µmol l-1 range Method 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 Detection Limit (MDL) Silicate analysis is based on a modified Armstrong et al. (1967) method. Silicate in seawater reacts with acidified ammonium molybdate to produce silicomolybdic acid. This solution will also react with phosphate producing a phosphomolybdic acid. Tartaric acid is introduced to remove this interference. Finally, Stannous Chloride (Tin II Chloride) is added to reduce silicomolybdic acid to the blue compound silicomolybdous acid which can be detected at 660 nm or 820 nm. Phosphate measurement is based on the original Murphy and Riley (1962) method with some modifications developed at the NIOZ-SGNOS Practical Workshop 2012 optimizing antimony catalyst/phosphate ratio and reduction of silicate interferences by pH. Phosphate in seawater forms a phosphomolybdenum blue complex with acidified ammonium molybdate reduced by ascorbic acid which can be detected at 880 nm. Nitrate is determined by first reducing to nitrite via a basic buffered copperized cadmium column before the colour reaction (Wood et al., 1967). Nitrite in seawater will react with sulphanilamide under acidic conditions to form a diazo compound. This compound couples with 1-N-naphthly- ethylenediamine di-hydrochloride to produce a reddish purple azo complex which can be detected at 520 nm. The ammonia method, developed by Roger Kérouel and Alain Aminot, IFREMER (1997 Mar.Chem.57), is based on the reaction of ammonium with orthophtaldialdehyde and sulfite at a pH of 9.0-9.5 producing an intensely fluorescent product; excitation 370 nm, emission 460 nm. Detailed SOPs can be obtained from the CSIRO Oceans and Atmosphere Hydrochemistry Group on request. 8 REFERENCES Armishaw, Paul, “Estimating measurement uncertainty in an afternoon. A case study in the practical application of measurement uncertainty.” Accred Qual Assur, 8, pp. 218-224 (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.381-389 (1967). Hood, E.M. (2010). “Introduction to the collection of expert reports and guidelines.” 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. Hydes, D., Aoyama, 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. Kérouel, 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. RV INVESTIGATOR CTD PROCESSING REPORT Voyage #: IN2016_V03 Voyage title: Monitoring Ocean Change and Variability along 170°W from the ice edge to the equator. Depart: Hobart, 0900 Tuesday, 26 April 2016 Return: Hobart, 0800 Thursday, 30 June 2016 Report compiled by: Steven Van Graas Contents 1 Summary 70 2 Voyage Details 71 2.1 Title 71 2.2 Principal Investigators 71 2.3 Voyage Objectives 71 2.4 Area of operation 71 3 Processing Notes 71 3.1 Background Information 71 3.2 Pressure and temperature calibration 73 3.3 Conductivity Calibration 73 3.4 Dissolved Oxygen Sensor Calibration 74 3.5 Other sensors 75 3.6 Bad data detection 75 3.7 Averaging 76 4 References 76 1 SUMMARY These notes relate to the production of quality controlled, calibrated CTD data from RV Investigator voyage in2016_v03, from 26 Apr 2016 – 30 Jun 2016. Data for 141 deployments were acquired using the Seabird SBE911 CTD 20, fitted with 36 ten litre bottles on the rosette sampler. CSIRO supplied calibrations were applied to the temperature, conductivity, oxygen, and pressure data. The data were subjected to automated QC to remove spikes and out-of-range values. The final conductivity calibration is based on multiple deployment groupings, due to sensor and deck box changes. Processing was performed on each unique sensor configuration in order to best account for the individual characteristics of each sensor. The final calibration from the primary sensor for casts 1-7 had a standard deviation (S.D) of 0.00088 PSU, a S.D of 0.00117 for casts 8-46, and S.D of 0.00114 for casts 47-141, well within our target of ‘better than 0.002 PSU’. The standard product of 1 dbar binned averaged were produced using data from the primary temperature and conductivity sensors, and the secondary Oxygen sensor. Similarly, the dissolved oxygen data were calibrated in groups of deployments due to sensor changes. The dissolved oxygen data calibration fit had a S.D. of 0.865uM for casts 1-7, S.D. of 0.906uM for casts 8-46, S.D. of 1.05uM for casts 47-63, 0.739uM for casts 64-83, S.D. of 0.874uM for casts 84-110, and a S.D. of 1.0479 for casts 111-141. The agreement between the CTD and bottle data was good. A Fluorometer, Transmissometer, and altimeter were also installed and logged on the auxiliary A/D channels of the CTD. 2 VOYAGE DETAILS 2.1 Title Monitoring Ocean Change and Variability along 170o W from the ice edge to the equator. 2.2 Principal Investigators Bernadette Sloyan – Leg 1, Susan Wijffels – Leg 2 2.3 Voyage Objectives The scientific objectives for in2016_v03 were outlined in the Voyage Plan. For further details, refer to the Voyage Plan and/or summary which can be viewed on the CSIRO Marine and Atmospheric Research web site. 2.4 Area of operation FIGURE 1. Area of operation for in2016_v03 3 PROCESSING NOTES 3.1 Background Information The data for this voyage were acquired with the CSIRO CTD unit #20 and #22, Seabird SBE911 with dual conductivity and temperature sensors. The CTD was additionally fitted with SBE43 dissolved oxygen sensors, an altimeter, Transmissometer and Fluorometer. Additionally the CTD unit provided power only for two SBE61 units. The sensors that were equipped are described in Table 1 below. TABLE 1: CTD Sensor configuration on in2016_v03 Description Sensor Casts Serial A/D Calibration Calibration No. Date Source --------------- ---------------- ------- ------ --- ----------- ------------- Pressure Digiquartz SBE9+ 1-7, 552 P 2016-03-09 CSIRO Cal Lab 47-141 Pressure Digiquartz SBE9+ 8-46 1243 P 2016-03-09 CSIRO Cal Lab Primary Seabird SBE3plus 1-46 4722 T0 2016-03-01 CSIRO Cal Lab Temperature Primary Seabird SBE3plus 47-141 6022 T0 2015-07-15 CSIRO Cal Lab Temperature Secondary Seabird SBE3plus 1-46 4522 T1 2016-03-01 CSIRO Cal Lab Temperature Secondary Seabird SBE3plus 47-93 6024 T1 2015-07-24 CSIRO Cal Lab Temperature Secondary Seabird SBE3plus 94-141 4718 T1 2015-10-29 CSIRO Cal Lab Temperature Primary Seabird SBE4C 1-46 3868 C0 2016-03-02 CSIRO Cal Lab Conductivity Primary Seabird SBE4C 47-141 4425 C0 2015-07-08 CSIRO Cal Lab Conductivity Secondary Seabird SBE4C 1-46, 4426 C1 2015-07-08 CSIRO Cal Lab Conductivity 114-141 Secondary Seabird SBE4C 47-88 2312 C1 2015-11-24 CSIRO Cal Lab Conductivity Secondary Seabird SBE4C 89-113 2235 C1 2015-11-24 CSIRO Cal Lab Conductivity Primary SBE43 1-46 3154 A0 2016-03-10 CSIRO Cal Lab Dissolved Oxygen Primary SBE43 47-141 1794 A0 2016-03-10 CSIRO Cal Lab Dissolved Oxygen Secondary SBE43 1-46, 3198 A1 2015-08-12 CSIRO Cal Lab Dissolved 111-141 Oxygen Secondary SBE43 47-111 3199 A1 2015-08-12 CSIRO Cal Lab Dissolved Oxygen Transmissometer C-Star 1-141 CST- A2 2015-08-14 Manufacturer 1421DR Altimeter PA500 1-141 5301. A3 2015-05-22 Manufacturer 228403 Fluorometer Chelsea 57-141 0088- A6 2014-02-06 Manufacturer Aquatracka III 3598C Water samples were collected using a Seabird SBE32, 24-bottle rosette sampler. Sampling was from 36 ten litre bottles which were fitted to the frame. There were 141 deployments. The raw CTD data were converted to scientific units and written to netCDF format files for processing using the Matlab-based, CapPro package. The CapPro software was used to apply automated QC and preliminary processing to the data. This included spike removal, identification of water entry and exit times, conductivity sensor lag corrections and the determination of the pressure offsets. The automatically determined pressure offsets and in-water points were inspected and adjusted where necessary. It also loaded the hydrology data and computed the matching CTD sample burst data. Filtering for bad data caused by ship heave affecting the velocity of the package was also applied to the binned average data. The bottle sample data were used to compute final conductivity and dissolved oxygen calibrations. These were applied to the data, after which files of binned 1dB averaged data were produced. 3.2 Pressure and temperature calibration The pressure offsets are plotted in Figure 2 below. The blue circles refer to initial out-of-water values and the red circles the final out-of-water values. The jump in the plot that is evident at cast 47 is due to changing the pressure sensor. FIGURE 2: CTD pressure offsets 3.3 Conductivity Calibration Discrepancies and possible sampling problems between bottle and CTD salinities for the primary conductivity sensor would show in Figure 4, the plot of calibrated (CTD - Bottle) salinity below, for all groups of deployments processed. The calibration was based upon the sample data for an overall total of 3654 of the total of 4720 samples taken during deployments (the outliers marked in Figure 4 below with the magenta diamonds are excluded from the calibration). FIGURE 4: CTD - bottle salinity plot. The final result for the primary conductivity sensor for casts 1 - 7 was – Scale Factor (a1) 0.99943 wrt. CSIRO calibration Offset (a0) -8.6338e-05 ditto Calibration S.D. (Sal) 0.00087776 PSU The final result for the primary conductivity sensor for casts 8 - 46 was – Scale Factor (a1) 0.99941 wrt. CSIRO calibration Offset (a0) -2.4759e-05 ditto Calibration S.D. (Sal) 0.0011708 PSU The final result for the primary conductivity sensor for casts 47 - 141 was – Scale Factor (a1) 1.0005 wrt. CSIRO calibration Offset (a0) -0.00069281 ditto Calibration S.D. (Sal) 0.0011492 PSU This is a good calibration. We normally aim for a S.D. of 0.002 psu for ‘typical’ oceanographic voyages. The above calibration factors were applied to all deployments in their respective calibration groups. Data from the primary conductivity and temperature sensors were used to produce the averaged salinities. The calibration using the secondary conductivity sensor was well beyond our acceptable standard deviation range, and as such was not applied. 3.4 Dissolved Oxygen Sensor Calibration 3.4.1 SBE calibration procedure Sea-Bird (2010a) describes the SBE43 as “a polarographic membrane oxygen sensor having a single output signal of 0 to +5 volts, which is proportional to the temperature-compensated current flow occurring when oxygen is reacted inside the membrane. A Sea-Bird CTD that is equipped with an SBE43 oxygen sensor records this voltage for later conversion to oxygen concentration, using a modified version of the algorithm by Owens and Millard (1985)”. Calibration involves performing a linear regression, as per Sea-Bird (2010b) to produce new estimates of the calibration coefficients Soc and Voffset. These new coefficients are used, along with the other, manufacturer-supplied coefficients, to derive oxygen concentrations from the sensor voltages. Results Deeper casts (>1000m) are known to be affected by pressure-induced hysteresis with this sensor. This is corrected automatically within CapPro using the method discussed by Sea-Bird (2010c). There is a small mismatch between downcast and upcast dissolved oxygen due to the response time of the sensor. No correction for the sensor lag effect has been applied. Multiple deployment calibration groups were used with the associated SBE43 up-cast data to compute the new Soc and Voffset coefficients, due to changes of sensors throughout the voyage. The old and new Soc and Voffset values for DO sensors are listed in Table 2 below. The Soc value is a linear slope scaling coefficient; Voffset is the fixed sensor voltage at zero oxygen. As expected, over time, the increasing Soc scale factors show the SBE43 sensor is losing sensitivity. The calibrations were applied for each sensor and the averaged files were created using the result from the primary sensor for casts 1-7, and the secondary sensor for casts 8 – 141. These groups were divided further due to changing the CTD unit. The primary oxygen sensor for casts 47-141 calibrated extremely poorly. TABLE 2: Dissolved oxygen calibrations Casts CSIRO calibration sensor Primary/ of sensor calibration Secondary ------- --------- ----------------- ----------- --------- 1-7 Voffset -0.50133997 -0.47032 Primary Soc 0.47520554 0.49124 Fit SD (uM) 0.86539 8-46 Voffset -0.4982 -0.45105 Secondary Soc 0.4241 0.42153 Fit SD (uM) -- 0.9063 47-63 Voffset -0.4873 -0.45033 Secondary Soc 0.5318 0.53553 Fit SD (uM) -- 1.0502 64-83 Voffset -0.4873 -0.45744 Secondary Soc 0.5318 0.5505 Fit SD (uM) -- 0.7398 84-110 Voffset -0.4873 -0.44407 Secondary Soc 0.5318 0.54158 Fit SD (uM) -- 0.87393 111-141 Voffset -0.4982 -0.41699 Secondary Soc 0.4241 0.40081 Fit SD (uM) -- 1.0479 3.5 Other sensors The Chelsea fluorometer was used for deployments 57 onwards. The fluorometer has been calibrated to give nominal outputs of 0-100 fsd (full scale deflection). 3.6 Bad data detection The limits for each sensor are configured in the CAP the CTD acquisition software and are written to the netCDF scan file. Typical limits used for the sensor range and maximum second difference are in Table 3 below. The rejection rate is recorded in the CapPro processing log file. TABLE 3: Sensor limits for bad data detection Sensor Range min Range max Max Second Diff ------------ --------- --------- --------------- temperature -2 40 0.05 conductivity -0.01 7 0.01 oxygen -1 500 0.5 fluorometer 0 100 0.5 3.7 Averaging The calibrated data were ‘filtered’ to remove pressure reversals and binned into the standard product of 1dbar averaged NetCDF files. The binned values were calculated by applying a linear, least-squares fit as a function of pressure to the sensor data for each bin, using this to interpolate the value for the bin mid-point. This method is used to avoid possible biases which would result from averaging with respect to time. Each binned parameter is assigned a QC flag. Our quality control flagging scheme is described in Pender (2000). The QC Flag for each bin is estimated from the values for the bin components. The QC Flag for derived quantities, such as Salinity and Dissolved Oxygen are taken to be the worst of the estimates for the parameters from which they are derived. 4 REFERENCES Sloyan, Wijffels., 2016: The RV Investigator. Voyage Plan IN2016_V03 - http://mnf.csiro.au/~/media/Files/Voyage-plans-and- summaries/Investigator/Voyage%20Plans%20summaries/2016/IN2016_V03%20Voy age%20Plan%2020160427%20FINAL.ashx Pender, L., 2000: Data Quality Control Flags. http://www.cmar.csiro.au/datacentre/ext_docs/DataQualityControlFlags.pdf Sea-Bird Electronics Inc., 2010a: Application Note No 64: SBE 43 Dissolved Oxygen Sensor -- Background Information, Deployment Recommendations, and Cleaning and Storage. http://www.seabird.com/pdf_documents/ApplicationNotes/appnote64Feb10.pdf Sea-Bird Electronics Inc., 2010b: Application Note No 64-2: SBE 43 Dissolved Oxygen Sen- sor Calibration and data Corrections using Winkler Titrations. http://www.seabird.com/pdf_documents/ApplicationNotes/Appnote64-2Feb10.pdf Sea-Bird Electronics Inc., 2010c: Application Note No 64-3: SBE 43 Dissolved Oxygen (DO) Sensor - Hysteresis Corrections. http://www.seabird.com/pdf_documents/ApplicationNotes/Appnote64-3Feb10.pdf CCHDO DATA PROCESSING NOTES • File Online Carolina Berys IN2016_V03 Voyage Summary.pdf (download) #78dd5 Date: 2017-04-11 Current Status: unprocessed • File Online Carolina Berys in2016_v03_HYD_ProcessingReport.pdf (download) #5b51f Date: 2017-04-11 Current Status: unprocessed • File Online Carolina Berys IN2016_V03CTD.pdf (download) #cc14c Date: 2017-04-11 Current Status: unprocessed • File Submission Bernadette Sloyan IN2016_V03CTD.pdf (download) #cc14c Date: 2017-04-11 Current Status: unprocessed Notes Voyage report for P15S. These include: Summary Hydrochemistry report. Flags used by the CSIRO hydrochemistry group have been converted to standard flags in the data submission. Please note I am working with Bob Key to get this completed, hopefully the data will be submitted by the end of the week CSIRO CTD processing report. Voyage report for P15S. These include: Summary Hydrochemistry report. Flags used by the CSIRO hydrochemistry group have been converted to standard flags in the data submission. Please note I am working with Bob Key to get this completed, hopefully the data will be submitted by the end of the week CSIRO CTD processing report. • File Submission Bernadette Sloyan IN2016_V03 Voyage Summary.pdf (download) #78dd5 Date: 2017-04-11 Current Status: unprocessed Notes Voyage report for P15S. These include: Summary Hydrochemistry report. Flags used by the CSIRO hydrochemistry group have been converted to standard flags in the data submission. Please note I am working with Bob Key to get this completed, hopefully the data will be submitted by the end of the week CSIRO CTD processing report. • File Online Carolina Berys P15S_ct.tar (download) #6b8ea Date: 2017-01-19 Current Status: unprocessed Dear CCHDO, Attached are the CTD and Hydro exchange files for the Australian occupation of the GO-SHIP P15S section (EXPOCODE = 096U20160426). The CTD oxygen data is flagged questionable as I am still working through calibration issues. The oxygen bottle data is of high quality and appropriately flagged. I am still working on the section report. I'll send this when completed. Please contact me if you have any question. Regards Bernadette