CRUISE REPORT HUDSON 96006 LABRADOR SEA WOCE LINE AR7W MAY 12 - JUNE 1, 1996 A. CRUISE NARRATIVE 1. Highlights a. WOCE Designation: WOCE Line AR7W b. Expedition Designation: Hudson 96006 c. Chief Scientist: John R. N. Lazier Ocean Circulation Section Ocean Sciences Division Department of Fisheries and Oceans Bedford Institute of Oceanography P.O. Box 1006 Dartmouth, NS, Canada B2Y 4A2 FAX 902 426 7827 Internet LazierJ@mar.dfo-mpo.gc.ca d. Ship: CSS Hudson e. Ports of Call: May 12 BIO, Dartmouth, NS, Canada June 1 Sydney, NS, Canada f. Cruise Dates: May 12, 1996 to June 1, 1996 2. Cruise Summary Information a. Cruise Track A cruise track is shown in Figure 1. Ship position at midnight on each day of the cruise is indicated with an asterisk. The day of the month (May) is also given beside the asterisk. The station positions are shown in Figures 2 and 3. Figure 2 shows the stations occupied along the Scotian Shelf and in the Gulf of St. Lawrence. Figure 3 shows stations along the WOCE line AR7W. Some station numbers are indicated for clarity Figure 1. Ship track for 18HU96006/1; * marks Hudson's position at 0000Z each day with some day labels indicated. Figure 2. Station positions and numbers for 18HU96006/1 on the Scotian Shelf, Newfoundland Shelf and Gulf of St. Lawrence. Figure 3. Station positions and numbers for 18HU96006/1 AR7W line. b. Total Number of Stations Occupied 44 full depth WHP small volume CTD stations with up to 23 rosette bottles. Depending on the station, water samples were analyzed for CFCs, carbon tetrachloride, methyl chloroform, total carbonate, alkalinity, oxygen, salinity, nutrients, tritium, helium, oxygen isotopes, chlorophyll, and dissolved organic carbon. 1 CTD cast with no water samples 29 full depth velocity profiles using a lowered ADCP attached to the CTD/rosette 2 ALACE float deployments 1 current meter mooring deployed 2 release test moorings deployed 1 current meter mooring recovered 1 current meter mooring partially recovered c. Floats and Drifters Deployed A total of two floats were launched during the cruise, both on the AR7W line. The two were P- ALACE (Profiling-Autonomous Lagrangian Circulation Explorer) floats launched for Ray Schmitt of WHOI. d. Moorings Deployed or Recovered In 1995, a multi-instrument mooring (BIO number M1194) was deployed during the BIO cruise to AR7W (WOCE Expocode 18HU95011/1). This mooring consisted of 6 Seacat temperature /conductivity recorders, 6 Aanderaa current meters, 1 acoustic doppler current profiler (ADCP), 1 WOTAN (weather observations through ambient noise) and 1 CTD with a device for measuring the partial pressure of dissolved gas in the water. It was intended to recover this mooring and deploy a duplicate mooring in the same location. During the recovery process, however, the weather deteriorated causing delays in grappling the upper float and excessive working of the buoyancy packages in the mounting seas. This in turn caused some seizing wire on the shackles to break leading to the mooring separating into two pieces. Recovery then proceeded from the bottom end of the mooring, but high winds pushed the ship breaking the mooring wire and the remainder of the mooring sank. The recovered components consisted of 2 current meters, 1 release, the WOTAN and CTD with dissolved gas instrumentation. A current meter mooring (BIO Number 1200) consisting of one current meter positioned 15 m off the bottom was recovered along the 1000 m isobath on the Labrador side of AR7W. This mooring was deployed during the 1995 cruise (Expocode 18HU95011/1). A duplicate mooring was deployed in the same location. A pair of release test moorings were deployed, one on the Scotian Shelf (shallow) and one along AR7W (deep). Both consisted of a Benthos Acoustic release with a backup EG&G release. These moorings are intended as a test of the Benthos release. 3. List of Principal Investigators Name Affiliation Responsibility John R. N. Lazier BIO CTD data, shipboard ADCP data, LazierJ@mar.dfo-mpo.gc.ca moored instrument data, salinity Erica Head BIO biological data Erica.head@maritimes.dfo.ca Robert Houghton LDEO oxygen ratio Houghton@ldeo.columbia.edu Peter Jones BIO oxygen, alkalinity, JonesP@mar.dfo-mpo.gc.ca carbonate, CFCs Robert Pickart WHOI lowered ADCP pickart@rsp.whoi.edu Peter Rhines UW moored instrument data Rhines@killer.ocean.washington.edu Peter Schlosser LDEO tritium, helium data Peters@ldeo.columbia.edu Peter Strain BIO nutrients StrainP@ mar.dfo-mpo.gc.ca See Section 7 for addresses. 4. Scientific Programme and Methods 4.1 Physical - Chemical Program One of the purposes of occupying the AR7W section each spring is to monitor the properties of the Labrador Sea Water (LSW) which is renewed in the central region of the sea via deep convection in winter. The depth of the convection varies with the severity of the winter and in recent years has reached 2300m in the exceptionally cold winters of the early 1990s, especially that of 1992-1993. The potential temperature and salinity (_-S) of the water mass also vary from year to year according to the inputs of heat and salt or freshwater brought about by convection and by eddy diffusion. The _-S values at the core of the LSW for each of the years between 1990 and 1996 except 1991, for which we have no CTD data, are shown in Figure 4. Temperature and salinity increased between 1995 and 1996 by 0.03 °C and 0.005, while the density remained constant. We think this is likely the result of horizontal eddy diffusion in the absence of convection. This is because the LSW presents a minimum in temperature and salinity in both vertical and horizontal planes and if there is no convection _-S must increase under eddy diffusion while the density remains unchanged. A calculation to check this possibility was performed using the data collected in 1994. The _ and S distributions on the _1.5 surfaces within the LSW across the Labrador Sea were determined then used as initial conditions in an estimate of the heat and salt fluxes from the boundaries into the centre of the section. When the boundary values were kept constant the fluxes toward the centre raised the _ and S by 0.05 °C and 0.007 in a year. These values are close enough to the observed values to support our hypothesis and gives us some confidence in suggesting that deep convection did not extend into the previously established LSW core during the 1995-1996 winter. Using the same argument, other years that do not show these _-S increases in the LSW core must have been influenced by vertical convection. This is certainly true of the years between 1990 and 1993 which were very severe and which show many features of active convection in the vertical profiles. The increases in salinity in these years is thought to be due to the convection layer increasing in thickness and incorporating higher salinity water from the layer below. The increase in _1.5 over these years is also an indication of a deepening convection layer. The _ decrease between 1993 and 1994 suggest that convection proceeded to the depth reached in the previous year but the decrease in salinity and the constancy of the _1.5 suggest it didn't penetrate any deeper than the previous year. The small changes between 1994 and 1995 suggest a near balance between the heat and salt losses associated with convection and the heat and salt gains due to eddy diffusion. Figure 4. The _-S values at the core of the LSW for each of the years between 1990 and 1996 except 1991. Biological Program 4.2.1 Zooplankton Sampling and Other Experimental Programmes (E. Head / L. Harris) 4.2.1.1 Estimation of the biomass and vertical distribution of zooplankton Vertical net tows were carried out between 100 m and the surface, using a 200 _m mesh net at a total of 49 stations (see Table 1 for station positions). The optical plankton counter (OPC) was deployed in vertical drops to within 15 m of the bottom or to 200 m, at 43 stations. The vertical net tows will provide information as to the species composition and biomass of the zooplankton (primarily copepods) and the OPC will provide information as to the vertical distribution of "particles", including copepods and at some stations large coagulated masses of phytoplankton. 4.2.1.2 Assessment of the suitability of the phytoplankton as a food source for zooplankton B. Irwin took chlorophyll profiles at many of the stations, in order to determine the biomass of phytoplankton present in the water column. In order to assess the value of this phytoplankton as food for copepods, samples were taken at the depth of the chlorophyll maximum and size fractionated at 3 mm. Particles smaller than this are unlikely to be a good food source for copepods. These samples will be analysed using high performance liquid chromatography, which will also indicate the presence of algae species thought to be noxious or toxic to zooplankton. The particulate organic carbon of the different size fractions will also be determined. 4.2.1.3 Assessment of differences between populations of Calanus finmarchicus occurring in the Labrador Sea, Scotian Shelf and Gulf of St. Lawrence In previous studies it has been found that there are differences in size-at-stage between stage V C. finmarchicus from the Labrador Sea and Scotian Shelf. This year the study was extended and samples were collected to see if there were also differences in the amounts of the heavy natural isotopes of nitrogen (N-15) and carbon (C-13). This was performed to see if these markers could be used to trace the movements of stocks of zooplankton in the region over a yearly time scale (lifetime of the animals). Samples were taken at 9 stations for these analyses. Samples were collected for Dr. A. Bucklin (U. of New Hampshire) for the analysis of the genetic make-up of C. finmarchicus females, which will allow the investigation of the movements of stocks of zooplankton over a time scale of several generations. Samples were taken at 9 stations for these analyses. Table 1. Stations samples by E. Head and L. Harris Biol. Stn.# . Position . Lat. . Deg. . . Position . . Lat. . . Min. . . . Position . . . Long. . . . Deg. . . . . Position . . . . Long. . . . . Min. . . . . . Date . . . . . . Ship's . . . . . . Time . . . . . . . Zooplankton . . . . . . . Sampling . . . . . . . Vertical Net . . . . . . . Tows . . . . . . . . OPC . . . . . . . . . Water . . . . . . . . . Sampling . . . . . . . . . CTD . . . . . . . . . . Water . . . . . . . . . . Sampling . . . . . . . . . . Pump . . . . . . . . . . . Chl. Max. . . . . . . . . . . . Depth (m) . . . . . . . . . . . . Metabollic . . . . . . . . . . . . Experiment . . . . . . . . . . . . Done . . . . . . . . . . . . . Samples . . . . . . . . . . . . . For N-15 . . . . . . . . . . . . . And C-13 . . . . . . . . . . . . . . Samples . . . . . . . . . . . . . . For . . . . . . . . . . . . . . genetic . . . . . . . . . . . . . . Studies 1 44 24 63 28 12.05 20.4 YES YES YES - 10 - - - 2 44 16 63 19 13.05 0.2 YES YES YES - 20 - - - 3 43 53 62 53 13.05 5 YES YES YES - 30 - YES - 4 43 29 62 27 13.05 14.4 YES YES YES - 40 - - - 5 43 11 62 6 13.05 18 YES YES YES - 50 - - - 6 42 52 61 44 13.05 23.45 YES YES YES - 30 - YES - 7 43 33 61 24 14.05 4.4 YES YES YES - 50 - - - 8 43 28 59 54 14.05 13.4 YES YES YES - 50 - - - 9 44 29 58 30 14.05 20.45 YES YES YES - 40 - - - 10 44 8 58 11 15.05 1 YES YES YES - 50 - YES - 11 43 47 57 50 15.05 3.2 YES YES YES - 40 - - - 12 44 25 57 2 15.05 10.4 YES YES - YES 50 - - - 13 44 42 56 12 15.05 15.2 YES - YES - 40 - - - 14 44 53 55 23 15.05 20 YES - YES - 30 - - - 15 45 13 54 0 16.05 2.2 YES - YES - 50 - - - 16 47 3 52 33 16.05 14.15 YES YES - YES 50 - - YES 17 48 1 52 30 16.05 19.1 YES YES - - - - - - 18 50 20 52 52 17.05 8 YES YES - YES 60 1 - YES 19 52 4 54 13 17.05 19.1 YES YES - - - - - - 20 53 40 55 33 18.05 7.15 YES YES - YES 10 2 - YES 21 54 13 55 2 18.05 16.05 YES YES - YES 30 - - - 22 54 45 54 29 18.05 22.22 YES YES - - - - - - 23 54 54 54 4 19.05 7.55 YES YES - YES 20 3 - YES 24 55 7 54 3 19.05 15.15 YES YES - YES 10 - YES - 25 55 16 53 59 19.05 18.15 YES YES - - - - - - 26 55 25 53 50 19.05 21.45 YES YES - - - - - - 27 55 51 53 24 20.05 6.04 YES YES - YES 10 4 YES YES 28 56 7 53 7 20.05 12.2 YES YES - YES 30 - - - 29 56 32 52 41 20.05 20.35 YES YES - - - - - - 30 57 22 51 51 22.05 7 YES YES - YES 10 5 - - 31 57 48 51 20 22.05 11.3 YES YES - YES 10 - - - 32 58 13 50 53 22.05 18.3 YES - - - - - - - 33 59 29 49 29 23.05 15.15 YES - - - - - - - 34 59 45 49 10 23.05 20.3 YES - - - - - - - 35 60 12 48 47 24.05 7.15 YES YES - YES 10 6 YES YES 36 60 18 48 32 24.05 10.45 YES YES - - - - - - 37 60 22 48 29 24.05 15.5 YES YES - YES 10 - - - 38 60 27 48 22 24.05 19.1 YES YES - - - - - - 39 60 32 48 15 24.05 21.3 YES YES - - - - - - 40 59 4 49 57 25.05 7.42 YES YES - YES 10 7 YES - 41 58 39 50 25 25.05 11.4 YES YES - YES 40 - - - 42 55 6 54 7 27.05 6.08 YES YES - YES 10 8 - - 43 54 46 54 29 27.05 14 YES YES - YES 30 - - - 44 52 23 54 51 29.05 6.5 YES YES - YES 40 9 - - 45 51 35 56 24 29.05 15.2 YES YES - YES 30 - - - 46 49 27 59 31 30.05 6.35 YES YES - YES 60 10 - YES 47 48 38 59 41 30.05 13.45 YES YES - YES 10 - - - 48 47 33 59 20 30.05 21.27 YES YES - - - - YES YES 49 46 41 59 48 31.05 2.1 YES YES - - - - YES YES 4.2.1.4 Measurements of copepod metabolic rates Rates of respiration, oxygen consumption and ammonia excretion were measured for communities of copepods in ten incubation experiments. Samples were also taken in five of these experiments for the determination of the rates of release of dissolved organic carbon and nitrogen. 4.2.2 Bacteria and Autofluorescent Particles (Paul Dickie) Profiles of heterotrophic bacterial activity with depth over the photic zone were estimated at 11 pump stations using radioactively labelled (3H) thymidine and leucine. These tracers were added to seawater and incubated in deck boxes cooled by surface seawater and simulating light levels roughly corresponding to the light at the depth where the seawater was obtained. Bacterial numbers will be found from DAPI stained samples of seawater from each incubation depth. Additional experiments were performed to test for the effects of predation in the incubation bottles and to measure the stimulatory effect of adding thymidine or leucine to the bacteria in the seawater samples. No results will be available until the samples can be processed at BIO. Samples were taken at 35 stations. The samples were drawn every 10 m from the surface to either the bottom, 150 m (CTD), or 100 m (Pump), for later flow cytometric analysis of autofluorescent particles by Dr. Bill Li at BIO. The samples were preserved with 1% para- formaldehyde and frozen in liquid nitrogen. The autofluorescent particles might include prokaryotes (cyanobacteria) or eukaryotes (small phytoplankton cells). As well, the samples _may_ be stained with a fluorescent nucleic dye to enumerate heterotrophic bacteria. Seawater of 4 different salinities was collected for use as sheath fluid in Dr. Li's flow cytometer. Phytoplankton samples were collected at 32 stations at 10m to determine actual numbers and assemblages of phytoplankton to correlate with the flow cytometer data, with chlorophyll values and possibly with Dr. E. Head's HPLC samples from the same water. 4.2.3 Feeding Experiments with Copepods Collected during Different Stages of the Spring Bloom in the North Atlantic Ocean and Labrador Sea (Catherine J. Stevens) L. Harris, using a 200 _m mesh net collected experimental animals (natural mixtures of copepods) in vertical net tows from 100 m to the surface. The abundance and vertical distribution of phytoplankton, as determined upon deployment of the biological pump, were used to assess the stage of the spring bloom (i.e., pre-bloom, mid-bloom, or post-bloom) and feeding history of the copepods. The copepods were starved for approximately 3 hours before the experiment was set up, allowing time for them to empty their guts of in situ food. The copepods were rinsed of adhering phytoplankton and divided into roughly equal numbers through systematic dilution with filtered seawater. They were then confined to 1 litre polycarbonate bottles (between 20 to 40 animals per bottle) and supplied with natural phytoplankton or one of two cultured diatoms, Thalassiosira and Coscinosira, over a series of five concentrations (see Table 2 for details about each experiment). At each food concentration, three experimental bottles (copepods and food) and one control bottle (food only) were set up. Initial and final samples (after about 10 hours) of control bottles were taken and frozen for HPLC analysis (high-performance liquid chromatography) and determination of total particulate chlorophyll by fluorometry. The entire contents of the experimental bottles (copepods, food and fecal pellets) were filtered for HPLC analysis. Samples of the experimental copepods were preserved in formalin for species identification and identification of copepodite stages within individual species. When natural phytoplankton was used as a food source, samples were taken and preserved with Lugol's solution for taxonomic analysis. In addition, samples of the experimental copepods and algae were taken and frozen in cryovials for enzyme assays. Analysis of the samples taken during the feeding experiments described above will allow the calculation of the following parameters: 1. the ingestion rates of the copepods in terms of phytoplankton pigment, 2. the percentage of the ingested pigment (chlorophylls and carotenoids) which has been converted into colorless residues (i.e., destroyed), and 3. the contribution of this destruction to CBEs (chlorophyll-bleaching enzymes) in both the experimental phytoplankton and copepods. Table 2. Feeding Experiments with Copepods from the North Atlantic and Labrador Sea Date Biol. Approximate Stage of Food Source Sta Location Spring # Bloom 14/05/96 8 off Sable Island post-bloom Thalassiosira 16/05/96 16 Laurentian Channel post-bloom natural phytoplankton 17/05/96 18 off St. John's, NF post-bloom Thalassiosira 18/05/96 20 beg. of WOCE line mid-bloom natural phytoplankton 19/05/96 23 Labrador Sea mid-bloom natural phytoplankton 20/05/96 27 Labrador Sea mid-bloom Thalassiosira 22/05/96 30 Labrador Sea pre-bloom Coscinosira 24/05/96 35 Labrador Sea (off Greenland) pre-bloom naturalphytoplankton 25/05/96 40 Labrador Sea pre-bloom Thalassiosira 27/05/96 42 Labrador Sea mid-bloom natural phytoplankton 29/05/96 54 Strait of Belle-Isle post-bloom Thalassiosira 30/05/96 56 Gulf of St. Lawrence post-bloom Thalassiosira 4.2.4 Respiration and the Size Fractionation of Dissolved Organic Carbon (DOC) (P. E. Kepkay / J. B. C. Bugden) The first direct measurements of microbial community respiration in the Labrador Sea were carried out on samples collected to depths of up to 100 m by the biological pump. Ten of the 28 sites on the WOCE line were sampled and respiration was typically measured at the three depths where phytoplankton productivity was established. Our application of the new pulsed-oxygen- electrode respirometer to these oceanic waters allowed us to carry out short-term (2 h) incubations at in-situ temperatures and minimize the artifacts generated by "bottle effects" associated with traditional long-term (1 to 5 d) incubations. Samples taken by pump for DOC analysis were ultrafiltered to size fractionate the DOC into colloidal organic carbon (COC) and low molecular weight organic carbon (LOC). This size fractionation of surface waters was performed on the same samples taken for respiration measurements. A selection of bottles from WOCE CTD casts were also sampled for DOC analysis to establish the organic carbon signal associated with the major water masses that had been defined by salinity, temperature and tracer measurements. Given the fact that DOC is by far the largest pool of organic carbon in the world's ocean and given the possible association of respiration with COC (the biologically-reactive component of DOC), we will use the data to establish: 1. The approximate age of DOC in the main water masses. 2. The contribution of DOC flux to the biological and/or physical pumps, which transport atmospheric CO2 into deep water. 3. The contribution that the respiration of COC makes to "preformed" TCO2 and the deep flux of atmospheric CO2 by the physical pump. 4.2.5 Primary Production Program (B. Irwin, J. Anning, A. Macdonald and J. Spry) Water samples for PI experiments were collected using the Biological Pump. Depths were selected on the basis of physical features or fluorescence structure. A total of 44 experiments were done at 21 locations. DATE LAT LONG DEPTHS May 15 44 27N 57 01W 10,30,50 May 16 47 02N 52 32W 10,30,50 May 17 50 20N 52 53W 10,30,50 May 18 53 41N 53 41W 10,30,50 May 18 54 13N 55 02W 10 May 19 54 55N 54 06W 10,20,30 May 19 55 07N 54 03W 10 May 20 55 51N 53 23W 10,20,40 May 20 56 07N 53 08W 30 May 22 57 22N 51 51W 10,20,40 May 22 57 47N 51 21W 10 May 24 60 12N 48 46W 10,30,50 May 24 60 22N 48 27W 10 May 25 59 04N 49 57W 10,30,50 May 25 58 38N 50 25W 40 May 27 55 06N 54 07W 10,20,30 May 27 54 46N 54 28W 30 May 29 52 23N 54 51W 10,30,50 May 29 51 35N 56 25W 30 May 30 49 27N 59 31W 10,20,30 May 30 48 37N 59 41W 10 At each of the sampled depths water was filtered for chlorophyll concentration, HPLC, Particulate Organic Carbon and Nitrogen. Pump profiles were from the surface to 100m or the bottom at shallow stations. Samples were collected at 10 m intervals for inorganic nutrients, chlorophyll concentration and total dissolved inorganic carbon. 4.2.6 Surface Water Continuous Monitoring System (B. Irwin, J. Anning, A. Macdonald and J. Spry) Water from approximately 4 m was pumped continuously up to the forward lab. The temperature, conductivity and fluorescence of this flow was continuously measured and logged every 30 seconds. The temperature and conductivity were measured with Seabird sensors and the fluorescence by a Wet Labs Inc. follow-through fluorometer. Incident Photosynthetically Active Radiation (PAR) was measured with a Biospherical PAR sensor and the data merged with the seawater parameters. Exact positions were logged at the same time from a Raytheon GPS. Discrete water samples were collected every 10 minutes by an auto sampler for later analysis for phosphate, nitrate and silicate. A NAS 2 nitrate analyzer, on loan from WS Ocean Systems for evaluation, was incorporated into the flowthrough system. Nitrate concentration was measured every 10 minutes. This data will be compared with the concentrations found in the discrete samples. 5. Major Problems and Goals Not Achieved The failed recovery of 70% of the mooring along AR7W is a major disappointment. The component of the mooring that sunk still contains a functioning release mechanism, thus enabling us to locate the end of the mooring line. An unsuccessful dragging attempt was made to recover the mooring line. We hope to attempt recovery of the mooring again in October 1996. Due to poor weather, the replacement mooring along AR7W at ca. 3500 m was not deployed. 6. Other Incidents of Note During equipment trials in Bedford Basin on Friday May 10, the CTD, LADCP and rosette were lost. A combination of mechanical failure and incorrect winch operation resulted in the package breaking free of the winch cable and falling to the bottom of Bedford Basin, in about 70 m of water. The package was recovered on Saturday May 11 using an underwater remotely operated vehicle, which was used to attach a line to the rosette frame. The package was found in an upright position on the bottom. The package was retrieved with minor damage, this being several broken spigots on the Niskin bottles. The duct system was flushed and cable was re-terminated. CTD equipment tests on Sunday May 12 showed problems with the pump power cable Y- splice. This Y-splice is required because of the dual system configuration on the package. The power cable is spliced to supply power to both pumps. A new splice corrected the problem. 7. List of Cruise Participants Name Responsibility Affiliation Jeff Anning Underway Sampling BIO Rick Boyce CTD/Watchkeeper BIO Jay Bugden "DOC levels, Respiration" JSE Paul Dickie Bacterial Abundance and activity BIO Bob Gershey CFC/Alkalinity/Carbonate BDR Research Les Harris Zooplankton BIO Albert Hartling Moorings/Watchkeeper BIO Erica Head Zooplankton BIO Mike Hingston CFC/Alkalinity/Carbonate BDR Research Brian Irwin "Phytoplankton, CO2" BIO Anthony Isenor Data Quality/Computers BIO Paul Kepkay "DOC levels, Respiration" BIO Samar Khatiwala Helium/Tritium Sampling LDEO John Lazier Chief Scientist BIO Al MacDonald Chlorophylls/Oxygens BIO Manon Poliquin Salinometer/Oxygens Murray Scotney Moorings/Watchkeeper BIO Jeff Spry Pump Sampling BIO Catherine Stevens Zooplankton Dal Igor Yashayaev Scientist/Watchkeeper Shirshov Frank Zemlyak CFC/Alkalinity/Carbonate BIO BIO Bedford Institute of Oceanography P.O. Box 1006 Dartmouth, NS, Canada, B2Y 4A2 BDR BDR Research Ltd. Box 652, Station 'M' Halifax, N.S., Canada, B3J 2T3 Dal Dalhousie University Halifax, Nova Scotia JSE J and S Envirotech Dartmouth, Nova Scotia LDEO Lamont-Doherty Earth Observatory of Columbia University Palisades, NY, 10964, USA B.UNDERWAY MEASUREMENTS 1. Navigation and Bathymetry (Anthony W. Isenor) The navigation system onboard CSS Hudson consisted of a Differential GPS receiver and AGCNAV. The system also broadcasts navigation NMEA strings throughout the ship's network about 1 Hz. The navigation data are then logged at one-minute intervals on a PC. This PC was running the AGCNAV software package; a PC based display, and waypoint setting software package developed at the Atlantic Geoscience Centre at BIO. This software graphically displayed ship position, waypoints, course, speed, etc. The echo sounder system consisted of a Raytheon Line Scan Recorder, Model LSR 1811-2 (serial number A117) connected to a hull mounted 12kHz transducer. The transducer beam width was 15 degrees. The sweep rate of the recorder was adjusted throughout the course of data collection to aid in identifying the bottom signal. The recorder was also linked to a clock, and thus could indicate 5 minute intervals on the sounder paper. The system was used to collect soundings at 5 minute intervals while underway for most of the cruise. 2. Acoustic Doppler Current Profiler (Murray Scotney) The Hudson was equipped with a hull mounted RDI Acoustic Doppler Current Profiler (ADCP). The transducer (serial number 177) had SC ADCP electronics (serial number 607) converted for ship board use. Logging, using Transect software on a 386 PC, was started on May 12, 1996 at 2221 Z along the Scotian Shelf. The configuration of the equipment resulted in a bin length of 4 metres and a total of 128 bins. The raw data were stored to disk and backed up every few days. The data was also averaged in real-time over 1 minute intervals. ADCP logging was stopped on June 1, 1996 at 1021 Z in Halifax Harbour. 3. XBT and XCTD No probes were used 4. Meteorological observations The ship's crew carried out routine reporting of meteorological variables. 5. Atmospheric Chemistry There was no atmospheric chemistry programme. C. HYDROGRAPHIC MEASUREMENTS - DESCRIPTIONS, TECHNIQUES AND CALIBRATIONS 1. CTD Measurements (Igor Yashayaev and Anthony W. Isenor) a. Description of the Equipment and Technique The CTD measurements were made with a standard SEABIRD model 9Plus CTD (S/N 09P 7356-0299, BIO System #4, deck unit S/N 11P9984-0353). This CTD was equipped with two model 3-02/F temperature sensors, two model 4-02/0 conductivity sensors, a paroscientific digiquartz model 410K-105 pressure sensor and two model 13-02 dissolved oxygen sensors. All but the pressure sensor were mounted in one of two ducts through which separate pumps pulled seawater. Hence the water flow past the actual sensors was independent of the lowering rate. The dual sensors used in the configuration consisted of the BIO System #4 as the primary set and BIO System #3 or #2 as secondary. Each set of sensors had a separate duct system for flowing water past the sensors. The sensors used for each System and the Systems used for each station are listed below. BIO System Number Sensor Serial Number System #4 (Primary) Temperature 031422 Conductivity 041124 Oxygen 130284 Pressure 53355 System #3 (Secondary) Temperature 031376 Conductivity 041076 System #2 (Secondary) Temperature 031205 Conductivity 040996 Secondary Oxygen Oxygen 130265 (both Systems #3 and #2) Station Number System Pairing (Primary, Secondary) 1-7 4,3 8-16 4,2 21-33 4,3 34-39 4,2 40-49 4,3 The Seabird CTD was mounted vertically within a custom designed and built CTD/Rosette frame. This frame was square rather than round to better accommodate the restricted space of Hudson's winch room and winch room door. All the pressure cases as well as the sample bottles were mounted vertically to improve the package's stability as it descended through the water column. In the centre of the frame was a 10 inch diameter aluminum tube, which contained at its upper end a General Oceanics Model 1015-24 bottle rosette unit (BIO rosette #3, S/N 1185). The bottom of this tube was designed to hold an RDI 150 kHz Broadband ADCP in a shortened pressure case. On another side was clamped the pressure case for the Seabird CTD. The CTD sensors and pump were mounted on the third side and on the fourth was clamped a rechargeable battery pack for the ADCP and below it a General Oceanics model 6000 12 kHz pinger unit. The rosette bottles were produced by the Physical and Chemical Oceanographic Data Facility located at the Scripps Institution of Oceanography. Six bottles were mounted to each side of the rosette frame. Each bottle collected 10 litres of water. A fluorometer was also attached to the CTD for measuring chlorophyll concentrations. b. Sampling Procedure and Data Processing Techniques The CTD was deployed with a lowering rate of 60 metres/min (40 metres/min in the upper 200 metres or deeper if the conditions were rough). It was recovered at a rate of 60 metres/min. The CTD data was recorded onto the disk of a 486 PC running SEABIRD SEASOFT Version 4.216 software. A screen display of temperature, oxygen and salinity profiles vs pressure were used to decide the depths at which bottles were to be tripped on the up cast. The bottles were tripped using the enable and fire buttons on the SEABIRD deck unit. At the end of each station, the SEASAVE software was used to create 1 and 2 dbar processed data files, an inflection point file and a processed rosette trip file. All the raw and processed data files associated with the station were then transferred to the ship's MicroVAX computer for archive and subsequent access and distribution to various users on the vessel. The data processing takes the following steps: DATCNV Converted the raw data to physical parameters. SPLIT Split the data into DOWN and UP cast. WILDEDIT This program took consecutive blocks of 12 scans and flagged all scans whose pressure, temperature and conductivity values differed from the mean by more than 2 standard deviations. Then the mean and standard deviation were recomputed using the unflagged data and all scans exceeding 4 standard deviations from this new mean were marked as bad. FILTER Low pass filtered pressure and conductivity channels. Time constant used for conductivity was 0.045 seconds, for pressure 0.150 seconds. LOOPEDIT Marked as bad, all cycles on the down trace for which the vertical velocity of the CTD unit was less than 0.1 meters/sec. ALIGNCTD Aligned the temperature, conductivity and oxygen values relative to the pressure values to account for the time delays in the system. The time offsets for the primary sensors were 0.010 seconds for conductivity, 0.000 seconds for temperature and 3.000 seconds for oxygen. The time offsets for the secondary sensors were 0.083 seconds for conductivity, 0.000 seconds for temperature and 3.000 seconds for oxygen (NOTE: the primary conductivity was adjusted by 0.073 seconds in the Deck unit while the secondary conductivity was not adjusted in the Deck unit.). CELLTM A recursive filter was used to remove the thermal mass effects from the conductivity data. Thermal anomaly amplitude and time constants of 0.0300 and 9.0000 were used. DERIVE Computed oxygen values. BINAVG Averaged the down cast into 1 and 2 dbar pressure bins. DERIVE Computed salinity, potential temperature and sigma-theta. ROSSUM Averaged 3 seconds of CTD data after every bottle trip. Used in comparison with water sample data. c. Calibration Data After considering the CTD temperature measurements as compared to the digital thermometers (see Reversing Thermometer Replicate Analysis section), we noted that the interthermometer comparison indicated differences of 0.002_C. The differences between the thermometers and the CTD were also about 0.002_C. Thus, we did not apply any temperature calibration to the CTD. However, oxygen and salinity calibrations were necessary. A calibration summary is presented in Table C1. Sensor Information 24 Hz Data 1 and 2 dbar data Parameter System of Shipboard First Second Sensors Processing Calibration Calibration Pressure System #4 1-16 21-49 Temperature System #2 8-16 8-16 34-39 (1) 34-39(1) I, II System #3 1-7 1-7(2) 21-33 21-33(2) 40-49 40-49(2) I, II System #4 1-16 1-16(3) 21-49 21-49(3) I, II Conductivity System #2 8-16 8-16(4) 34-39 34-39(4) I, II System #3 1-7 1-7(5) 21-33 21-33(5) 40-49 40-49(5) I, II System #4 1-16 1-16(6) 21-49 21-49(6) I, II Salinity System #2 8-16 8-16(9) 34-39 34-39(9) I, IV System #3 1-7 1-7(10) 21-33 21-33(10) 40-49 40-49(10) I, IV System #4 1-16 1-16(11) 21-49 21-49(11) I, IV Oxygen Systems #2 1-16 1-16(7) 21-49 21-49(7) I, III System #4 1-16 1-16(8) 21-49 21-49(8) I, III Table C1. CTD Calibration Summary. Shipboard Processing, First Calibration and Second Calibration represent sections in the text. The numerals I, II, III and IV represent procedures that were followed to determine the applied coefficients. These procedures are described in section (iv) Calibration Procedure. The numerics (e.g. 8 - 20) represent station numbers. Superscripts represent equation numbers in sections (ii) and (iii). i. Shipboard Processing The CTD calibrations used during this cruise were supplied by Seabird Electronics. The slope and offset applied to the various sensors was based on calibrations determined at BIO. The applied calibrations are as follows: BIO SEABIRD CTD System #4 During the cruise the temperature sensor for System #4 used two different sets of slope and offset pairings. The most recent BIO calibration slope and offset were specified for the System #4 temperature sensor when the system pair (4,3) was being used. However, the slope and offset for the System #4 temperature sensor were slightly different when the system pair (4,2) was being used. During the reprocessing of the CTD data, both system pairs used the most recent temperature sensor coefficients originally specified for the (4,2) system pair. Temperature Sensor (031422) T = 1/{a + b[ln(fo/f)] + c[ln2[fo/f] + d[ln3(fo/f)]} - 273.15 where ln indicates a natural logarithm, f is the frequency a = 3.68096068 E-03 b = 5.98528033 E-04 c = 1.47933699 E-05 d = 2.18572143 E-06 fo = 6142.890 slope = 1.00013300, offset = 0.0044 (Calibration dated Feb. 13, 1996) {used by the (4,3) system pairing} slope = 1.00013650, offset = 0.0043 {used by the system (4,2) pairing} Pressure Sensor (53355) pressure = c (1 - To2/T2) (1 - d[1 - To2/T2]) where T is the pressure period c = c1 + c2 U + c3 U2 d = d1 + d2 U To = T1 + T2 U + T3 U2 + T4 U3 + T5 U4 U is the temperature c1 = -4.290243 E+04 psia c2 = 5.13724 E-01 psia/_C c3 = 1.33407 E-02 psia/_C2 d1 = 4.0395 E-02 d2 = 0 T1 = 2.993058 E+01 _sec T2 = -8.85537 E-05 _sec/_C T3 = 3.59773 E-06 _sec/_C2 T4 = 5.58385 E-09 _sec/_C3 T5 = 0 AD590M = 1.146000 E-02 AD590B = -8.11354 E+00 slope = 1, offset = 0 (Seabird calibration, Feb. 2, 1993) Conductivity Sensor (041124) conductivity = (afm + bf2 + c + dt)/[10(1-{CPcor p})] where f is the frequency, p is pressure in dbar, t is the temperature m = 4.2 a = 1.35924955 E-05 b = 4.87959496 E-01 c = -4.19483432 E+00 d = -1.04684736 E-04 CPcor = -9.5700 E-08 Slope = 1.000560 E+00, Offset = -9.60 E-04 (Calibration dated Feb. 15, 1996) Oxygen Sensor (130284) Oxygen = where Soc = 2.5328 oc is the oxygen sensor current (_amps) oc = mV + b m = 2.4528 E-07 V is the oxygen temperature sensor voltage signal b = -3.9245 E-09 tau = 2.0 is the time derivative of oc Boc = -0.0322 OXSAT is the oxygen saturation value dependent on T and S T is the water temperature (_C) S is salinity (psu) e is natural log base tcor = -0.033 wt = 0.670 To oxygen sensor internal temperature (_C) To = kV + c k = 8.9625 c = -6.9161 pcor = 1.5 E-04 P is the pressure (psia) BIO SEABIRD CTD System #3 Temperature Sensor (031376) T = 1/{a + b[ln(fo/f)] + c[ln2[fo/f] + d[ln3(fo/f)]} - 273.15 where ln indicates a natural logarithm, f is the frequency a = 3.68093833 E-03 b = 6.00726775 E-04 c = 1.51819564 E-05 d = 2.19535579 E-06 fo = 6482.310 slope = 1.000148, offset = -0.000800 (Calibration dated Jan. 23-24, 1996) Conductivity Sensor (041076) conductivity = (afm + bf2 + c + dt)/[10(1-{CPcor p})] where f is the frequency p is pressure in dbar t is the temperature m = 4.1 a = 2.21442246 E-05 b = 5.67193159 E-01 c = -4.19781901 E+00 d = -1.23661793 E-04 CPcor = -9.5700 E-08 Slope = 1.000524 E+00, Offset = -1.130 E-03 (Calibration dated Jan. 26, 1996) BIO SEABIRD CTD System #2 Temperature Sensor (031205) T = 1/{a + b[ln(fo/f)] + c[ln2[fo/f] + d[ln3(fo/f)]} - 273.15 where ln indicates a natural logarithm f is the frequency a = 3.68701470 E-03 b = 6.04767412 E-04 c = 1.60190147 E-05 d = 2.56736249 E-06 fo = 6167.520 slope = 1.000150, offset = 6.100 E-03 (Calibration dated Jan. 23-24, 1996) Conductivity Sensor (040996) conductivity = (afm + bf2 + c + dt)/[10(1-{CPcor p})] where f is the frequency p is pressure in dbar t is the temperature m = 4.1 a = 2.53328870 E-05 b = 5.95111155 E-01 c = -4.22225011 E+00 d = -2.08943055 E-04 CPcor = -9.5700 E-08 Slope = 1.00078920, Offset = -1.330 E-03 (Calibration dated Jan. 26, 1996) Oxygen Sensor (130265) Oxygen = where Soc = 2.4323 oc is the oxygen sensor current (_amps) oc = mV + b m = 2.4608 E-07 V is the oxygen temperature sensor voltage signal b = -4.9216 E-10 tau = 2.0 is the time derivative of oc Boc = -0.0397 OXSAT is the oxygen saturation value dependent on T and S T is the water temperature (_C) S is salinity (psu) e is natural log base tcor = -0.033 wt = 0.670 To oxygen sensor internal temperature (_C) To = kV + c k = 8.9939 c = -6.8210 pcor = 1.5 E-04 P is the pressure (psia) ii. First Calibration The generated shipboard 1dbar downcast ODF (Ocean Data Format, specific to BIO) data and the water sample data were used to determine calibrations (given below) for all primary and secondary sensors. All of these calibrations were applied on June 1, 1996. Only the slope and offset changed for the temperature and conductivity sensors. Only the coefficients SOC, BOC, tcor and pcor changed for the oxygen sensors. These new calibrations were then applied to the raw 24 Hz data. a) Temperature sensor coefficients for System #2 were changed according to Eqn. 1 below. b) Temperature sensor coefficients for System #3 were changed according to Eqn. 2 below. c) Temperature sensor coefficients for System #4 in the con file for the (4,3) system pair were changed to the ones used for (4,2) system pair according to Eqn. 3 below. d) Conductivity sensor coefficients for System #2 were changed according to Eqn. 4 below. e) Conductivity sensor coefficients for System #3 were changed according to Eqn. 5 below. f) Conductivity sensor coefficients for System #4 were changed according to Eqn. 6 below. g) Secondary oxygen sensor coefficients for System #2 were changed according to Eqn. 7 below. h) Primary oxygen sensor coefficients for System #4 were changed according to Eqn. 8 below. a) Temperature Sensor #2 (031205) T = 1/{a + b[ln(fo/f)] + c[ln2[fo/f] + d[ln3(fo/f)]} - 273.15 Eqn. 1 where ln indicates a natural logarithm f is the frequency a = 3.68701470 E-03 b = 6.04767412 E-04 c = 1.60190147 E-05 d = 2.56736249 E-06 fo = 6167.520 slope = 1.00016000, offset = 5.600 E-03 b) Temperature Sensor #3 (031376) T = 1/{a + b[ln(fo/f)] + c[ln2[fo/f] + d[ln3(fo/f)]} - 273.15 Eqn. 2 where ln indicates a natural logarithm, f is the frequency a = 3.68093833 E-03 b = 6.00726775 E-04 c = 1.51819564 E-05 d = 2.19535579 E-06 fo = 6482.310 slope = 1.000141, offset = 0 (Calibration dated June 1, 1996) c) Temperature Sensor #4 (031422) T = 1/{a + b[ln(fo/f)] + c[ln2[fo/f] + d[ln3(fo/f)]} - 273.15 Eqn. 3 where ln indicates a natural logarithm, f is the frequency a = 3.68096068 E-03 b = 5.98528033 E-04 c = 1.47933699 E-05 d = 2.18572143 E-06 fo = 6142.890 slope = 1.000137, offset = 0.004300 (Seabird calibration dated February 13, 1996) d) Conductivity Sensor #2 (040996) conductivity = (afm + bf2 + c + dt)/[10(1-{CPcor p})] Eqn. 4 where f is the frequency p is pressure in dbar t is the temperature m = 4.1 a = 2.53328870 E-05 b = 5.95111155 E-01 c = -4.22225011 E+00 d = -2.08943055 E-04 CPcor = -9.5700 E-08 Slope = 1.000780, Offset = -5.60 E-04 e) Conductivity Sensor #3 (041076) conductivity = (afm + bf2 + c + dt)/[10(1-{CPcor p})] Eqn. 5 where f is the frequency p is pressure in dbar t is the temperature m = 4.1 a = 2.21442246 E-05 b = 5.67193159 E-01 c = -4.19781901 E+00 d = -1.23661793 E-04 CPcor = -9.5700 E-08 Slope = 1.000550, Offset = -1.310 E-03 f) Conductivity Sensor #4 (041124) conductivity = (afm + bf2 + c + dt)/[10(1-{CPcor p})] Eqn. 6 where f is the frequency, p is pressure in dbar, t is the temperature m = 4.2 a = 1.35924955 E-05 b = 4.87959496 E-01 c = -4.19483432 E+00 d = -1.04684736 E-04 CPcor = -9.5700 E-08 Slope = 1.000563, Offset = -8.300 E-04 g) Oxygen Sensor #2 (130265) Oxygen = where Soc = 1.33 oc is the oxygen sensor current (_amps) oc = mV + b m = 2.4608 E-07 V is the oxygen temperature sensor voltage signal b = -4.9216 E-10 tau = 2.0 is the time derivative of oc Boc = 0.446 OXSAT is the oxygen saturation value dependent on T and S T is the water temperature (_C) S is salinity (psu) e is natural log base tcor = -5.00 E-03 wt = 0.670 To oxygen sensor internal temperature (_C) To = kV + c k = 8.9939 c = -6.8210 pcor = 5.35 E-05 P is the pressure (psia) h) Oxygen Sensor #4 (130284) Oxygen = where Soc = 2.29 oc is the oxygen sensor current (_amps) oc = mV + b m = 2.4528 E-07 V is the oxygen temperature sensor voltage signal b = -3.9245 E-09 tau = 2.0 is the time derivative of oc Boc = 0.322 OXSAT is the oxygen saturation value dependent on T and S T is the water temperature (_C) S is salinity (psu) e is natural log base tcor = -6.00 E-03 wt = 0.670 To oxygen sensor internal temperature (_C) To = kV + c k = 8.9625 c = -6.9161 pcor = 8.00 E-05 P is the pressure (psia) iii. Second Calibration The second calibration was applied to the 1 and 2 dbar data sets that resulted from the first calibration, section (ii). The second calibration is represented in Eqns. 9 - 11. System #2 Sensor (secondary sensor for stations 8 - 16 and 34 - 39) SCAL = SUN - 0.000318 Eqn. 9 System #3 Sensor (secondary sensor for stations 1 - 7, 21 - 33 and 40 - 49) SCAL = SUN + 0.00051 - 2.827E-07 * P Eqn. 10 System #4 Sensor (primary sensor for all stations) SCAL = SUN + 0.000554 + 7.9841E-07 * P - 8.2712E-10 * P2 + 1.34E-13 * P3 Eqn. 11 where SCAL : Salinity Calibrated SUN : Salinity Uncalibrated P : Pressure iv. Calibration Procedure The calibration procedures for calibrating the CTD conductivity (see equations 4 - 6), CTD oxygen data (see equations 7 - 8) and CTD salinity data (see equations 9 - 11) are listed below. The CTD conductivity sensors only required modified offsets to be calculated. The CTD Oxygen sensors required new non-linear 'hardware' coefficients to be computed. The CTD salinity data required corrections based on CTD Pressure. The calibration parameters for the CTD oxygen data and the CTD salinity data were based on down trace CTD data and measurements of water sample oxygen concentration from bottles tripped on the uptrace. Although these data sets are inconsistent (to some degree) in time and spatial location, they were considered the only reliable source of information for calibration of CTD oxygen and CTD salinity data. The procedure for finding the calibrations to be applied to the CTD data were divided into four stages. Stage I applied only to the CTD conductivity data, stages II and III applied to the downcast CTD oxygen and stages II and IV applied to the downcast CTD salinity. Both stages II and III were iterative procedures. I. Creating a calibration file, II. Compute new offsets, III. Computing non-linear 'hardware' coefficients, IV. Computing corrections of residual effects of pressure, temperature and salinity (secondary correction). I. Creating a Calibration File 1) The calibration file is used for finding and testing calibrations (set of coefficients) later applied to the CTD data, while computing CTD Oxygen. A base for this file consisted of discrete CTD readings of temperature, pressure, salinity, etc.; averaged over three seconds at the depth and time of bottle tripping. The calibration file creation steps are outlined below; 2) Water sample salinity and oxygen concentration determined onboard were added to the calibration file; 3) For initial 'indirect' check of quality, the differences between water sample and calibrated CTD salinity were computed. If the absolute difference exceeded 0.004 the point (record) containing this data was considered unreliable and discarded from further analysis; 4) Next, a search and selection was performed for each record of the calibration file. The goal is to find a point in a downtrace profile in the same general water type. _ data from a downtrace profile were restricted to a certain pressure (or/and) density (or/and) temperature (or/and) salinity vicinity of the uptrace point (the calibration file). This defines a group. Typical criteria (definition of vicinity): differences between uptrace and downtrace pressure 25 dbar, potential temperature 0.5K, and salinity 0.02. [Note: For some upcast data points, no downcast point was found within the defined criteria. In these cases, the CTD oxygen in the SEA file is indicated with a null value of -9.0 and a quality flag of 9, not sampled.] _ find a point in the group which is closest to the uptrace data point (from the calibration file) in multidimensional space, where dimensions are normalized (weighted or rescaled) pressure, potential temperature, salinity and density. Normalization for each axis was done according to expected variability within a water type. In ultimate cases only one or two dimensions were chosen. The found point was identified as being "closest" to the upcast CTD data point at the time of bottle trip. At this point, the downtrace CTD data has been added to the calibration file. 5) Next the data set was split into sets based on distinct changes in the sensors behavior. The set represented quasi-steady periods of oxygen sensor behavior. This avoided extreme temporal drifts in any of the sets and allowed the use of the same non-linear coefficients for each set. II. Compute new offsets Temperature Sensor Calibration Using the calibration file, the median temperature difference between the two temperature sensors was computed and used for each deep station. The computed medians were then used to determine the adjustment to the temperature sensor's coefficients. Note: At this point the CTD data was reprocessed using the new temperature coefficients. Conductivity Sensor Calibration The calibration file was used to compare the conductivity acquired by the CTD with the water sample conductivity. The water sample salinities were converted to conductivities using the temperature measured by the CTD at the time of the bottle firing. In computing the new coefficients for the three conductivity sensors used on the cruise, the slopes changed only slightly from the original values, while the offsets changed more significantly. Note: At this point the CTD data was reprocessed using the new conductivity coefficients. III. Computing Non-linear 'Hardware' Coefficients 1) A nonlinear multiparametric least square technique was used to determine the oxygen sensor processing coefficients (soc, boc, tcor, and bcor) using oxygenws vs. downcast temperaturectd, salinityctd, pressurectd, oxygen currentctd and oxygen temperaturectd (where the ws/ctd subscripts represents water sample/CTD data). 2) Applying the results of step III.1, the oxygenctd was derived. 3) Compute oxygenws - oxygenctd. Statistics of the difference were computed and the records that produced outliers (no matter if the outliers were produced by oxygenws or oxygenctd) were marked or deleted from the calibration file. 4) Checking the oxygenws - oxygenctd distributions: _ if the differences (oxygenws - oxygenctd) are randomly distributed versus all parameters (temperature, pressure, oxygen current, and oxygen temperature) and there are no evident outliers, proceed to stage IV, _ otherwise, using the cleaned calibration file (derived in stage I and cleaned according to III.3) repeat all the steps of stage III until the first part of the check III.4 is true (typically, it requires 10 to 15 iterations to clean the calibration file and determine the oxygen sensor processing coefficients soc, boc, tcor, and bcor). Note: After stage III the CTD data was reprocessed using the Seabird software and the new oxygen coefficients. IV. Computing corrections of residual effects of pressure and salinity 1) Use the set of stations (as defined in I.5) to compute a polynomial fit of the differences (residuals) between the CTD salinity and water sample salinity given in the calibration file (first iteration on this stage) or IV.2 (second and higher iteration), individually for pressure and then salinity. 2) Subtract the polynomial correction, derived in IV.1, from the differences computed in IV.1. Check if there are any outliers. _ If these (new IV.2) residuals don't depend on pressure, salinity or time and their statistics is not improving with any sequential iteration (distribution getting tighter) advance to IV.3. _ Otherwise, use the results of step IV.2 and repeat step IV.1 until the first bulleted part of IV.2 is true. This iteration typically requires 7 to 14 repetitions. 3) Finalize calibration coefficients. v. CTD Quality Flagging and Data Delivery The processed 2 dbar CTD was quality flagged by applying "bad" flags to the near-surface data. These data would have been collected before the system pump was activated, and thus do not represent measurements from a properly operating system. This typically meant that the temperature, salinity and oxygen data above 10 dbar were flagged using WOCE flag "4". As well, some at-depth points were flagged as either questionable or bad, depending on subjective assessment of the density profile. Only the CTD data from the primary sensors are reported to the WOCE DAC. BIO archives data from both sensors. The Marine Environmental Data Service, MEDS, (Canada's NODC) will receive data from all sensors. 2. Salinity (Manon Poliquin) a. Description of Equipment and Technique Salinity samples were analyzed on one of two Guildline Autosal model 8400 salinometers, serial numbers 61083 and 60968. Samples were drawn in 150 ml medicine bottles. New caps, equipped with plastic liners, were placed on the sample bottles for each use. The salinometer cell was filled and rinsed three times with sample water before readings were recorded. Three readings of the salinometer were recorded for every sample and standardization. The last two readings were averaged and entered into the water sample database as the conductivity of the water sample. b. Sampling Procedure and Data Processing Technique Salinity samples were drawn into 150 ml medicine bottles after three rinses. The bottles were filled up to the shoulders and then capped with new caps with plastic liners. One conductivity file for the entire cruise was prepared. The file consisted of a sequential record number, the bath temperature, sample ID number, average conductivity ratio and a quality flag. A PC based program running under a commercial DBMS computed the salinity using the average conductivity ratio and the standard IAPSO formula. Any changes in the salinometer readings between successive standardizations were assumed to have occurred as a linear drift of the instrument. Thus, the program applied a correction to the ratios, which varied linearly with the samples analyzed. The salinity data was then placed in the water sample database. A total of 594 salinity values were obtained for this cruise. c. Laboratory and Sample Temperatures Full cases of samples were taken from the winch room to the GP lab where they were left for a period of at least 10 hours to equilibrate to laboratory temperature before being analyzed. The baths in both salinometers were kept at 24_C for all stations. d. Replicate Analysis A duplicate salinity sample was drawn from one of the rosette bottles on most casts. A total of 24 duplicate salinity samples were drawn and statistically analyzed. Statistics of the duplicate differences follow. Only acceptable values were used in calculating the duplicate differences. All of the duplicate sample values and their quality flags are listed in Table C.2 below. Statistic Value Number of Points 23 Minimum 0.0000 Maximum 0.0024 Mean 0.0006 Median 0.0004 Standard Deviation 0.0006 e. Standards Used The salinometer was standardized on May 14, 1996 using IAPSO standard water, Batch P124, prepared on January 18, 1994. A check on the standardization using a new ampoule was carried out at the beginning and end of every 32 bottle case and at intermediate points during a case if instrument drift was suspected. Table C.2 Replicate water sample salinity values with their quality flags. Sample ID Salinity WOCE QF Number 158186 32.8470 2 158186 32.8462 2 158190 33.0984 2 158190 33.0990 2 158194 33.2849 2 158194 33.2858 2 158204 33.5019 2 158204 33.5020 2 158211 33.0533 2 158211 33.0534 2 158217 34.2151 2 158217 34.2140 2 158225 34.8606 2 158225 34.8608 2 158237 34.8868 2 158237 34.8874 2 158254 34.8919 2 158254 34.8932 2 158292 34.8648 3 158292 34.8690 3 158316 34.8771 2 158316 34.8775 2 158340 34.8929 2 158340 34.8930 2 158368 34.8872 2 158368 34.8869 2 158391 34.8893 2 158391 34.8893 2 158413 34.8721 2 158413 34.8733 2 158438 34.9003 2 158438 34.9004 2 158472 34.8470 2 158472 34.8471 2 158483 34.8921 2 158483 34.8917 2 158518 34.8319 2 158518 34.8322 2 158529 34.8815 2 158529 34.8821 2 158552 34.8970 2 158552 34.8976 2 158595 34.9035 2 158595 34.9035 2 158614 34.8996 2 158614 34.9020 2 158630 32.8430 2 158630 32.8422 2 3. Oxygen (Manon Poliquin) a. Description of Equipment and Technique The oxygen samples were analyzed using an automated procedure developed by the Ocean Sciences Division (OSD) of the Bedford Institute of Oceanography (BIO) from a manual titration system (Levy et al. 1977). The OSD procedure was a modified Winkler titration from Carritt and Carpenter (1966), using a whole bottle titration. In this method there was no starch indicator and a wetting agent (Wetting Agent A, BDR) was introduced to reduce bubble formation. The automated titration system consisted of an IBM PC linked to a Brinkmann PC800 colorimeter and a Metrohm 665 Multi-Dosimat Automatic Titrator. A full description of the system and method can be found in Jones, et al. (1992) with the following exception: Pages 2-4, section 2.3 Method - Sample titration should read, 'The stopper is not replaced and the acid rinsed down the stopper's end into the flask. The end is then rinsed into the flask with deionized water. One drop of wetting agent and the magnetic stirring bar are then added.' b. Sampling Procedure and Data Processing Technique The sampling bottles were 125ml Iodine flasks with custom ground stoppers (Levy et al. 1977). The flask volumes were determined gravimetrically. The matched flasks and stoppers were etched with Identification numbers and entered into the Oxygen program database. For this cruise 10 litre rosette bottles were used to obtain the original sample. The oxygen subsamples were drawn immediately following the drawing of the CFC, DOC and helium subsamples. The oxygen subsamples were drawn through the bottle's spigot with a latex or silicone tube attached so as to introduce the water to the bottom of the flask. The flask and its stopper were thoroughly rinsed and filled to overflowing. The flow was allowed to continue until at least two to three flask volumes overflowed. The flask was then slowly retracted with continuous low flow to ensure that no air got trapped in the flask. The flask was then brought to the reagent station and one ml each of the Alkaline Iodide and Manganous Chloride Reagents were added. The stoppers were then carefully inserted; again ensuring that no air got into the flasks. The flasks were thoroughly shaken then carried to the lab for analysis. Some problems were encountered with the processing software. In particular, the oxygen program initially used to compute the end point and titrant volume failed. No immediate reason for the failure could be determined. The software would not load and resulted in the PC being hung. Reloading the software did not solve the problem. A second, newer version of the software was then loaded and functioned properly. The problem resulted in samples 158423 and 158424 being lost. The first sample used for the second version of the software was sample ID number 158425. It is unclear why the PC initially had the older version of the software. Due to the processing software problem noted above, we recommend upgrading the IBM PC- 2000 (XT) to a newer model. This change would involve adapting the database program to run on a 486 model. With a newer version of the computer it would be easier to switch to another computer in case of a malfunction. With the XT it is almost impossible to do so because of the scarcity of such models. Furthermore, having a complete backup copy of the database program on floppy disk is recommended for future missions. More complete version control tracking of the software is also required to allow traceability in the data processing. c. Replicate Analysis There were 657 unique sample id numbers that were analyzed for dissolved oxygen, of which 546 had one sample value, 35 had two sample values, 75 had three sample values and one had four sample values. At least a single replicate oxygen sample was drawn from one of the rosette bottles on every cast. On one cast, duplicate samples were drawn from five rosette bottles. All sample id numbers that had oxygen samples for stations two through eight had triplicate oxygen samples drawn. Statistics of the replicate differences follow. Only acceptable values were used in calculating the replicate differences. The calculated replicate statistics used the absolute value of the replicate differences. All of the replicate sample values and their quality flags are listed in Table C.3 below. Number of replicate differences = (34) sample id numbers having one replicate * (1) possible difference + (77) sample id numbers having two replicates * (3) possible differences = 265 Median of [(absolute difference/sample mean concentration of all samples) * 100%] = 0.38 % Statistic Value (_moles/kg) Minimum 0.0 Maximum 20.6 Mean 1.9 Median 1.0 Standard Deviation 2.6 Cumulative Frequency Oxygen Difference (_moles/kg) 50 % _ 1.0 68 % _ 1.9 95 % _ 6.5 Table C.3 Replicate water sample oxygen values in (moles/kg, along with their quality flags. Sample ID Oxygen WOCE QF Number 158001 327.3 2 158001 327.8 2 158001 326.7 2 158003 336.0 2 158003 336.7 2 158003 336.7 2 158004 345.7 2 158004 344.4 2 158004 344.9 2 158005 350.1 2 158005 349.4 2 158005 349.4 2 158006 357.6 2 158006 358.1 2 158006 358.3 2 158007 361.5 2 158007 360.9 2 158007 361.2 2 158008 361.5 2 158008 356.0 2 158008 354.1 2 158009 351.4 2 158009 351.5 2 158009 357.8 2 158010 204.5 2 158010 207.3 2 158010 209.2 2 158013 287.4 2 158013 288.8 2 158013 308.0 2 158015 305.0 2 158015 306.0 2 158015 306.2 2 158017 311.2 2 158017 311.7 2 158017 315.2 2 158019 338.9 2 158019 340.8 2 158019 339.6 2 158020 343.8 2 158020 344.1 2 158020 346.8 2 158021 346.3 2 158021 346.4 2 158021 347.7 2 158022 357.6 2 158022 358.2 2 158022 358.3 2 158023 355.8 2 158023 356.8 2 158023 357.6 2 158024 357.0 2 158024 357.1 2 158024 358.8 2 158025 354.7 2 158025 358.8 2 158025 357.0 2 158026 148.4 2 158026 150.0 2 158026 150.8 2 158027 150.9 2 158027 152.0 2 158027 152.0 2 158028 150.1 2 158028 155.8 2 158028 156.5 2 158029 150.8 2 158029 152.7 2 158029 152.9 2 158030 155.4 2 158030 157.5 2 158030 157.7 2 158032 166.2 2 158032 162.1 2 158032 160.6 2 158034 184.2 2 158034 192.1 2 158034 182.5 158036 184.5 2 158036 183.3 2 158036 184.8 2 158038 204.6 2 158038 205.0 2 158038 206.2 2 158040 238.7 2 158040 238.1 2 158040 238.5 2 158042 314.8 2 158042 315.3 2 158042 316.2 2 158043 335.7 2 158043 334.0 2 158043 335.7 2 158044 344.6 2 158044 339.8 2 158044 337.6 2 158045 335.6 2 158045 335.7 2 158045 339.4 2 158046 335.9 2 158046 337.7 2 158046 338.0 2 158047 209.7 2 158047 210.5 2 158047 211.2 2 158048 256.8 2 158048 256.9 2 158048 259.0 2 158049 314.5 2 158049 313.7 2 158049 313.8 2 158050 335.9 2 158050 334.8 2 158050 334.0 2 158051 323.9 2 158051 326.2 2 158051 330.5 2 158052 325.3 2 158052 326.4 2 158052 327.7 2 158053 323.6 2 158053 324.4 2 158053 328.3 2 158054 325.5 2 158054 326.1 2 158054 328.6 2 158056 259.9 2 158056 262.6 2 158056 263.4 2 158058 305.5 2 158058 306.5 2 158058 305.5 2 158059 315.8 2 158059 316.3 2 158059 316.7 2 158060 334.8 2 158060 335.3 2 158060 339.4 2 158061 338.2 2 158061 338.5 2 158061 339.8 2 158062 322.0 2 158062 324.9 2 158062 325.7 2 158063 324.2 2 158063 324.2 2 158063 326.5 2 158064 325.1 2 158064 323.9 2 158064 324.7 2 158065 172.5 2 158065 174.4 2 158065 174.7 2 158066 213.0 2 158066 213.6 2 158066 214.4 2 158067 227.1 2 158067 226.4 2 158067 226.5 2 158070 241.5 2 158070 238.2 2 158070 239.2 2 158072 245.0 2 158072 245.6 2 158072 246.0 2 158074 259.6 2 158074 259.2 2 158074 259.2 2 158076 293.9 2 158076 293.9 2 158076 293.4 2 158077 304.2 2 158077 300.2 2 158077 300.6 2 158078 321.7 2 158078 322.1 2 158078 324.6 2 158079 335.0 2 158079 335.3 2 158079 337.2 2 158080 331.4 2 158080 332.7 2 158080 334.8 2 158081 328.2 2 158081 326.5 2 158081 328.1 2 158082 327.8 2 158082 327.6 2 158082 327.5 2 158083 179.9 2 158083 182.2 2 158083 185.1 2 158084 184.2 2 158084 184.3 2 158084 185.0 2 158085 223.7 2 158085 223.8 2 158085 226.1 2 158088 243.0 2 158088 243.3 2 158088 244.1 2 158090 227.7 2 158090 230.2 2 158090 234.7 2 158092 233.4 2 158092 234.8 2 158092 234.4 2 158094 266.0 2 158094 266.6 2 158094 266.7 2 158095 293.5 2 158095 293.7 2 158095 294.0 2 158096 314.3 2 158096 316.4 2 158096 316.6 2 158097 313.5 2 158097 313.5 2 158097 316.9 2 158098 312.9 2 158098 314.1 2 158098 314.7 2 158099 311.4 2 158099 313.2 2 158099 311.3 2 158100 312.0 2 158100 312.6 2 158100 313.3 2 158185 336.3 2 158185 339.1 2 158189 318.5 2 158189 319.2 2 158196 401.7 2 158196 402.3 2 158198 322.5 2 158198 317.6 2 158206 341.1 2 158206 341.4 2 158208 306.5 2 158208 317.6 2 158214 291.5 2 158214 288.7 2 158224 290.9 2 158224 290.8 2 158234 286.6 2 158234 286.9 2 158251 292.0 2 158251 293.7 2 158271 302.5 2 158271 302.7 2 158296 275.6 2 158296 286.2 2 158318 285.5 2 158318 275.6 2 158337 291.2 2 158337 303.9 2 158360 300.7 2 158360 300.9 2 158374 295.7 2 158374 298.7 2 158388 297.2 2 158388 304.8 2 158412 303.1 2 158412 304.0 2 158412 304.9 2 158414 298.4 2 158414 298.6 2 158421 299.7 2 158421 299.8 2 158434 303.3 2 158434 303.3 2 158440 282.6 2 158440 281.9 2 158442 282.0 2 158442 285.4 2 158444 298.6 2 158444 298.9 2 158446 298.8 2 158446 299.0 2 158457 305.1 2 158457 305.3 2 158480 296.1 2 158480 303.1 2 158505 300.4 2 158505 300.5 2 158526 303.3 2 158526 303.5 2 158553 288.0 2 158553 287.3 2 158572 294.0 2 158572 294.5 2 158596 286.2 2 158596 287.4 2 158613 285.0 2 158613 285.5 2 158627 340.8 2 158627 341.5 2 158631 355.7 2 158631 355.5 2 4. Nutrients a. Description of Equipment and Technique Nutrient samples for this cruise were analyzed at the Bedford Institute of Oceanography. The samples were drawn and stored as described below. b. Sampling Procedure and Data Processing Technique Duplicate nutrient subsamples were drawn into 30 ml HDPE (Nalge) wide mouth sample bottles from 10 L Niskins. The bottles were 10% HCl washed, rinsed once with tap water, three times with Super-Q and oven dried at >100 _F. Within about 30 minutes of drawing, the samples were placed in a deep freezer and stored at -13 _C. c. Replicate Analysis A total of 1234 seawater samples were analyzed for silicate, phosphate and NO2+NO3. Included in these samples were a total of 615 duplicate samples and 1 quadruplicate samples. Statistics relating to the precision of the sample values follow. All values are given in _moles/kg. Only the samples that had acceptable replicate values were included in the statistics. All replicate values and their quality flags are given in Table C.4. Precision is a measure of the variability of individual measurements and in the following analysis two categories of precision were determined: field and analytical precision. Analytical precision is based on the pooled estimate of the standard deviation of the check standards over the course of a complete autoanalyzer run and is a measure of the greatest precision possible for a particular analysis. Field precision is based on the analysis of two or more water samples taken from a single Niskin sampling bottle and has an added component of variance due to subsampling, storage and natural sample variability. Both categories of precision were determined by computing the variance, , of each replicate set, where "i" is the index of the replicate set. In the case of analytical (field) precision, a replicate set consisted of all the check standards (duplicate samples). Given p replicate sets and n samples within any replicate set, the mean standard deviation, , was determined from The precision expressed in percent was based on the mean concentration (M) of the check standards (analytical precision) or water samples (field precision) and was given by The following table indicates the analytical and field precision obtained for this cruise. Statistic Silicate Phosphate NO2+NO3 Number of Samples 1234 2068 1231 Number of Replicates 577 577 574 Mean concentration ((moles/kg) 7.59 0.90 11.34 Field Precision ((moles/kg) 0.81 0.07 1.08 Field Precision (%) 10.73 7.72 9.48 Analytical Precision ((moles/kg) 0.32 0.05 0.20 Analytical Precision (%) 0.88 3.26 1.07 Detection Limit ((moles/kg) 0.30 0.02 0.10 The laboratory temperature during all analyses was between 21 and 23 °C. The conversion to mass units for the analytical precision and detection limits used a standard density of 1.02443 kg/litre corresponding to 33 ppt and 15_C. The conversion of individual sample values from volume to mass units used a potential density with a fixed temperature of 15_C. Duplicate samples were drawn from each rosette bottle for the determination of silicate, phosphate and nitrate concentrations. The nutrient detection limits noted in the above table were applied to the dataset. All values at or below the detection limits were set to zero. Table C.4 Replicate nutrient water sample values in (moles/kg, along with their quality flags. ID SiO2 PO4 NO2+NO3 QF 158001 2.38 0.76 1.18 222 158001 2.29 0.73 1.23 222 158002 1.94 0.70 1.12 222 158002 1.99 0.71 1.12 222 158003 1.44 0.66 0.88 222 158003 1.49 0.67 0.92 222 158004 0.98 0.65 0.75 222 158004 1.00 0.61 0.74 222 158005 0.88 0.61 0.70 222 158005 0.88 0.62 0.75 222 158006 0.78 0.60 0.67 222 158006 0.78 0.59 0.65 222 158007 0.60 0.53 0.30 222 158007 0.62 0.52 0.32 222 158008 0.79 0.50 0.18 222 158008 0.80 0.51 0.19 222 158009 0.81 0.52 0.17 222 158009 0.84 0.51 0.17 222 158010 12.82 1.21 12.91 222 158010 12.85 1.22 13.09 222 158011 11.98 1.20 12.50 222 158011 11.98 1.20 12.42 222 158012 9.48 1.11 10.30 222 158012 9.53 1.11 10.21 222 158013 6.65 1.03 6.58 222 158013 6.65 1.01 6.53 222 158014 5.35 0.88 4.89 222 158014 5.26 0.88 4.88 222 158015 4.89 0.82 4.67 222 158015 4.94 0.80 4.74 222 158016 4.59 0.88 4.56 222 158016 4.66 0.92 4.68 222 158017 4.29 0.81 4.16 222 158017 4.32 0.79 4.19 222 158018 3.02 0.76 2.94 222 158018 3.03 0.75 2.89 222 158019 1.29 0.61 0.81 222 158019 1.28 0.60 0.83 222 158020 0.81 0.54 0.29 222 158020 0.76 0.53 0.30 222 158021 1.02 0.56 0.83 222 158021 1.04 0.55 0.83 222 158022 0.50 0.48 0.18 222 158022 0.51 0.50 0.21 222 158023 0.33 0.36 0.00 222 158023 0.35 0.39 0.00 222 158024 0.33 0.37 0.00 222 158024 0.34 0.36 0.00 222 158025 0.40 0.39 0.00 222 158025 0.39 0.38 0.00 222 158026 17.34 1.29 20.29 222 158026 17.38 1.34 20.27 222 158027 15.78 1.46 19.75 222 158027 15.83 1.30 19.69 222 158028 14.40 1.24 19.16 222 158028 14.43 1.24 19.42 222 158029 13.13 1.25 18.55 222 158029 14.16 1.30 20.90 222 158030 12.36 1.22 18.06 222 158030 12.45 1.22 18.36 222 158031 11.78 1.19 17.59 222 158031 11.78 1.21 17.80 222 158032 11.86 1.15 17.12 222 158032 11.87 1.17 17.12 222 158033 10.61 1.08 15.64 222 158033 10.62 1.06 15.56 222 158034 10.09 1.03 14.90 222 158034 10.16 1.00 15.13 222 158035 8.80 0.98 13.59 222 158035 8.77 0.99 13.59 222 158036 9.66 1.03 15.08 222 158036 9.68 1.02 15.21 222 158037 9.64 0.92 13.72 222 158037 9.65 0.95 13.66 222 158038 8.90 0.97 12.95 222 158038 8.92 0.98 12.85 222 158039 8.02 1.01 11.55 222 158039 8.07 0.98 11.54 222 158040 7.24 0.96 10.60 222 158040 7.24 0.96 10.57 222 158041 3.70 0.72 4.44 222 158041 3.71 0.70 4.48 222 158042 2.90 0.67 3.07 222 158042 2.91 0.64 3.03 222 158043 2.33 0.53 0.43 222 158043 2.36 0.53 2 29 158044 0.65 0.32 0.26 222 158044 0.69 0.30 0.28 222 158045 0.62 0.30 0.26 222 158045 0.62 0.30 0.23 222 158046 0.60 0.12 0.19 222 158046 0.63 0.04 0.21 222 158047 10.10 0.13 12.36 222 158047 10.21 0.99 12.64 222 158048 4.73 0.22 7.12 222 158048 4.66 0.22 7.22 222 158049 1.65 0.18 1.66 222 158049 1.64 0.21 1.64 222 158050 0.87 0.39 0.00 222 158050 0.89 0.39 0.00 222 158050 0.97 0.41 0.00 222 158050 0.99 0.35 0.00 222 158051 0.66 0.14 0.31 222 158051 0.75 0.22 0.40 222 158052 0.82 0.40 0.15 222 158052 0.83 0.40 0.24 222 158053 0.46 0.32 0.16 222 158053 0.44 0.31 2 29 158054 0.62 0.12 0.21 222 158054 0.68 0.13 0.22 222 158055 5.26 0.14 6.99 222 158055 5.58 0.18 7.48 222 158056 5.87 0.20 7.95 222 158056 5.93 0.18 8.05 222 158057 3.81 0.22 5.49 222 158057 3.86 0.22 5.46 222 158058 2.49 0.69 3.20 222 158058 2.50 0.66 3.46 222 158059 1.79 0.67 2.11 222 158059 1.80 0.63 2.09 222 158060 0.66 0.49 0.58 222 158060 0.69 0.53 0.62 222 158061 0.54 0.40 0.18 222 158061 0.49 0.41 0.18 222 158062 0.56 0.35 0.14 222 158062 0.57 0.30 0.13 222 158063 0.59 0.39 2 29 158063 0.59 0.37 0.13 222 158064 0.62 0.38 0.13 222 158064 0.63 0.38 0.15 222 158065 10.28 1.24 17.92 222 158065 10.33 1.23 18.01 222 158066 9.54 1.09 15.47 222 158066 9.52 1.07 15.31 222 158067 7.81 0.99 13.26 222 158067 7.78 1.01 13.29 222 158068 8.02 0.91 12.41 222 158068 8.06 0.92 12.48 222 158069 7.48 0.89 11.77 222 158069 7.49 0.88 11.81 222 158070 6.93 0.86 11.04 222 158070 6.97 0.86 11.14 222 158071 7.26 0.83 11.56 222 158071 7.25 0.86 11.71 222 158072 6.50 0.80 10.52 222 158072 6.53 0.83 10.65 222 158073 5.77 0.75 9.12 222 158073 5.83 0.76 9.11 222 158074 5.76 0.82 9.23 222 158074 5.77 0.79 9.18 222 158075 4.22 0.71 6.55 222 158075 4.25 0.72 6.78 222 158076 4.61 0.75 5.72 222 158076 4.56 0.73 5.63 222 158077 4.42 0.80 5.43 222 158077 4.22 0.80 5.04 222 158078 1.37 0.50 1.45 222 158078 1.38 0.50 1.62 222 158079 0.55 0.46 0.50 222 158079 0.56 0.43 0.54 222 158080 0.41 0.40 0.18 222 158080 0.47 0.39 0.18 222 158081 0.00 0.38 0.18 222 158081 0.31 0.40 0.23 222 158082 0.29 0.39 0.16 222 158082 0.00 0.37 0.16 222 158083 11.35 1.31 19.31 222 158083 11.37 1.28 19.41 222 158084 10.62 1.27 19.51 222 158084 10.62 1.31 19.77 222 158085 8.71 1.04 15.05 222 158085 8.73 1.02 14.90 222 158086 7.55 0.93 13.69 222 158086 7.58 0.96 13.79 222 158087 7.62 0.95 13.67 222 158087 7.63 0.92 13.61 222 158088 6.97 0.89 12.59 222 158088 7.00 0.88 12.48 222 158089 4.91 0.68 8.49 222 158089 4.98 0.70 8.55 222 158090 6.36 0.83 11.67 222 158090 6.28 0.82 11.74 222 158091 6.21 0.80 11.48 222 158091 6.27 0.82 11.67 222 158092 5.60 1.25 9.71 222 158092 5.60 1.26 9.69 222 158093 5.55 0.79 9.65 222 158093 5.59 0.77 9.63 222 158094 3.97 0.75 7.35 222 158094 3.99 0.77 7.41 222 158095 2.00 0.65 3.44 222 158095 1.96 0.60 3.47 222 158096 1.14 0.46 1.01 222 158096 1.10 0.45 0.97 222 158097 0.82 0.28 0.15 222 158097 0.89 0.32 0.24 222 158098 0.75 0.30 0.19 222 158098 0.78 0.30 0.27 222 158099 0.68 0.34 0.23 222 158099 0.70 0.33 0.12 222 158100 0.61 0.31 0.12 222 158100 0.69 0.34 0.24 222 158101 5.70 0.87 5.96 222 158101 5.64 0.86 5.98 222 158102 5.66 0.85 5.97 222 158102 5.68 0.87 5.95 222 158103 5.23 0.87 5.67 222 158103 5.28 0.87 5.67 222 158104 4.02 0.85 4.55 222 158104 4.22 0.82 4.80 222 158105 3.16 0.96 4.05 222 158105 3.18 0.96 3.97 222 158106 1.13 0.73 1.57 222 158106 1.13 0.75 1.64 222 158107 0.85 0.61 0.69 222 158107 0.87 0.61 0.73 222 158108 0.58 0.45 0.16 222 158108 0.59 0.46 0.18 222 158109 0.45 0.39 0.00 222 158109 0.47 0.37 0.00 222 158110 0.51 0.39 0.00 222 158110 0.54 0.40 0.00 222 158111 0.52 0.40 0.00 222 158111 0.46 0.38 0.00 222 158112 1.69 0.61 0.18 222 158112 1.76 0.60 0.18 222 158113 1.73 0.63 0.19 222 158113 1.74 0.64 0.17 222 158114 1.86 0.64 0.10 222 158114 1.90 0.63 0.15 222 158115 1.44 0.59 0.00 222 158115 1.60 0.57 0.00 222 158116 0.36 0.43 0.00 222 158116 0.57 0.45 0.00 222 158117 0.44 0.40 0.00 222 158117 0.45 0.42 0.00 222 158118 0.00 0.41 0.31 222 158118 0.30 0.39 0.31 222 158119 6.18 0.84 6.06 222 158119 6.14 0.84 5.74 222 158120 7.43 0.94 6.71 222 158120 7.55 0.92 6.77 222 158121 8.14 1.00 7.82 222 158121 8.17 1.00 7.76 222 158122 4.18 0.89 5.03 222 158122 4.24 0.92 5.12 222 158123 2.97 0.91 4.73 222 158123 2.99 0.92 4.74 222 158124 1.42 0.81 2.85 222 158124 1.39 0.79 2.78 222 158125 0.50 0.52 0.56 222 158125 0.44 0.51 0.60 222 158126 0.00 0.45 0.00 222 158126 0.00 0.44 0.00 222 158127 0.00 0.44 0.00 222 158127 0.00 0.38 0.00 222 158128 0.00 0.38 0.00 222 158128 0.00 0.36 0.00 222 158129 0.00 0.39 0.00 222 158129 0.00 0.39 0.00 222 158130 4.11 0.66 8.43 222 158130 4.08 0.63 8.45 222 158131 4.24 0.71 8.48 222 158131 4.30 0.69 8.95 222 158132 3.64 0.66 7.19 222 158132 3.69 0.66 7.37 222 158133 3.42 0.63 6.81 222 158133 3.49 0.65 6.91 222 158134 2.03 0.49 3.47 222 158134 2.05 0.50 3.38 222 158135 1.43 0.50 1.66 222 158135 1.52 0.51 1.66 222 158136 1.31 0.44 0.83 222 158136 1.34 0.43 0.83 222 158137 0.54 0.35 0.00 222 158137 0.54 0.32 0.00 222 158138 0.00 0.32 0.00 222 158138 0.00 0.27 0.00 222 158139 0.00 0.31 0.00 222 158139 0.00 0.28 0.00 222 158140 0.00 0.35 0.00 222 158140 0.00 0.33 0.00 222 158141 6.95 0.89 7.80 222 158141 6.97 0.89 7.81 222 158142 4.86 0.79 5.46 222 158142 4.90 0.77 5.45 222 158143 4.22 0.79 5.13 222 158143 4.18 0.81 5.14 222 158144 3.05 0.78 4.13 222 158144 2.75 0.76 3.86 222 158145 5.30 0.81 7.94 222 158145 5.41 0.84 7.84 222 158146 2.02 0.86 4.35 222 158146 2.02 0.83 4.41 222 158147 0.00 0.42 0.17 222 158147 0.00 0.42 0.15 222 158148 0.00 0.36 0.00 222 158148 0.00 0.35 0.00 222 158149 0.00 0.41 0.00 222 158149 0.00 0.42 0.00 222 158150 0.00 0.43 0.00 222 158150 0.00 0.43 0.00 222 158151 0.00 0.40 0.00 222 158151 0.00 0.40 0.00 222 158152 8.62 0.40 11.49 222 158152 8.69 0.99 11.44 222 158153 6.12 0.87 9.46 222 158153 6.06 0.88 9.36 222 158154 6.83 0.89 8.39 222 158154 6.79 0.94 8.44 222 158155 4.94 0.80 6.68 222 158155 4.99 0.79 6.71 222 158156 4.66 0.44 5.41 222 158156 4.70 0.72 5.40 222 158157 3.26 0.37 3.37 222 158157 3.30 0.64 3.51 222 158158 0.56 0.48 0.34 222 158158 0.56 0.81 0.35 222 158159 0.37 0.47 0.13 222 158159 0.00 0.46 0.13 222 158160 0.00 0.55 0.17 222 158160 0.00 0.36 0.17 222 158161 0.00 0.31 0.28 222 158161 0.30 0.42 0.30 222 158162 0.00 0.33 0.00 222 158162 0.00 0.34 0.00 222 158163 5.75 0.32 10.30 222 158163 5.76 0.72 10.21 222 158164 4.56 0.71 8.88 222 158164 4.60 0.68 8.80 222 158165 4.08 0.64 8.43 222 158165 4.10 0.66 8.44 222 158166 3.74 0.55 7.31 222 158166 3.79 0.64 7.30 222 158167 3.60 0.56 6.09 222 158167 3.59 0.60 6.13 222 158168 4.09 0.69 4.97 222 158168 4.13 0.62 4.99 222 158169 1.44 0.57 1.88 222 158169 1.52 0.55 1.89 222 158170 0.33 0.45 0.18 222 158170 0.33 0.45 0.20 222 158171 0.00 1.21 0.00 232 158171 0.00 1.17 0.00 232 158172 0.00 0.39 0.00 222 158172 0.00 0.37 0.00 222 158173 0.00 0.40 0.00 222 158173 0.00 0.42 0.00 222 158175 1.62 0.64 1.86 222 158175 1.63 0.68 1.88 222 158176 0.59 0.53 0.73 222 158176 0.64 0.52 0.77 222 158177 0.42 0.64 0.32 222 158177 0.43 0.47 0.30 222 158178 0.00 0.42 0.00 222 158178 0.00 0.40 0.00 222 158179 0.00 0.40 0.00 222 158179 0.00 0.38 0.00 222 158180 0.00 0.46 0.00 222 158180 0.00 0.44 0.00 222 158185 10.98 1.13 8.50 222 158185 11.27 0.95 8.93 222 158186 8.30 0.79 6.41 333 158186 10.30 0.94 8.05 333 158187 6.59 0.73 3.86 222 158187 6.67 0.76 3.50 222 158188 1.55 0.48 0.10 333 158188 2.60 0.46 0.11 333 158189 9.62 0.92 8.29 333 158189 11.64 0.99 10.11 333 158190 10.67 0.95 9.21 333 158190 13.79 0.94 9.59 333 158191 10.81 0.97 8.38 333 158191 17.14 0.98 8.29 333 158192 3.29 0.51 1.25 222 158192 4.35 0.65 1.41 222 158193 6.47 0.47 0.08 333 158193 2.41 0.53 0.54 333 158194 9.99 0.81 7.69 333 158194 13.01 1.05 10.60 333 158195 8.49 0.83 7.24 333 158195 10.16 0.80 7.24 333 158196 2.72 0.51 0.67 333 158196 3.07 0.57 0.42 333 158197 3.62 0.52 0.23 222 158197 3.65 0.54 0.10 222 158198 11.18 0.97 9.47 222 158198 11.56 0.92 9.83 222 158199 8.61 0.81 7.16 222 158199 10.20 0.88 8.70 222 158200 3.04 0.65 0.90 222 158200 3.70 0.54 0.87 222 158201 2.33 0.41 0.27 222 158201 2.18 0.53 0.00 222 158203 11.21 0.93 11.22 222 158203 11.60 1.01 11.22 222 158204 9.89 0.83 9.77 222 158204 10.28 0.86 9.73 222 158205 9.08 0.80 7.53 333 158205 10.43 0.96 8.71 333 158206 9.80 0.89 7.79 222 158206 10.66 0.98 8.34 222 158207 2.70 0.57 0.00 222 158207 1.96 0.49 0.27 222 158208 8.98 0.82 9.84 222 158208 7.25 0.74 8.55 222 158209 10.24 0.91 10.74 222 158209 10.65 1.00 10.85 222 158210 9.07 0.77 9.20 222 158210 10.16 0.85 10.63 222 158211 7.58 0.77 6.81 333 158211 12.06 0.97 9.13 333 158212 8.72 0.77 6.75 333 158212 10.75 0.96 7.87 333 158213 2.23 0.48 0.16 222 158213 2.02 0.45 0.32 222 158214 9.13 0.88 12.11 333 158214 9.97 1.03 13.25 333 158215 10.00 1.03 12.99 222 158215 10.14 0.93 12.63 222 158216 7.24 0.77 9.86 333 158216 10.81 0.90 14.29 333 158217 8.23 0.76 10.40 333 158217 10.61 0.92 12.20 333 158218 9.69 0.91 11.17 222 158218 9.97 0.92 11.60 222 158219 7.90 0.78 8.70 333 158219 10.35 0.94 10.90 333 158220 7.45 0.75 7.76 333 158220 10.60 0.99 11.28 333 158221 10.19 0.97 8.26 222 158221 9.11 0.86 6.96 222 158222 3.50 0.58 0.61 222 158222 3.77 0.50 0.50 222 158223 7.68 0.99 12.53 333 158223 13.28 1.04 16.34 333 158224 7.48 0.85 12.59 323 158224 8.08 0.90 13.50 323 158225 10.02 1.11 16.65 333 158225 13.30 0.91 14.98 333 158226 9.76 1.08 16.84 333 158226 8.28 0.96 13.87 333 158227 9.65 1.06 16.11 222 158227 9.11 1.03 16.09 222 158228 8.91 0.97 15.46 222 158228 9.02 1.06 15.86 222 158229 9.69 1.05 15.93 222 158229 9.91 0.98 14.89 222 158230 7.39 0.85 12.63 222 158230 8.26 0.89 13.00 222 158231 11.74 0.77 10.28 333 158231 10.20 1.10 13.59 333 158232 8.70 0.90 11.78 222 158232 10.36 0.94 12.24 222 158233 7.93 0.74 7.04 222 158233 8.07 0.82 7.56 222 158234 11.08 1.05 16.14 222 158234 11.22 1.04 16.26 222 158235 11.21 1.04 16.28 222 158235 11.28 1.05 16.16 222 158236 11.23 1.05 16.70 222 158236 10.95 1.05 16.56 222 158237 10.98 1.06 16.78 222 158237 10.86 1.06 16.27 222 158238 10.59 1.07 16.63 222 158238 10.81 1.08 16.76 222 158239 10.07 0.89 16.78 222 158239 10.29 1.08 16.80 222 158240 9.84 0.87 16.75 222 158240 10.00 1.08 16.58 222 158241 9.94 1.09 17.02 222 158241 10.01 1.05 16.66 222 158242 9.94 1.02 16.65 222 158242 9.74 1.05 17.03 222 158243 9.66 1.08 16.83 222 158243 9.73 1.02 17.14 222 158244 9.50 1.08 16.91 222 158244 9.57 1.04 16.82 222 158245 9.32 1.09 16.66 242 158245 9.40 1.03 16.73 222 158246 9.07 0.94 16.08 222 158246 9.27 1.05 16.59 222 158247 8.59 1.03 15.85 222 158247 8.67 1.00 15.94 222 158248 8.28 0.98 15.91 222 158248 8.36 1.05 15.44 222 158249 8.09 0.95 14.65 222 158249 8.09 0.85 14.63 222 158250 2.66 0.61 6.68 222 158250 2.62 0.58 6.75 222 158251 10.16 0.90 14.01 333 158251 11.28 0.82 15.77 333 158252 11.59 1.02 15.72 222 158252 11.64 1.00 15.72 222 158253 11.57 0.99 15.76 222 158253 11.77 0.97 15.99 222 158254 11.55 1.02 16.14 222 158254 11.66 1.04 15.87 222 158255 11.61 1.03 15.93 222 158255 11.53 1.00 16.32 222 158256 11.42 0.98 16.32 222 158256 11.38 1.05 16.24 222 158257 10.89 1.06 16.54 222 158257 11.02 1.00 16.47 222 158258 10.46 1.04 16.71 222 158258 10.58 1.04 16.61 222 158259 9.88 1.08 16.75 222 158259 9.94 1.06 16.79 222 158260 9.26 1.03 15.35 223 158260 10.76 0.97 15.19 223 158261 9.00 1.01 15.32 333 158261 7.97 0.93 13.61 333 158262 9.68 1.07 17.03 222 158262 9.94 1.11 17.01 222 158263 9.21 1.07 16.45 222 158263 9.24 1.08 16.51 222 158264 9.13 1.07 16.60 222 158264 9.16 1.06 16.76 222 158265 9.40 1.09 16.84 222 158265 9.42 1.09 16.66 222 158266 8.37 0.92 16.02 222 158266 8.55 1.01 15.68 222 158267 8.60 0.92 16.02 222 158267 8.66 1.03 15.68 222 158268 8.98 1.01 15.95 222 158268 9.10 1.02 15.84 222 158269 8.30 0.85 14.64 222 158269 8.33 1.00 14.73 222 158270 3.25 0.69 8.43 222 158270 3.33 0.66 8.16 222 158271 10.98 0.98 14.86 222 158271 10.60 0.97 14.77 222 158272 10.42 0.99 15.35 222 158272 10.71 1.01 15.22 222 158273 10.65 0.96 15.15 222 158273 10.88 0.99 14.87 222 158274 10.80 0.99 15.30 222 158274 10.86 1.03 15.00 222 158275 11.83 1.03 15.97 222 158275 11.96 1.03 15.81 222 158276 11.56 1.11 16.19 242 158276 11.67 0.96 16.14 222 158277 10.99 1.06 16.53 222 158277 11.19 1.09 16.55 222 158278 8.10 0.92 12.69 333 158278 10.48 1.08 17.00 333 158279 10.28 1.10 16.66 222 158279 10.23 1.12 17.04 222 158280 9.91 1.12 16.97 222 158280 10.01 1.13 16.88 222 158281 9.76 1.12 16.87 222 158281 10.42 1.14 17.23 222 158282 10.02 1.23 16.73 222 158282 10.22 1.22 16.67 222 158283 9.87 1.23 16.87 222 158283 9.98 1.25 17.08 222 158284 10.22 1.25 16.45 222 158284 10.04 1.24 16.93 222 158285 9.83 1.23 16.55 222 158285 9.77 1.14 16.72 222 158286 8.79 1.19 15.89 222 158286 8.88 1.19 15.92 222 158287 8.91 1.17 15.55 222 158287 8.94 1.18 15.33 222 158288 8.88 1.16 14.83 222 158288 10.74 1.17 15.25 222 158289 8.10 1.07 13.37 333 158289 8.07 0.98 11.33 333 158290 7.33 0.93 11.04 222 158290 9.23 0.93 10.56 222 158291 10.85 1.12 14.46 222 158291 10.88 1.12 14.72 222 158292 9.30 1.06 12.91 333 158292 10.49 1.06 14.34 333 158293 9.72 1.10 13.70 242 158293 9.95 1.07 13.81 222 158294 11.37 1.15 15.50 222 158294 10.25 1.06 13.54 222 158295 11.85 1.21 15.63 222 158295 11.46 1.17 14.97 222 158296 10.39 1.14 14.09 222 158296 11.99 1.22 15.67 222 158297 9.47 1.05 12.71 333 158297 11.78 1.19 15.91 333 158298 11.06 1.18 15.84 222 158298 11.24 1.20 16.10 222 158299 10.23 1.12 15.08 333 158299 11.23 1.24 16.47 333 158300 10.79 1.25 17.05 222 158300 10.47 1.23 16.17 222 158301 8.36 1.13 14.16 333 158301 12.15 1.25 16.93 333 158302 8.21 1.08 13.41 333 158302 9.96 1.28 17.01 333 158303 10.10 1.25 16.67 222 158303 10.63 1.28 16.82 222 158304 9.33 1.21 15.79 222 158304 9.72 1.23 16.35 222 158305 8.24 1.08 13.66 333 158305 11.93 1.28 17.04 333 158306 5.29 0.67 6.63 333 158306 10.12 1.24 16.86 333 158307 8.61 1.04 14.31 222 158307 9.62 1.10 14.88 222 158308 8.97 1.19 16.16 222 158308 9.38 1.13 14.73 222 158309 7.87 1.09 13.90 333 158309 9.14 1.22 16.86 333 158310 8.11 1.13 14.79 222 158310 7.96 1.14 14.79 222 158311 8.55 1.07 15.80 322 158311 10.84 1.17 15.21 322 158312 7.10 1.00 12.20 333 158312 8.10 1.16 14.37 333 158313 3.31 0.69 6.84 222 158313 3.37 0.73 7.41 222 158314 12.77 1.00 12.64 222 158314 9.62 0.99 13.06 222 158315 9.71 1.00 13.08 222 158315 10.65 1.13 14.70 222 158316 10.74 1.15 15.08 222 158316 11.03 1.14 14.79 222 158317 11.47 1.12 14.81 222 158317 11.91 1.15 15.44 222 158318 12.02 1.18 15.54 222 158318 11.49 1.13 15.07 222 158319 11.17 1.13 14.52 222 158319 13.05 1.19 15.81 222 158320 11.75 1.21 15.91 222 158320 12.22 1.23 16.30 222 158321 8.79 1.00 12.05 333 158321 11.25 1.21 16.42 333 158322 9.34 1.04 13.86 333 158322 11.13 1.24 16.49 333 158323 12.03 1.16 15.28 222 158323 9.45 1.05 13.61 222 158324 9.68 1.18 17.13 222 158324 8.60 1.15 14.96 222 158325 8.01 1.08 14.10 333 158325 9.12 1.16 15.75 333 158326 8.54 1.13 14.70 333 158326 9.85 1.25 17.01 333 158327 9.53 0.94 12.85 333 158327 10.26 1.23 17.25 333 158328 10.02 1.26 16.99 222 158328 10.58 1.24 16.61 222 158329 22.02 1.24 16.95 422 158329 12.13 1.19 16.11 422 158330 9.04 1.11 15.47 222 158330 9.54 1.19 16.19 222 158331 7.06 0.95 12.13 222 158331 8.22 1.06 13.46 222 158332 7.71 1.03 13.18 222 158332 9.76 1.22 16.54 222 158333 10.11 1.16 15.97 322 158333 12.12 1.16 15.38 322 158334 6.32 0.93 10.94 333 158334 8.97 1.14 15.90 333 158335 7.94 1.08 14.24 222 158335 9.26 1.16 15.40 222 158336 6.12 0.81 9.06 322 158336 8.05 0.81 9.14 322 158337 11.48 1.11 14.92 222 158337 11.26 1.07 14.52 222 158338 10.96 1.07 14.56 222 158338 11.00 1.07 14.98 222 158339 11.34 1.10 15.11 222 158339 11.43 1.08 15.30 222 158340 12.94 1.15 15.69 222 158340 13.03 1.14 15.91 222 158341 13.34 1.16 16.33 222 158341 13.65 1.17 16.30 222 158342 12.92 1.19 16.22 333 158342 11.84 1.14 15.03 333 158343 12.84 1.34 16.50 222 158343 12.55 1.18 16.52 222 158344 11.55 1.18 15.54 333 158344 12.06 1.20 16.67 333 158345 11.27 1.19 16.62 222 158345 11.52 1.23 16.95 222 158346 10.06 1.18 16.58 222 158346 10.17 1.21 16.95 222 158347 10.10 1.19 17.06 222 158347 9.57 1.18 16.16 222 158348 9.41 1.15 15.75 333 158348 9.97 1.20 16.99 333 158349 9.93 1.18 16.53 222 158349 10.00 1.18 16.70 222 158350 9.98 1.20 16.70 222 158350 10.04 1.20 16.88 222 158351 9.94 1.19 16.66 222 158351 10.00 1.22 17.09 222 158352 10.29 1.20 17.03 333 158352 9.25 1.15 15.78 333 158353 9.62 1.19 16.44 222 158353 9.48 1.18 16.35 222 158354 9.15 1.12 15.95 222 158354 9.20 1.16 16.32 222 158355 8.96 1.16 16.17 222 158355 9.11 1.14 16.32 222 158356 8.83 1.14 15.99 222 158356 8.86 1.17 15.97 222 158357 7.04 1.02 12.61 333 158357 8.79 1.11 15.68 333 158358 7.21 0.95 11.96 333 158358 6.23 0.87 9.71 333 158359 5.21 0.81 8.51 222 158359 5.39 0.78 8.86 222 158365 10.81 1.05 14.85 222 158365 10.95 1.04 14.96 222 158366 10.74 1.08 14.86 222 158366 10.89 1.06 14.89 222 158367 10.32 1.05 14.38 222 158367 10.71 1.05 15.01 222 158368 11.88 1.11 15.41 222 158368 11.89 1.10 15.67 222 158369 12.50 1.12 15.98 222 158369 12.79 1.13 15.89 222 158370 12.49 1.15 16.37 222 158370 12.63 1.14 16.26 222 158371 12.03 1.18 16.41 222 158371 12.00 1.15 16.57 222 158372 7.84 1.04 13.77 222 158372 7.89 1.02 13.88 222 158373 9.66 1.11 15.18 333 158373 10.91 1.17 16.59 333 158374 9.98 1.17 16.61 222 158374 10.01 1.18 16.83 222 158375 9.66 1.14 16.80 222 158375 9.89 1.13 16.52 222 158376 9.91 1.16 16.71 222 158376 9.71 1.17 16.73 222 158377 9.72 1.16 16.80 222 158377 9.33 1.08 16.25 222 158378 8.67 1.07 15.37 222 158378 9.68 1.17 16.93 222 158379 9.08 1.13 15.98 222 158379 9.14 1.14 16.29 222 158380 9.36 1.15 16.57 222 158380 9.87 1.16 16.75 222 158381 9.15 1.14 16.42 222 158381 9.15 1.15 16.31 222 158382 9.22 1.16 16.70 222 158382 9.11 1.15 16.71 222 158383 8.66 1.18 16.58 222 158383 8.67 1.22 16.53 222 158384 8.18 1.12 15.93 222 158384 8.26 1.13 15.65 222 158385 8.17 1.12 15.34 222 158385 8.32 1.13 15.68 222 158386 6.43 0.94 11.15 222 158386 6.44 0.90 11.22 222 158387 6.00 0.86 10.61 222 158387 6.15 0.85 11.01 222 158388 9.96 1.09 14.86 222 158388 10.04 1.07 14.88 222 158389 8.81 1.15 16.05 222 158389 9.08 1.18 15.98 222 158390 10.59 1.07 15.15 222 158390 10.61 1.10 15.07 222 158391 11.77 1.12 15.78 222 158391 11.78 1.18 15.70 222 158392 12.64 1.16 16.16 222 158392 12.40 1.16 16.28 222 158393 12.18 1.15 16.19 222 158393 12.19 1.16 16.28 222 158394 11.73 1.17 16.29 222 158394 11.75 1.15 16.53 222 158395 11.51 1.17 16.99 222 158395 11.52 1.17 16.91 222 158396 10.89 1.20 17.06 222 158396 10.92 1.06 17.23 222 158397 9.75 1.13 15.97 333 158397 10.40 1.20 16.88 333 158398 8.38 1.08 15.09 333 158398 9.34 1.16 16.65 333 158399 8.82 1.12 16.33 222 158399 9.24 1.02 16.94 222 158400 9.22 1.15 16.91 222 158400 9.21 1.15 16.93 222 158401 9.39 1.18 16.84 222 158401 9.48 1.18 16.98 222 158402 9.46 1.20 17.17 222 158402 9.49 1.19 16.96 222 158403 9.41 1.17 17.41 222 158403 9.53 1.16 17.31 222 158404 8.95 1.15 16.86 222 158404 9.07 1.16 17.13 222 158405 8.85 1.16 16.68 222 158405 8.61 1.14 16.72 222 158406 8.93 1.17 16.67 222 158406 8.83 1.17 16.59 222 158407 8.56 1.14 16.63 222 158407 8.63 1.17 16.62 222 158408 7.84 1.08 15.62 222 158408 7.99 1.09 15.47 222 158409 7.38 1.04 14.20 222 158409 7.42 1.06 14.17 222 158410 5.70 0.84 10.53 222 158410 5.84 0.82 10.42 222 158411 9.78 1.05 14.90 222 158411 9.71 1.03 14.90 222 158412 9.81 1.04 14.78 222 158412 9.89 1.04 14.42 222 158413 9.51 1.05 14.61 333 158413 9.58 1.03 12.74 333 158414 10.02 1.07 14.80 333 158414 10.44 0.97 11.71 333 158415 11.66 1.06 15.64 222 158415 11.75 1.12 15.68 222 158416 11.56 1.05 14.25 333 158416 12.51 1.13 16.24 333 158417 11.76 1.14 16.03 333 158417 12.88 1.16 14.15 333 158418 10.73 1.11 15.83 222 158418 10.83 1.06 15.71 222 158419 10.46 1.15 16.73 222 158419 9.25 1.01 14.63 222 158420 9.22 1.09 14.55 222 158420 9.87 1.13 16.89 222 158421 7.04 0.80 12.09 333 158421 9.21 1.14 16.84 333 158422 9.31 1.18 16.56 333 158422 9.32 1.14 16.60 333 158423 7.43 0.95 13.28 333 158423 9.38 1.13 16.90 333 158424 9.63 1.14 16.93 222 158424 9.42 1.14 16.77 222 158425 9.33 1.12 16.55 333 158425 5.72 0.76 10.23 333 158426 7.29 0.89 11.95 333 158426 9.11 1.14 16.78 333 158427 6.86 0.91 13.52 333 158427 8.79 1.11 16.61 333 158428 5.64 0.74 9.30 333 158428 8.73 1.11 16.61 333 158429 7.54 1.00 14.10 333 158429 6.41 0.86 12.17 333 158430 7.22 0.94 13.76 333 158430 8.24 1.10 15.63 333 158431 6.39 0.86 12.03 333 158431 8.48 1.06 15.27 333 158432 7.85 0.94 13.18 222 158432 7.94 0.95 12.94 222 158433 4.85 0.70 7.96 333 158433 6.09 0.81 10.10 333 158434 10.10 1.01 14.36 222 158434 9.92 1.01 14.76 222 158435 9.92 1.07 15.28 222 158435 9.83 1.07 15.24 222 158436 9.83 1.03 14.71 222 158436 10.02 1.04 14.83 222 158437 11.48 1.06 15.01 333 158437 11.93 1.10 15.41 333 158438 13.27 1.12 15.79 222 158438 13.27 1.24 15.97 242 158439 12.61 1.05 15.70 333 158439 13.07 1.11 16.02 333 158440 12.37 1.15 16.07 222 158440 12.22 1.13 16.26 222 158441 8.70 1.07 15.20 333 158441 9.16 1.10 15.97 333 158442 11.59 1.16 16.45 333 158442 11.86 1.21 16.93 333 158443 8.98 1.04 14.22 333 158443 10.38 1.15 16.26 333 158444 8.50 1.03 14.62 333 158444 10.08 1.15 16.64 333 158445 9.17 1.10 15.38 333 158445 9.93 1.16 16.69 333 158446 9.78 1.20 16.77 222 158446 9.93 1.14 16.70 222 158447 9.82 1.12 16.58 222 158447 9.88 1.10 16.49 222 158448 10.07 1.13 16.60 333 158448 9.67 1.15 16.88 333 158449 9.71 1.16 16.79 333 158449 9.77 1.13 16.56 333 158450 9.01 1.10 15.70 222 158450 9.04 1.12 15.93 222 158451 8.77 1.09 15.25 333 158451 9.44 1.16 16.83 333 158452 7.96 1.06 14.91 222 158452 8.63 1.12 15.71 222 158453 8.54 1.09 15.74 222 158453 8.26 1.09 15.71 222 158454 8.36 1.08 15.42 222 158454 8.15 1.09 15.56 222 158455 7.52 0.95 13.27 333 158455 7.98 0.98 13.89 333 158456 6.62 0.84 10.80 222 158456 6.77 0.84 10.72 222 158457 9.43 0.97 14.67 222 158457 9.53 0.97 14.52 222 158458 10.65 1.04 14.68 222 158458 10.77 1.03 14.68 222 158459 10.74 1.07 15.26 222 158459 10.44 1.05 14.90 222 158460 12.62 1.10 15.62 222 158460 12.74 1.12 15.68 222 158461 12.59 1.10 15.97 222 158461 12.68 1.12 15.75 222 158462 11.05 0.99 13.05 333 158462 13.02 1.12 15.79 333 158463 9.61 0.96 12.29 333 158463 10.97 0.99 14.52 333 158464 11.52 1.12 15.80 222 158464 11.58 1.09 16.07 222 158465 10.87 1.14 16.85 222 158465 11.01 1.15 16.75 222 158466 8.97 1.08 15.52 222 158466 9.10 1.11 16.06 222 158467 6.41 0.87 11.07 333 158467 9.74 1.13 16.68 333 158468 9.59 1.14 16.72 222 158468 9.65 1.16 16.27 222 158469 9.59 1.15 16.87 333 158469 6.82 0.94 11.82 333 158470 7.09 0.95 12.26 333 158470 8.51 1.04 14.57 333 158471 9.39 1.14 16.66 222 158471 9.66 1.13 16.72 222 158472 7.40 0.96 12.91 333 158472 9.31 1.08 16.34 333 158473 8.74 1.10 16.03 222 158473 8.80 1.09 16.40 222 158474 8.68 1.10 16.23 222 158474 8.77 1.10 15.71 222 158480 9.38 1.00 14.46 222 158480 9.53 1.03 14.78 222 158481 8.57 0.91 12.37 222 158481 8.63 0.96 12.48 222 158482 10.74 1.04 15.21 222 158482 10.26 1.04 14.28 222 158483 11.83 1.08 15.54 222 158483 12.01 1.09 15.40 222 158484 12.68 1.03 15.27 222 158484 12.86 1.04 15.83 222 158485 9.64 0.89 12.18 333 158485 13.02 1.07 16.21 333 158486 9.16 0.93 12.74 333 158486 11.70 1.06 16.03 333 158487 11.28 1.06 16.40 222 158487 10.74 1.05 15.46 222 158488 10.62 1.06 16.03 222 158488 9.57 1.03 14.74 222 158489 6.48 0.86 10.58 333 158489 10.12 1.11 16.72 333 158490 8.38 1.02 14.19 333 158490 9.70 1.08 16.76 333 158491 9.68 1.10 16.58 222 158491 9.77 1.08 16.95 222 158492 6.20 0.76 10.85 333 158492 7.14 0.88 12.48 333 158493 7.98 0.94 13.88 333 158493 6.06 0.84 10.79 333 158494 8.56 1.01 15.19 222 158494 9.35 1.08 16.78 222 158495 6.70 0.88 11.75 333 158495 9.23 1.08 16.35 333 158496 5.75 0.81 10.59 333 158496 9.03 1.07 16.49 333 158497 8.73 1.06 16.39 222 158497 8.88 1.08 16.25 222 158498 8.49 1.06 16.12 222 158498 8.62 1.08 15.92 222 158499 7.81 1.05 14.68 222 158499 8.38 1.06 16.12 222 158500 7.98 1.01 15.39 222 158500 8.13 1.03 15.73 222 158501 7.80 0.95 13.82 333 158501 7.26 0.94 12.61 333 158502 7.30 0.90 12.69 222 158502 7.42 0.92 12.69 222 158503 9.89 0.98 14.53 222 158503 10.13 1.01 14.53 222 158504 9.48 0.97 13.74 222 158504 9.81 1.00 14.74 222 158505 9.51 1.00 14.47 222 158505 10.15 1.00 15.08 222 158506 11.11 1.05 15.30 222 158506 6.42 0.76 8.94 222 158507 12.33 1.06 15.77 333 158507 10.61 0.92 13.29 333 158508 11.65 1.04 15.54 222 158508 11.89 1.01 15.65 222 158509 11.15 1.07 15.58 222 158509 11.32 1.13 15.87 222 158510 10.88 1.10 16.37 222 158510 11.00 1.12 16.09 222 158511 10.46 1.13 15.89 222 158511 9.89 1.13 16.03 222 158512 10.11 1.12 16.51 222 158512 10.20 1.12 16.64 222 158513 8.32 1.05 13.46 333 158513 9.79 1.12 16.39 333 158514 9.55 1.13 16.82 222 158514 10.33 1.14 16.19 222 158515 8.62 1.07 15.24 222 158515 9.55 1.15 16.45 222 158516 9.77 1.14 16.81 333 158516 8.30 1.05 13.98 333 158517 9.46 1.11 16.51 222 158517 9.27 1.12 16.79 222 158518 9.07 1.12 16.55 222 158518 9.10 1.10 16.27 222 158519 8.71 1.10 16.29 222 158519 8.87 1.10 16.39 222 158520 8.18 1.06 15.44 222 158520 8.45 1.11 16.00 222 158521 8.18 1.07 15.17 222 158521 8.48 1.07 15.18 222 158522 8.40 1.09 15.62 222 158522 8.10 1.07 15.72 222 158523 8.11 1.06 15.48 222 158523 8.77 1.09 15.13 222 158524 6.53 0.86 11.23 222 158524 7.07 0.87 12.01 222 158525 7.08 0.92 11.88 222 158525 7.25 0.90 12.20 222 158526 9.64 1.00 14.63 222 158526 10.12 1.00 14.04 222 158527 9.31 0.97 13.64 222 158527 9.49 1.01 14.39 222 158528 9.86 0.97 13.92 222 158528 10.20 1.03 14.79 222 158529 11.08 1.05 15.17 222 158529 11.86 1.00 14.33 222 158530 12.59 1.10 15.57 222 158530 11.96 1.06 15.13 222 158531 12.87 1.11 16.27 222 158531 12.89 1.10 15.91 222 158532 11.78 1.00 15.65 222 158532 12.51 1.15 16.02 222 158533 11.46 1.07 15.96 222 158533 11.55 1.06 16.08 222 158534 7.93 0.84 12.04 333 158534 9.46 0.97 14.08 333 158535 10.27 1.06 16.28 222 158535 10.09 1.07 16.60 222 158536 9.59 1.05 16.36 333 158536 8.09 0.97 13.95 333 158537 9.47 1.07 16.43 222 158537 9.51 1.08 16.59 222 158538 8.85 1.16 16.23 222 158538 9.42 1.07 16.37 222 158539 9.45 1.08 16.02 222 158539 9.55 1.08 16.70 222 158540 8.32 0.93 14.43 222 158540 8.40 0.92 14.99 222 158541 9.49 1.07 16.66 222 158541 9.17 1.06 15.84 222 158542 8.62 1.05 15.75 222 158542 8.85 1.06 16.43 222 158543 6.57 0.88 12.23 333 158543 8.61 1.03 15.75 333 158544 6.21 0.84 11.76 333 158544 7.96 1.00 14.79 333 158545 8.20 1.01 15.36 222 158545 8.37 1.03 15.60 222 158546 7.82 0.97 13.98 222 158546 8.07 0.86 14.67 222 158547 5.19 0.69 7.96 222 158547 6.43 0.78 9.99 222 158548 5.81 0.70 9.00 222 158548 6.22 0.75 9.79 222 158549 8.33 0.87 12.88 333 158549 9.87 0.97 14.89 333 158550 9.92 0.98 14.64 222 158550 10.13 1.00 15.04 222 158551 10.78 1.01 15.21 222 158551 10.77 1.03 15.06 222 158552 12.14 1.03 15.13 222 158552 12.43 1.05 15.31 222 158553 10.60 0.98 14.18 222 158553 11.16 1.01 14.84 222 158554 11.66 1.05 15.66 222 158554 11.92 1.06 16.10 222 158555 10.06 0.98 13.75 222 158555 11.97 1.06 16.33 222 158556 9.73 0.98 14.59 222 158556 10.70 1.07 16.03 222 158557 9.84 1.00 14.89 222 158557 10.20 1.05 15.71 222 158558 10.15 1.06 16.34 222 158558 10.19 1.09 16.22 222 158559 9.99 1.08 16.56 222 158559 9.78 1.09 16.54 222 158560 9.55 1.09 16.39 222 158560 9.59 1.09 16.45 222 158561 9.78 1.12 16.95 222 158561 10.08 1.09 16.47 222 158562 8.21 0.98 14.22 333 158562 9.77 1.11 16.68 333 158563 9.54 1.10 16.32 222 158563 9.96 1.13 17.04 222 158564 8.72 1.02 15.02 333 158564 7.25 0.86 12.62 333 158565 9.36 1.07 16.07 222 158565 8.54 1.03 15.15 222 158566 7.61 0.97 13.66 333 158566 8.80 1.07 15.77 333 158567 8.01 0.99 14.58 222 158567 8.39 1.05 15.44 222 158568 7.33 0.97 13.85 333 158568 8.04 1.04 15.24 333 158569 5.50 0.80 10.09 333 158569 7.85 1.00 14.54 333 158570 7.74 0.93 12.81 222 158570 7.72 0.94 13.19 222 158571 7.10 0.86 11.47 222 158571 7.39 0.90 11.97 222 158572 8.95 0.87 13.01 333 158572 10.44 1.02 15.24 333 158573 6.34 0.76 9.04 333 158573 9.02 0.95 13.08 333 158574 9.62 0.95 13.48 333 158574 10.35 1.02 14.72 333 158575 9.05 0.94 12.84 333 158575 10.83 1.05 15.33 333 158576 8.04 0.84 11.41 333 158576 9.56 0.97 13.28 333 158577 7.99 0.86 11.52 333 158577 9.28 0.91 12.59 333 158578 8.87 0.92 12.55 333 158578 7.38 0.78 10.32 333 158579 5.61 0.70 8.31 333 158579 8.29 0.85 12.29 333 158580 8.43 0.87 13.33 333 158580 10.42 1.01 16.26 333 158581 7.57 0.88 12.79 222 158581 8.58 0.93 14.53 222 158582 6.33 0.79 10.78 222 158582 8.53 0.92 14.35 222 158583 7.92 1.04 12.94 222 158583 6.85 0.81 11.63 222 158584 9.94 1.01 16.87 222 158584 8.17 0.89 13.99 222 158585 5.34 0.71 9.27 333 158585 8.11 0.92 14.13 333 158586 8.16 0.98 14.50 222 158586 9.11 1.04 16.25 222 158587 7.57 0.89 13.51 222 158587 8.01 0.91 14.22 222 158588 7.46 0.87 13.96 333 158588 5.71 0.69 10.94 333 158589 6.93 0.82 12.24 222 158589 7.71 0.90 13.74 222 158590 7.36 0.80 12.04 222 158590 7.46 0.82 11.81 222 158591 7.02 0.75 10.52 222 158591 7.13 0.76 10.73 222 158592 6.43 0.71 9.31 222 158592 6.45 0.70 9.07 222 158593 11.12 0.95 15.70 222 158593 10.99 0.93 14.89 222 158594 11.23 0.95 15.18 222 158594 11.10 0.95 14.95 222 158595 10.30 0.93 14.91 222 158595 11.08 0.97 15.63 222 158596 6.60 0.67 9.79 333 158596 10.52 0.89 15.43 333 158597 9.14 0.86 13.46 333 158597 11.07 0.95 16.07 333 158598 6.94 0.71 10.84 333 158598 9.68 0.92 14.74 333 158599 10.61 1.02 16.41 333 158599 7.33 0.77 11.06 333 158600 8.17 0.84 13.16 333 158600 9.80 0.94 15.79 333 158601 9.56 0.94 15.75 222 158601 10.01 0.96 16.47 222 158602 7.72 0.78 11.91 333 158602 9.92 0.99 16.41 333 158603 9.92 1.00 16.68 222 158603 9.98 0.97 16.28 222 158604 7.33 0.77 12.24 222 158604 7.84 0.77 13.86 222 158605 7.35 0.77 12.95 222 158605 7.92 0.85 14.05 222 158606 6.42 0.72 11.40 222 158606 7.34 0.80 12.26 222 158607 6.95 0.80 12.82 222 158607 7.34 0.84 13.49 222 158608 6.55 0.77 12.39 222 158608 6.86 0.82 12.84 222 158609 7.84 0.89 14.43 222 158609 7.81 0.89 14.83 222 158610 7.65 0.82 12.75 222 158610 7.68 0.83 12.90 222 158611 7.29 0.71 10.14 222 158611 7.32 0.71 10.08 222 158612 3.56 0.43 4.76 333 158612 6.07 0.61 7.94 333 158613 5.39 0.62 8.53 333 158613 8.90 0.91 15.40 333 158614 9.57 0.93 16.35 222 158614 9.72 0.93 16.16 222 158615 8.60 0.90 14.54 222 158615 9.52 0.95 16.18 222 158616 7.33 0.82 12.61 333 158616 9.00 0.92 15.93 333 158617 8.83 0.92 15.82 222 158617 7.97 0.87 14.15 222 158618 6.17 0.66 8.36 222 158618 6.55 0.66 8.99 222 158619 4.99 0.65 9.40 333 158619 6.29 0.72 11.33 333 158620 6.85 0.72 11.66 222 158620 7.34 0.79 12.87 222 158621 6.08 0.65 9.41 222 158621 6.28 0.66 9.33 222 158622 6.56 0.70 9.84 222 158622 6.34 0.66 9.12 222 158623 6.04 0.62 7.87 222 158623 5.07 0.57 6.83 222 158624 4.71 0.43 3.85 222 158624 5.11 0.46 4.19 222 158627 5.30 0.57 6.97 222 158627 5.86 0.60 7.93 222 158628 4.47 0.48 4.95 222 158628 4.81 0.50 5.23 222 158629 3.89 0.41 4.48 222 158629 3.73 0.39 2.91 222 158630 2.55 0.30 0.73 222 158630 2.59 0.29 0.71 222 158631 3.97 0.46 4.73 222 158631 4.71 0.52 5.69 222 158632 4.76 0.54 5.76 222 158632 4.81 0.54 5.80 222 158633 3.55 0.34 1.71 222 158633 3.65 0.36 1.74 222 158634 2.21 0.23 0.10 222 158634 2.15 0.22 0.12 222 5. Dissolved Inorganic Carbon in Seawater (Bob Gershey) a. Description of Equipment and Technique The total dissolved inorganic carbon content of seawater is defined as the total concentration of carbonate ion, bicarbonate ion and unionized species of carbon dioxide. Before analysis, the sample was treated with acid to convert all ionized species to the unionized form, which was then separated from the liquid phase and subsequently measured using a coulometric titration technique. This involved the reaction of carbon dioxide gas with a dimethysulfoxide solution of ethanolamine to produce hydroxyethylcarbamic acid. The acidic solution was titrated with hydroxide ions formed by the electrolytic decomposition of water. The progress of the titration was followed through colorimetric measurement of the absorbance of a pH indicator dye (thymolphthalein) in the ethanolamine solution. A known volume of seawater was dispensed into a stripping chamber from a pipet of known volume and temperature controlled to within 0.4 _C. It was then acidified with ten percent of its volume of a 10% solution of carbon dioxide-free phosphoric acid. The solution was stripped of carbon dioxide gas by bubbling with a stream of nitrogen gas directed through a glass frit. The carrier gas exiting the stripper passed through a magnesium perchlorate trap that removed water vapour and acidic water droplets. The gas stream was then directed into the coulometric titrator where the total amount of carbon dioxide gas was quantified. The coulometer was calibrated in two ways. Calibration using gas loops was accomplished by filling stainless steel sample loops (1.5, 2.5 ml) with 99.995% carbon dioxide gas and injecting these into the coulometer. The temperature and pressure of the gas within the loops must be known to within 0.05 _C and 20 Pa respectively. The system was also calibrated using Certified Reference Materials obtained from the Scripps Institute of Oceanography. These samples were treated in the same manner as a seawater sample. Values will be reported in units of _mol/kg. The overall precision of the analysis should be at least 1.5 _mol/kg for samples with concentrations in the range of 1800-2300 _mol/kg. b. Sampling Procedure and Data Processing Technique Water samples were initially collected using a 10 litre rosette bottle. Samples for analysis of total inorganic carbon were drawn immediately following the drawing of the salinity samples in order to minimize exchange of carbon dioxide gas with the headspace in the sampler. This exchange will typically result in a loss of carbon dioxide. It is desirable that the samples be drawn before half the sampler is emptied and within ten minutes of recovery. Clean borosilicate glass bottles are rinsed twice with 30 - 50 ml of the sample. The bottle is then filled from the bottom using a length of vinyl tubing attached to the spigot of the sampler. The sample is overflowed by at least a half of the volume of the bottle (typically 250 ml). A headspace of 1% is left to allow for expansion without leakage. If samples are not to be analyzed within four to five hours, the sample is poisoned with 100 _l/250 ml of 50% saturated mercuric chloride solution. The bottle is tightly sealed and stored preferably at the temperature of collection in the dark. c. Replicate Analysis The precision of this data was estimated as 4.2 _mol/kg. In total, 25 replicate carbonate measurements were obtained for 24 sample id numbers; 23 sample id numbers had one replicate, while one sample id number had three replicates. But two of the sample id numbers having one replicate, had data that was questionable. The following is a statistical summary of the absolute value of the replicate differences; only acceptable values were used in calculating the statistics. Table C.5 lists all replicate measurements. Number of Replicate Differences = 1 id had two replicates * 3 possible differences + 21 ids had one replicate * 1 possible difference = 3 + 21 = 24 Statistic Value Number of Replicate Differences 24 Minimum (_moles/kg) 0.1 Maximum (_moles/kg) 4.1 Mean (_moles/kg) 1.7 Median (_moles/kg) 1.2 Standard Deviation (_moles/kg) 1.2 Table C.5 Replicate water sample total carbon values in (moles/kg. Sample ID Total WOCE Number Carbon QF 158186 2109.5 2 158186 2106.7 2 158192 2056.0 2 158192 2057.8 2 158195 2107.3 2 158195 2107.9 2 158197 2014.3 2 158197 2015.5 2 158197 2018.5 2 158200 2048.1 2 158200 2051.0 2 158205 2109.6 2 158205 2110.5 2 158206 2111.2 2 158206 2109.0 2 158209 2109.6 2 158209 2110.1 2 158215 2139.2 2 158215 2140.4 2 158227 2145.8 2 158227 2146.2 2 158235 2150.7 2 158235 2151.9 2 158252 2154.2 2 158252 2151.1 2 158272 2150.3 2 158272 2152.3 2 158284 2151.8 2 158284 2153.2 2 158338 2147.5 2 158338 2148.3 2 158366 2146.7 2 158366 2147.7 2 158389 2146.0 3 158389 2148.6 3 158418 2149.5 2 158418 2150.6 2 158482 2151.8 2 158482 2148.6 2 158520 2144.4 3 158520 2147.5 3 158594 2152.1 2 158594 2155.7 2 158615 2148.0 2 158615 2148.1 2 158628 2073.3 2 158628 2073.9 2 158632 2075.3 2 158632 2074.9 2 6. Alkalinity (Bob Gershey) a. Description of Equipment and Technique The total alkalinity of seawater is defined as the number of moles of hydrogen ion equivalent to the excess of proton acceptors (bases formed from weak acids with dissociation constants of less than K=10-4.5) over proton donors (acids with K>10-4.5) in a one kilogram sample. An automated potentiometric titration system is used to determine this quantity. During the course of the titration the pH is measured using a Ross combination electrode standardized using a Hansson seawater buffer. A known volume (~25 ml) of sample is measured in a calibrated, thermostated pipette and dispensed in to an open cup. The alkalinity of the sample is estimated from its salinity and acid equivalent to 0.7 of this amount is added and the pH measured. A further three aliquots of acids are added to bring the titration to 90% completion. The Gran Function F3 (Stumm and Morgan, 1970) is then applied to these points to obtain a more refined estimate of the alkalinity. Five additional aliquots are then added to complete the titration. b. Sampling Procedure and Data Processing Technique Samples were collected using the same procedure as for Dissolved Inorganic Carbon (see Section 5b). The pH values for the last five points of the titration were used to evaluate the Gran Function F1 from which the final estimate of the equivalence point was obtained. Values are reported in units of _mol/kg. The overall precision of the analysis is 1.5 _mol/kg for samples with concentrations in the range of 1900-2400 _mol/kg. c. Replicate Analysis The precision of the alkalinity data was 9.5 _mol/kg. The alkalinity replicates consisted of 22 duplicate measurements. But eight of these sample id numbers had questionable or bad data. A statistical summary of the absolute value of the replicate differences is below. Only acceptable sample values were used when calculating replicate differences. All replicates and their quality flags are given in Table C.6. Statistic Value Number of Replicate Differences 14 Minimum (_moles/kg) 0.0 Maximum (_moles/kg) 19.6 Mean (_moles/kg) 3.5 Median (_moles/kg) 2.2 Standard Deviation (_moles/kg) 5.0 Table C.6 Replicate water sample total alkalinity values in (moles/kg. Sample ID Total WOCE Number Alkalinity QF 158188 2164.6 2 158188 2161.4 2 158191 2207.2 2 158191 2212.7 2 158195 2178.2 2 158195 2197.8 2 158199 2202.3 2 158199 2203.2 2 158210 2205.7 2 158210 2210.6 2 158215 2252.8 2 158215 2252.8 2 158216 2252.2 2 158216 2249.6 2 158226 2275.5 3 158226 2290.7 2 158236 2280.1 2 158236 2285.5 2 158253 2281.7 3 158253 2293.4 3 158273 2283.6 2 158273 2284.5 2 158294 2336.3 4 158294 2272.1 4 158314 2290.1 2 158314 2292.9 2 158339 2283.1 2 158339 2284.8 2 158367 2301.0 2 158367 2301.7 2 158368 2299.9 3 158368 2316.1 3 158412 2312.8 3 158412 2322.7 3 158435 2360.1 4 158435 2301.2 3 158459 2261.0 4 158459 2308.9 3 158511 2287.7 2 158511 2287.9 2 158551 2287.3 3 158551 2295.6 3 158613 2297.4 2 158613 2297.3 2 7. CFCs (Mike Hingston) a. Description of Equipment and Technique The analyses were carried out on two Purge and Trap systems developed at the Bedford Institute of Oceanography. The water samples were injected into the systems directly from the syringes. To ensure proper rinsing, at least two volumes of water were passed through the sample pipette before the actual sample volume. The samples were purged for 4 minutes with ultra high purity nitrogen at a flow rate of 80 ml/min. The components were trapped in Porapak-N trap which were then cooled to a temperature of less than 10_C. The trap was heated up to at least 170_C causing the components to be desorbed. The contents of the trap were then passed through a 75 m DB-624 megabore column. b. Sampling Procedure and Data Processing Technique All samples were collected directly from the Niskin bottles using 100 ml syringes. The syringes were rinsed three times before they were filled. To prevent contamination, the CFC samples were the first samples collected from the Niskin bottles. The samples were stored in a water bath of surface seawater that flowed continuously until analysis. Air samples were taken in the winch room at the start of the cruise to ensure that it was not contaminated. The analyses of the samples were always completed within 24 hours after they had been drawn. c. Replicate analysis A total of 22 unique sample id numbers had triplicate CFC water samples drawn. Replicates were taken at most stations, with some of these being run on each system to ensure that the results were comparable. A statistical summary of the absolute value of the replicate differences is below. Only acceptable sample values were used when calculating replicate differences. All replicates and their quality flags are given in Table C.7. Statistic CFC11 CFC12 CFC113 Carbon Tet. Methyl Chl. # of Replicate Differences 66 62 49 59 37 Minimum (pmoles/kg) 0.009 0.001 0.000 0.007 0.015 Maximum (pmoles/kg) 0.338 0.520 0.222 0.655 1.861 Mean (pmoles/kg) 0.125 0.087 0.060 0.185 0.633 Median (pmoles/kg) 0.109 0.064 0.039 0.131 0.589 Standard Dev. (pmoles/kg) 0.086hu 0.091 0.060 0.164 0.425 Detection Limits (pmoles/kg) 0.14 0.10 0.13 0.29 0.63 Table C.7 Replicate water sample CFC values in pmoles/kg. Sample ID Carbon Methyl Number Freon 11 Freon 12 Freon 113 Tet. Chl. WOCE QF 158187 5.824 2.999 0.347 9.712 12.348 22224 158187 6.120 2.905 0.442 9.466 15.579 22224 158187 6.064 3.037 0.000 9.095 14.801 22422 158193 6.192 3.067 0.000 9.708 14.949 22442 158193 6.290 3.172 0.364 10.828 13.088 22232 158193 6.222 3.173 0.370 11.571 14.207 22232 158207 6.126 3.119 0.443 9.541 14.999 22222 158207 6.068 3.039 0.512 9.256 14.456 22222 158207 5.788 0.000 0.000 8.911 10.566 24424 158208 4.964 2.434 0.376 7.231 11.513 22224 158208 5.049 2.391 0.427 7.159 13.610 22222 158208 4.948 2.402 0.349 7.460 13.357 22222 158216 4.123 2.161 0.296 5.632 8.661 22224 158216 4.089 2.184 0.335 5.693 7.973 22224 158216 4.162 2.152 0.499 5.562 10.047 22222 158228 4.058 1.973 0.182 5.899 11.194 22224 158228 3.933 1.922 0.265 5.832 9.630 22222 158228 4.020 1.906 0.382 6.487 9.327 22222 158242 3.445 1.604 0.000 5.486 9.079 22424 158242 3.646 1.693 0.000 5.283 10.355 22422 158242 3.628 1.706 0.000 5.353 10.670 22422 158260 3.415 1.994 0.222 6.421 8.769 22242 158260 3.594 1.849 0.000 5.252 10.851 22224 158260 3.393 2.003 0.199 5.285 7.856 22222 158286 3.938 2.033 0.305 5.809 8.107 22224 158286 4.096 2.083 0.000 5.854 10.676 22422 158286 4.051 2.020 0.293 5.775 10.346 22222 158299 2.023 0.963 0.205 3.333 3.811 22224 158299 2.211 1.063 0.261 3.645 6.822 22222 158299 2.136 1.061 0.277 3.415 4.119 22224 158329 3.662 1.704 0.242 5.255 10.511 22222 158329 3.469 1.604 0.208 5.142 8.806 22224 158329 3.650 1.697 0.247 5.083 10.222 22222 158354 3.905 2.109 0.320 6.227 9.207 22222 158354 3.973 2.099 0.381 5.846 9.169 22222 158354 4.169 2.038 0.299 5.936 11.491 22224 158374 3.297 1.556 0.210 4.943 9.737 22222 158374 3.078 1.512 0.224 4.748 9.563 22222 158374 3.316 1.537 0.243 4.854 9.548 22222 158404 3.429 1.731 0.255 5.240 10.053 22222 158404 3.460 1.915 0.328 5.791 9.355 22222 158404 3.699 1.787 0.000 5.562 10.641 22422 158421 3.326 1.749 0.275 5.080 10.292 22222 158421 3.553 1.724 0.326 5.111 10.509 22222 158421 3.516 1.759 0.258 5.250 11.289 22222 158450 3.551 1.805 0.238 5.205 10.819 22224 158450 3.393 1.835 0.352 5.364 8.503 22222 158450 3.342 1.844 0.353 5.082 9.514 22222 158460 2.069 1.177 0.000 3.472 5.132 22224 158460 2.222 1.011 0.132 3.464 7.162 22222 158460 2.234 0.978 0.138 3.457 6.950 22222 158485 1.704 0.781 0.000 2.875 5.323 22222 158485 1.822 0.717 0.000 3.055 5.710 22222 158485 1.732 1.020 0.000 2.791 4.504 22222 158516 3.598 1.585 0.249 5.186 10.557 22222 158516 3.635 1.738 0.000 5.240 11.072 22422 158516 3.499 1.667 0.248 5.096 9.897 22222 158544 3.913 2.136 0.307 6.074 8.819 22222 158544 3.879 2.033 0.278 5.948 9.437 22222 158544 4.100 2.052 0.283 5.974 10.206 22222 158601 3.071 1.395 0.000 4.542 9.382 22422 158601 3.167 1.589 0.166 4.821 9.276 22222 158601 3.062 2.056 0.185 6.171 8.793 24242 158620 3.989 1.810 0.338 5.785 9.038 22222 158620 4.202 2.110 0.286 5.859 9.948 22222 158620 4.185 2.330 0.289 5.844 9.735 22222 d. Standards Used Standardization was carried out using gas standards made up at Brookhaven National Laboratories. Standard volumes were corrected for lab temperature and pressure. Results were reported in units of pmol/kg of seawater. Clean air samples were also analyzed with each station, as a check on the standardization. 8. Reversing Thermometers (Anthony W. Isenor) a. Description of Equipment and Technique Sensoren-Instrumente-Systeme digital reversing thermometers model RTM 4002 were used to verify CTD thermistor readings on some stations. These thermometers have a depth range of up to 10000 m. The pressure housing is made of a glass tube closed at the ends by metal stoppers. One end contains the platinum sensor and the other end is the battery compartment. The thermometers were placed on bottles 2 and 4 on the rosette, thus sampling temperature at the second and forth deepest bottle trips. The thermometers were placed in standard reversing thermometer racks on the Niskin bottles. Before deployment, a magnet was passed over the thermometers to clear the display and place the thermometer in sample mode. A new temperature was then recorded upon reversal of the thermometer. b. Sampling Procedure and Data Processing Technique The digital thermometers indicated the temperature reading via a digital display. The temperature was read and noted on log sheets. The readings were later digitized and corrections applied using the water sample database system. The following table lists the number of readings from each thermometer. Thermometer Serial Number Number of Readings 000T347 12 000T352 12 000T878 11 000T881 10 In total, 59 readings were obtained. Of these, 14 had problems with either tripping or soaking time. Thus, 45 valid comparisons with the CTD thermistor can be made. c. Calibration Data The digital reversing thermometers were calibrated at BIO in February 1996. d. Replicate Analysis Typically, a rack containing two thermometers would be tripped when the second and forth Niskin bottles were fired. Thus, we would obtain two independent temperature readings. However, due to the removal of the thermometers during rough weather, many stations near the end of the cruise did not have thermometer readings. Statistics calculated using the differences of all duplicate temperatures from the digital reversing thermometers are as follows: Statistic Value Number of Points 29 Median 0.002 _C Mean 0.043 _C Minimum 0.000 _C Maximum 0.723 _C Standard Deviation 0.153 _C All of the replicate reversing thermometer temperature values, along with the reversing thermometer pressure values are given in Table C.8. Using the median difference as a measure of the inter-thermometer comparison (the mean is influenced equally by all points, including outliers), we noted that the estimated thermometer difference is 0.002 _C. Thus, the difference between thermometers was the same as the difference between thermometers and the CTD. Therefore, we could not distinguish the difference between the thermometers and the CTD. Consequently, we did not apply any temperature calibration to the CTD based on the thermometer data. Table C.8 Replicate Reversing Thermometer samples. Temperature is in (C and ITS-90 scale. Sample ID Thermometer Main Corrected WOCE QF Number Serial Number 158002 T347 2.022 2 158002 T352 2.025 2 158004 T878 1.801 2 158004 T881 1.805 2 158011 T347 6.874 2 158011 T352 6.876 2 158013 T878 2.784 2 158013 T881 2.794 2 158027 T347 10.047 2 158027 T352 10.045 2 158029 T878 10.304 2 158029 T881 10.302 2 158048 T347 6.386 2 158048 T352 6.437 2 158050 T878 4.630 2 158050 T881 4.683 2 158056 T347 7.339 2 158056 T352 7.340 2 158058 T878 4.686 2 158058 T881 4.683 2 158066 T347 7.644 2 158066 T352 7.642 2 158068 T878 7.559 2 158068 T881 7.602 2 158084 T347 8.116 2 158084 T352 8.839 2 158086 T878 9 158086 T881 9 158186 T347 -1.697 2 158186 T352 -1.698 2 158188 T878 -0.718 2 158188 T881 -0.730 2 158209 T347 -0.668 2 158209 T352 -0.669 2 158211 T878 -1.461 2 158211 T881 -1.465 2 158235 T347 9 158235 T352 9 158237 T878 9 158237 T881 9 158252 T347 2.241 2 158252 T352 2.241 2 158254 T878 2.380 2 158254 T881 2.378 2 158272 T347 9 158272 T352 9 158274 T878 9 158274 T881 9 158292 T347 9 158292 T352 9 158294 T878 9 158294 T881 9 158315 T347 1.641 2 158315 T352 1.661 2 158338 T347 1.690 2 158338 T352 1.693 2 158340 T878 2.192 2 158340 T881 2.189 2 9. Helium/Tritium (Samar Khatiwala) Samar Khatiwala collected a total of 246 He and 252 Tr samples for Peter Schlosser of Lamont- Doherty Earth Observatory, Columbia University. a. Description of Equipment and Technique He samples were collected through tygon tubing into copper tubes (40 g capacity) bolted into aluminum channels for support and protection. Tr samples were collected into one-litre Argon filled brown glass bottles, directly from the Niskin spigot. b. Sampling Procedure and Data Processing Technique He samples were drawn after CFCs and occasionally after DOC (WOCE parameter 43). Delivery was through tygon tubing, cured in seawater to reduce bubbles, which was monitored for air bubbles. All detected bubbles were worked out of the line. After which the metal channel holding the copper sample tube was struck several times on one side with a ratchet in a pattern from the intake end towards the outflow end of the copper tube in order to pass any air bubbles out of the sample tube. Flushing of the copper tube took place during both parts of the bubble- removing procedure. When air removal and flushing were complete, both ends of the copper tube were sealed by tightening the two bolts at each end with a ratchet wrench, starting with the outflow end. GMT time of sampling was routinely noted for each sample. These samples were shipped to Lamont for analysis. Tritium samples were collected into argon-filled bottles without rinsing or flushing, after all other samples were collected from the rosette. The bottle caps were secured with electrical tape at the completion of each station. These samples were shipped to Lamont for analysis. Occassionally, the Niskins were drained before the tritium was collected. Careful rinsing of all samples helped alleviate this problem. Replacement watches were handed out to all persons in the scientific party and the winch drivers who normally wore luminous-dial watches, and a sign was posted at each rosette room door to avoid wearing luminous-dial watches inside the room. 10. Oxygen Isotopes (Anthony W. Isenor) a. Sampling Procedure Water samples were initially collected using a 10 litre rosette bottle. Samples for salinity isotope analysis were collected last in the sampling. A total of about 550 isotope samples were drawn. Duplicates were drawn on some stations. Samples were collected in 15 ml sample bottles. Samples were sent to Bob Houghton at Lamont Geological Earth Observatory, Columbia University, Palisades, NY. D. MOORED MEASUREMENTS - DESCRIPTIONS, TECHNIQUES AND CALIBRATIONS 1. Current Meter Moorings (John R. N. Lazier) a. Description of the Equipment and Technique There was one partial recovery (M1194), one full recovery (M1200) and three deployments (M1227, M1229 & M1230) of BIO deep-sea moorings on cruise 96006. Mooring 1194 consisted of 6 Seacat temperature / conductivity recorders, 6 Aanderaa current meters, 1 acoustic doppler current profiler, 1 WOTAN (weather observations through ambient noise) and 1 CTD with a device for measuring the partial pressure of dissolved gas in water. It was intended to recover this mooring and deploy a duplicate mooring in the same location. However, during the recovery process the weather deteriorated causing delays in grappling the upper float and excessive working of the buoyancy packages in the mounting seas. This in turn caused some seizing wire on the shackles to break, the shackle pins worked loose, and the mooring separated into two pieces. Recovery then proceeded from the bottom end of the mooring, but high winds pushed the ship breaking the mooring wire and the remainder of the mooring sank. The recovered components consisted of 2 current meters, 1 release, the WOTAN and CTD with dissolved gas instrumentation. The recovered mooring (M1200) and its replacement (M1227) had the same configuration (see figure 5 below) of one main float called a Hibernia Package, one Aanderaa Current Meter, two backup buoyancy packages and one acoustic release. Both of the other two deployed moorings (M1229 and M1230) had the same configuration (see figures 6 and 7 below) of one main float called a Hibernia Package, one Benthos acoustic release, two backup buoyancy packages and one acoustic release. All three deployed moorings were constructed using 3/16_ jacketed wire. Stainless steel shackles and swivels were used to connect the instruments and backup buoyancy packages. All shackles were secured with a short piece of wire. The acoustic releases were 723A EG&G DACs. The moorings were designed for a 12-month deployment. The back-up buoyancy packages consisted of two 17_ glass balls contained in plastic hard hats and fastened to a stainless steel tension bar one meter in length. These backup buoyancy packages were shackled together to form doubles and triples before they are shackled into the mooring line. b. Sampling Procedure and Data Processing Techniques The recovered Aanderaa current meters recorded at a sampling interval of three hours. The data was processed using standard software packages within the BIO Oceans suite of programs. This processing consisted of the following steps: _ sensor calibrations were applied to compute engineering units from instrument encoder numbers. This applied to all parameters. _ compass direction was converted to degrees True _ initial and end records during the deployment and recovery period were removed from the dataset. Data points out of range were also removed. c. Calibration Data The temperature, pressure and direction sensors of the Aanderaa current meters were calibrated in the laboratory prior to deployment. These calibrations were not included in this cruise report. Recovery Log Mooring No. 1194 Ship: Hudson Cruise No: 96006 Date: 21/05/1996 Mooring Technician: Scotney/Hartling/Boyce Sea State: 03-Apr Weather Conditions: 25kt wind, cloudy, cool Time (Z) May 21, 1996 Instrument Remarks 0921 Release Release command accepted - Release 504801 Heavy weather - difficulty getting close and grappled 1203 Mooring hooked and float lifted on board 1205 Main float and CTD/GTD (IOS) on board 1207 CM4355 on board 1212 WOTAN on board 1215 1 Hard hat package on board - broken from remainder 1222 Yellow balls sighted - 3 groups 1330 Package caught on 3rd attempt - Bottom group 1335 Release 504801 and bottom package on board 1340 CM4195 on board Pulling in line with yellow balls - "Line Parted" Position is 56( 44.300 N, 52( 27.550 W Recovery Log Mooring No. 1200 Ship: Hudson Cruise No: 96006 Date: 19/05/1996 Mooring Technician: Scotney/Hartling Sea State: 2-3 Weather Conditions: Cloudy / cool 1335 Release Release contacted - transponder working Using Benthos gear to find range = 1370 m (slant range) 1337 Release Release command accepted 1403 Floats On the surface Light flashing 1430 CM 5577 Out of the water - on deck - rotor spinning 1438 Release and lower floats on board Deployment Log Mooring No: 1227 Geographic Area: Labrador Slope Intended Duration: 1 year Ship: CSS Hudson Cruise Number: Date: May 19/96 Sea State: Weather Conditions: cloudy and cool Mooring Tech.: Scotney/Hartling Navigation Inst.: GPS Latitude: 55 07.209 N Longitude: 54 05.103 W Time of Fix: 1739Z Depth Raw: Depth Corrected: Main Float Type: 4 Yellow Balls Main Float Markings: nil Radio Beacon Type: No Beacon Radio Beacon Freq.: Light Type: OAR Light Colour and Rate: White Mooring Line Type: Yellow Jacketed wire Mooring Line Colour: Yellow Release Type: EG&G S/N: Release Code: Time (Z) Instrument Remarks Release Test OK 1637 Mooring assembly on foredeck Light working Wait while oil spill on port side attended to 1737 RCM 6404 Over the side - in water 1740 Anchor released 1755 Release disabled Figure 5. Mooring No. 1227 Deployment Log Mooring No: Geographic Area: Emerald Basin Intended Duration: 1 year Ship: Hudson Cruise no.: Date: May 13/96 Sea State: Weather Conditions: clear and windy Mooring Tech.: Scotney/Hartling Navigation Inst.: DGPS Latitude: 43 53.17 N Longitude: 62 51.89 W Time of Fix:: 1206Z Raw Depth: 256 m Corrected Depth: 261 m Main Float Type: Hibernia Main Float Markings: Radio Beacon Type: Radio Beacon Freq.: Light Type: Light Colour and Rate: Mooring Line Type: Jacketed wire Mooring Line Colour Yellow Release Type: EG&G Release S/N: Release Code: Release Type: Benthos Release S/N: Release Code: C Time (Z) Instrument Remarks 1206 Anchor away Figure 6. Mooring No. 1229 Deployment Log Mooring No: 1230 Geographic Area: Hamilton Bank Intended Duration: 1 year Ship: Hudson Cruise no.: Date: May 25/96 Sea State: Weather Conditions: sunny and clear Mooring Tech.: Scotney/Hartling/Boyce Navigation Inst.: GPS Latitude: 58 37.86 N Longitude: 50 24.64 W Time of Fix:: 1657Z Raw Depth: 3450 m Corrected Depth: 3456 m Main Float Type: Hibernia Main Float Pack Markings: Radio Beacon Type: Radio Beacon Freq.: Light Type: Novatech Light Colour & Rate: white Mooring Line Type: Jacketed wire Mooring Line Colour: Yellow Release Type: EG&G Release S/N: Release Code: Release Type: Benthos Release S/N: Release Code: D Time (Z) Instrument Remarks 1657 Mooring away 1746 Mooring on bottom 1750 Releases disabled Figure 7. Mooring No. 123 E. REFERENCES Carritt, D.E. and J.H. Carpenter. 1966. Comparison and Evaluation of Currently Employed Modifications of the Winkler Method for Determining Dissolved Salinity in Seawater. A NASCO Report, Jour. Mar. Res., 24, 268-318. Clarke, R. Allyn, Jean-Guy Dessureault and Geoff Lebans. 1995. Upper Ocean Profiling from Vessels Underway, Sea Technology, February 1995. Jones, E.P., F. Zemlyak and P. Stewart. 1992. Operating Manual for the Bedford Institute of Oceanography Automated Dissolved Salinity Titration System. Can. Tech. Rep. of Hydrography and Ocean Sci. 138: iv+51p. Levy, E.M., C.C. Cunningham, C.D.W. Conrad and J.D. Moffatt. 1977. The Determination of Dissolved Salinity in Sea Water, Bedford Institute of Oceanography Report Series, BI-R-77-9, August 1977. Stumm, W. and J.J. Morgan. 1970. Aquatic Chemistry: An Introduction Emphasizing Chemical Equilibria in Natural Waters. Wiley-Interscience, New York, 583 pp.