RV Pelagia Cruise Report: Cruise 64PE95N/1, Project TripleB, WHP repeat area AR12 H.M. van Aken Chief Scientist Bay of Biscay Boundary NIOZ, Texel, 199 Table of contents nr. Chapter page 1 Cruise Narrative 5 1.1 Highlights 5 1.2 Cruise Summary Information 5 Cruise Track 5 Number of Hydrographic Stations 6 Hydrographic Sampling 7 Drifters and Moorings 7 *.SUM file 8 1.3 List of Principal Investigators 9 1.4 Scientific Programme and Methods 9 Preliminary Results 10 1.5 Major Problems Encountered during the Cruise 15 1.6 Additional Observations 16 1.7 List of Cruise Participants 16 2 Underway Measurements 17 2.1 Navigation 17 2.2 Echo Sounding 17 2.3 Thermo-Salinograph Measurements 17 3 Hydrographic Measurements - Descriptions, Techniques, and Calibrations 19 3.1 Rosette Sampler and Sampler Bottles 19 3.2 Temperature Measurements 19 3.3 Pressure Measurements 20 3.4 Salinity Measurements 21 3.5 Oxygen Measurements 22 3.6 Nutrient Measurements 25 3.7 Transmissometer Measurements 26 3.8 CTD Data Collection and Processing 27 Appendix A Tables with duplicate samples 29 Table 1 Reversing electronic thermometers 30 Table 2 Sample salinity 34 Table 3 Sample oxygen 36 Table 4 Dissolved silica 40 Table 5 Dissolved nitrate 42 Table 6 Dissolved nitrite 44 Table 7 Dissolved phosphate 46 The research reported here was funded by the Foundation for Geological, Oceanographic and Atmospheric Research (GOA), subsidiary of the Netherlands Organization for Scientific Research (NWO) 1 Cruise Narrative 1.1 Highlights a: WOCE Repeat Section AR12, RV Pelagia cruise 95N/1 in the Bay of Biscay b: Expedition Designation (EXPOCODE): 64PE95N/1 c: Chief Scientist: Dr. Hendrik M. van Aken Netherlands Institute for Sea Research (NIOZ) P.O.Box 59 1790AB Den Burg/Texel The Netherlands Telephone: 31(0)222-369416 Telefax: 31(0)222-319674 Internet: aken@nioz.nl d: Ship: RV Pelagia Call Sign: PGRQ length 66 m. beam 12.8 m draft 4 m maximum speed 12.5 knots e: Ports of Call: Texel, the Netherlands to Brest, France f: Cruise dates: July 18, 1995 to August 14, 1995 1.2 Cruise Summary Information Cruise Track The cruise was carried out in the Bay of Biscay east of 12_W. The cruise track is shown in figure 1. Figure 1. Cruise track in the Bay of Biscay. The topography of the ocean basin is indicated with isobaths, depth im m. Number of Hydrographic Stations A total of 106 CTD/rosette casts (figure 2) were occupied along sections A to I, using a General Oceanics rosette, equipped with 24 10-litre NOEX water sample bottles, and a SBE 911+ CTD, equipped with a SensorMedic oxygen sensor, a Sea Tech Inc. 0.25 m path transmissometer and a Chelsea fluorometer. Additional to these CTD-rosette casts 7 CTD-casts were recorded for test purposes, an two CTD-yo-yo stations were occupied. A bottom switch with the weight at 4 m below the CTD sensors was used to indicate the proximity of the bottom. Figure 2. Positions of CTD sections and stations. Hydrographic Sampling A total of 1990 water samples was collected. The following water sample measurements were made: salinity, oxygen, silica, nitrite, nitrate, and phosphate. The vertical distance between the samples amounted to 250 m or less, depending on the total water depth (figure 3). The deepest sample from each cast was collected within 10 m from the bottom. On sample bottles 2, 4, 6, and 8 racks with SIS reversing electronic thermometers and pressure sensors were mounted for calibration purposes. Figure 3. Location of the 10 litre water samples collected during the cruise. Drifters and Moorings A total of 10 ARGOS mixed layer surface drifters was deployed (figure 4). These drifters were drogued with a holey sock drogue, centred at de depth of 15 m. A total of 8 long term current meter moorings were deployed for an intended period of one year (BB1 to BB8). Additional a benthic lander fitted with 2 ADCPs and two thermistor string moorings (T1 and T2) were deployed and recovered for periods of 24 days and 1.5 days respectively. The positions of these moorings is shown in figure 5. Figure 4. Deployment positions of the ARGOS surface drifters. The labels give the PTT numbers. Figure 5. Positions of the moorings, deployed during the cruise. The labels show the mooring identification as used in the *.SUM file. *.SUM file A hard copy of the preliminary *.SUM file describing all stations is added in the appendix B. 1.3 List of Principal Investigators Name Responsibility Affiliation Dr. H.M. van Aken Ocean hydrography, ARGOS drifters. NIOZ/Texel Drs. C. Veth Current measurements. NIOZ/Texel Ing. S. Ober CTD & rosette-technology NIOZ/Texel Dr. J. van Haren Boundary mixing NIOZ/Texel Drs. F.-P. Lam Tide-topography interaction NIOZ/Texel J. van Haren and F.-P. Lam did not participate during the cruise, but they are responsible for the data processing and interpretation. 1.4 Scientific Programme and Methods The goal of the research carried out during the cruise was to establish the structure, course and transport of the eastern boundary current in the Bay of Biscay, as well as the hydrographic structure of the Bay of Biscay and the nearby eastern North Atlantic, as it is affected by the eastern boundary current. For this purpose a hydrographic survey has been carried out in the Bay of Biscay up to 12*W, 8 long term current meter moorings and 10 ARGOS surface drifters have been deployed. The hydrographic survey covers a large part of the WOCE Hydrographic Research Programme repeat area AR12. The CTD-rosette frame was weighted in order to secure a fast enough falling rate. This package was lowered with a velocity between 1 and 1.5 m/s, except in the lowest 100 m, where the veering velocity was reduced. Measurements during the down-cast went on to within 4 m from the bottom, until the bottom switch indicated the proximity of the bottom. During the up-cast water samples where taken at prescribed depths, when the CTD winch was stopped. After each cast the CTD/rosette frame was placed on deck. Subsequently water samples were drawn for the determination of dissolved oxygen, salinity and nutrients, and the readings of the electronic reversing thermometers and pressure sensor were recorded. Additional to the main hydrographic research programme ADCP observations have been carried out by means of a benthic lander to study the low frequency turbulent mixing over the continental slope. Short term high frequency temperature observations have been performed with moored thermistor strings and with CTD yo-yos at two different locations to study internal solitons and other internal waves in the seasonal thermocline as well as in the bottom boundary layer over the continental slope, generated by tide-topography interaction. At test stations previous to station 13 a new type of rosette sampler, fitted with a new type of the NOEX sample bottles underwent its first field test. During part of the CTD-casts the CTD was additionally fitted with a new type of SBE temperature sensor which should reduce the heating of the temperature probe by dissipation in the viscous sub-layer around the sensor. Also experiments have been carried out with a new type SBE electronic reference thermometer (SBE35) which, in the future, should be the main temperature reference for the CTD temperature sensor. Preliminary Results As an example of the hydrography of the Bay of Biscay, observed during the Pelagia cruise we present here the results, as observed along section A from the French continental shelf towards the Spanish shelf. The distribution of the potential temperature (THETA) shows some eddy activity in the permanent thermocline (figure 6). The lowest observed potential temperatures were slightly above 2_C. Figure 6. Distribution of potential temperature (THETA) along section A. The salinity distribution (CTDSAL, figure 7) clearly shows a high salinity core (>35.6) at a pressure of about 1000 dbar, connected with the presence of a core of Mediterranean Sea Water. At about 2000 dbar occasionally low salinity cores are observed (<35.0), connected with the presence, in the north-western part of the Bay of Biscay of cores of Labrador Sea Water. The geostrophic velocity relative to the __=27.88 kg m-3 potential density anomaly surface across section A (figure 8) shows a sub-surface eastward inflow over the Spanish continental slope with typical velocities of several tens of cm/s, coinciding with salinities over 35.85 in the Mediterranean Water core. Over the French continental slope a similar sub-surface velocity core is observed, here directed in north-western direction. North of the Spanish continental slope a near surface anti-cyclonic eddy is observed which was already present there about one month earlier (B. Le Cann, pers. comm.). Figure 7. Distribution of salinity (CTDSAL) along section A. Figure 8. Geostrophic velocity across section A (cm/s), relative to the __=27.88 kg/m3 surface. Positive velocities (full line) are eastwards, negative velocities (dashed lines) are westwards. Contour spacing is 2.5 cm/s. The distribution of dissolved oxygen (OXYGEN, figure 9) shows minima, connected with the Mediterranean Sea Water core and maxima, connected with the low salinity Labrador Sea water core. The nutrients silica and nitrate (SILCAT & NITRAT, figures 10 and 11) do not show any sub-surface extremes related to either Mediterranean Water or Labrador Sea Water Figure 9. Distribution of dissolved oxygen (average of OXYGEN and CTDOXY) in _mol/kg from water samples along section A. Figure 10. Distribution of dissolved silica (SILCAT) in _mol/kg from water samples along section A. Figure 11. Distribution of dissolved nitrate (NITRAT) in _mol/kg from water samples along section A. The water mass structure as observed during the cruise can also be discerned from the potential temperature-salinity plot (figure 12) and other potential temperature-property plots (figure 13). Whereas both Mediterranean water and Labrador Sea Water can be recognized from the salinity and oxygen extremes, such maxima and minima are not observed in the nutrients. However the THETA- nutrient plots still show clear property cores, connected with these water types. The distributions of nitrate and phosphate are highly correlated (figure 13 c, d) but the water below the Labrador Sea Water core, that is Lower Deep Water with a high Antarctic Bottom Water content, have a lower N/P ratio than the shallower water types, well above the canonical Redfield ratio of 16 (figure 14). Figure 12. Potential temperature (THETA)-salinity (CTDSAL) diagram for all water samples. Figure 13. Dissolved oxygen and nutrients in _mol/kg (a, OXYGEN; b, SILCAT; c, NITRAT; d, PHSPHT) versus potential temperature (THETA). Figure 14. Nitrate (NITRAT) versus phosphate (PHSPHT) for all samples. The dashed line shows the canonical Redfield ratio N/P=16. 1.5 Major Problems Encountered during the Cruise No major problems were encountered during the cruise. The fair weather during our four weeks in the Bay of Biscay limited the strain on the instrumentation as well as on the personnel. One of the minor problems was the fact that the shipboard computer network was not completely compatible with the NIOZ network. Recent updates of software, already implemented at NIOZ, were missing aboard Pelagia. The software, generating on-line PC-readable files from the ABC data logging system produced erroneous results on some days, while the format of these file sometimes changed from day to day. This problem was solved by generating dumps of the ABC data under UNIX, which were consecutively transformed to DOS files and reduced to 1 minute average readings, readable by EXCEL, by means of some specially written applications. A second problem we encountered was the deformation of one of the sides of the newly acquired cable drum of the CTD winch. Due to the partial widening of the spooling width on the drum (~8 mm) the spooling of the cable was not as smooth as wished, but no serious damage to the cable was observed. 1.6 Additional Observations In order to study the generation of internal solitons in the seasonal thermocline two moorings. fitted with thermistor string (T1 and T2, see figure 5) were moored on the continental shelf, while over the continental slope a 25 hours CTD yo-yo station was occupied on august 1 and 2. Two trains of solitons were observed to pass the yo-yo site, with a time difference of the first soliton of precisely one semi- diurnal tidal period. A deep CTD yo-yo, covering the lowest 400 m over the continental slope below the Mediterranean Water Core was performed for 12.5 hours on August 12. The ship was kept in position with a RMS distance to the central point of about 100 m. The bottom slope amounted about 20%. Strong temperature observations were observed with the character of an internal tidal wave, shoaling on the continental slope. 1.7 Lists of Cruise Participants Scientific crew Person Responsibility Institute H.M. van Aken Chief Scientist/ARGOS drifters NIOZ C. Veth Current Measurements/Hydro Watch NIOZ J. Thieme Preparation Current Meters and Lander/Hydro Watch NIOZ S. Ober CTDO2 sytem/Hydro Watch NIOZ M. Manuels Oxygen Determination NIOZ M. Hiehle Salinity Determination/Data Management NIOZ K. Bakker Nutrients NIOZ E. van Weerlee Nutrients NIOZ J. Derksen Data Logging System/Acoustic Releases/Hydro Watch NIOZ E. Bos Mooring Deployment/CTD Winch Operations NIOZ C. Willems Mooring Deployment/CTD Winch Operations NIOZ W. Kwak Oxygen determination IMAU M. Zachariasse Hydro-Watch IMAU M. de Graaf Hydro-Watch IMAU C. Reijmer Salinity Determination IMAU Ships crew A Souwer captain M. van Duyn first mate A. Schoo second mate J. Pieterse first engineer J. Seepma second engineer C. Stevens technician P. Saalmink technician D. Benne cook R. van der Heide able seaman 2 Underway Measurements 2.1 Navigation RV Pelagia has several different navigational systems. We used the Differential GPS receiver for the determination of the position. The data from this receiver were recorded every second in the ABC data logging system. After removal of a few spikes these data were reduced to one minute average positions. 2.2 Echo Sounding The 3.5 kHz echo sounder was used on board to determine the water depth. The uncorrected depths from this echo sounder was recorded in the ABC data logging system. Over the steepest parts of the continental slope the depth digitizer was occasionally not able to find a reliable depth. Preceding the deployment of the benthic ADCP lander and the current meter moorings on the continental slope a small echo sounder survey was carried out to determine the exact deployment locations. The SIMRAD EK 500 multiple frequency echo sounder was used to observe the variations in the depth of the scattering layer due to internal waves in the seasonal thermocline. Whenever the ship was near the continental slope data from this instrument were recorded on the ship's computer as well as on a colour printer. 2.3 Thermo-Salinograph Measurements The Sea Surface Temperature and Salinity (figures 15 and 16) were measured with an AQUAFLOW thermo-salinograph with a water intake at a depth of about 3 m. The primary temperature sensor, mounted near the water inlet, had been calibrated just prior to the cruise. For the calibration of the salinity sensor water samples were taken three times per day. From the salinity determined from these samples a calibration for the cruise has been determined. The RMS value of the difference of the calibrated AQUAFLOW salinity and the water sample salinity amounted to 0.03. Figure 15. Horizontal distribution of the sea surface temperature, as recorded with the thermo- salinograph. The dots give the ship's position every 30 minutes. Figure 16. Horizontal distribution of the sea surface salinity, as recorded with the thermo- salinograph The dots give the ship's position every 30 minutes. The sea surface temperature (SST, figure 15) and the sea surface salinity (SSS, figure 16) as recorded with the thermo-salinograph, show the effects of the very shallow salinity stratification over the shelves in the south-eastern Bay of Biscay due to river runoff from Spanish and French rivers. Due to the resulting salinity stratification seasonal warming was restricted to a thin surface layer. 3 Hydrographic measurements - Descriptions, Techniques, and Calibrations 3.1 Rosette Sampler and Sampler Bottles A General Oceanics 24 position rosette sampler was used, fitted with 10 litre NOEX sampler bottles. Their general behaviour was good, but a number of bottles had to be replaced during the cruise. This was mainly because of failure of the silicon rubber tubes of the closing system causing failures of closing in time. The sampling had a resulting failure rate of 6 percent because of malfunctioning of the bottles. No errors in the functioning of the rosette sampler itself could be detected. 3.2 Temperature Measurements On sampler bottles 2, 4, 6, and 8 thermometer racks were mounted, fitted with SIS electronic reversing thermometers with a numerical resolution of 1 mK. These thermometers were calibrated before as well as after the cruise at the water triple point as well as at a number of other temperatures in the intermediate and deep water temperature range. During the cruise a number of these thermometers were checked in a specially developed water triple point cell. The differences between the radings of paired SIS reversing thermometers amounted to 1.9 mK, suggesting a precision of individual readings of 1.3 mK and of the average of paired readings of about 1.0 mK. The duplicates are given in table 1. For a total of 334 samples temperatures (REVTMP) were obtained with the SIS electronic reversing thermometers. Of these 53 had to be discarded as outliers, generally connected with either bad duplicates (quality flag 4) or a high background temperature gradient (quality flag 3). The resulting temperatures were in the range from 2.47 to 13.51_C, and were obtained from the sub-surface layer (~50 m) to below 5 km depth. From the comparison of REVTMP and the raw CTDTMP values a pressure dependent calibration was determined of the form: CTDTMP=CTDTMP(raw) - 0.0038 - 1.8 10-7*CTDPRS (1) The resulting correction was larger than the manufacturers calibration. This is possibly caused by heating of the temperature probe due to viscous dissipation in a thin sub-layer along the probe in the flushed sensor system. For some time an extra non-flushed temperature sensor was added to the system. The latter gave temperatures which were systematically 3 to 4 mK lower than those from the flushed probe. And also the the SBE35 reference thermometer indicated similar differences. According to the manufacturer part of the temperature probes may have a slight pressure dependence as we have observed. The manufacturer's calibration is performed without flushing of the sensor. CTDTMP in all CTD casts was corrected according to (1). The resulting difference between REVTMP and CTDTMP had an RMS value of 2.1 mK (281 samples, figure 17). When only those samples were considered, obtained in the low gradient part of the water column below the Mediterranean Sea Water (CTDPRS > 2500 dbar), the RMS value of the difference was reduced to 1.8 mK (187 samples) Figure 17. Plot of CTDTMP versus REVTMP for al samples with quality flags 2 or 6. 3.3 Pressure Measurements In each of the thermometer racks, mounted on sampler bottles 2, 4, 6, and 8, also a SIS electronic reversing pressure sensor was placed. Before as well as after the cruise these sensors were calibrated by the manufacturer. A total of 326 reliable pressures were obtained. The difference between the pressure, as measured with the electronic reversing pressure sensor (REVPRS) and with the CTD (CTDPRS) had a RMS value of 3.3 dbar (figure 18), a value of the order of the manufacturers specification of the accuracy of the SIS reversing pressure sensors after correction for temperature effects. No further correction of the pressure was applied. Figure 18. Plot of CTDPRS versus REVPRS for all samples with quality flag 2. 3.4 Salinity Measurements Water was drawn from the samplers into a 0.5 litre glass sample bottle for the salinity determination after 3 times rinsing. The sample bottles had a massive rubber stopper as well as a screw lid. Salinity of water samples (SALNTY) was determined by means of an Guildline Autosal 8400A salinometer. The readings of the instrument were performed by computer, giving the average and statistics of 10 consecutive readings. For each samples 3 salinity determinations were carried out. The standard water used was from batch P119 with a K15 ratio of 0.99990 From each deep CTD/rosette cast an extra duplicate sample was drawn. Salinity determinations from the duplicate samples were used to determine the reproducibility of the salinity determination (table 2). The RMS value the salinity difference between the duplicate samples amounted to 0.0005 (94 samples). From comparison of CTDSAL with SALNTY 994 samples were available over the whole water column, with values between 34.40 and 36.14. It appeared that the error in CTDSAL was both time (station number) and pressure dependent. Therefore a correction for CTDSAL was applied of the form of: CTDSAL = CTDSAL(raw) + a + b*CTDPRS + c* STNNBR (2) For stations 13 to 80 the correction constants a, b an c were -0.0029, 4.4 10-7 dbar-1 and 7.1 10-5 respectively. For stations 81 to 125 no time dependence was found (c=0.0) while a and b amounted to +0.0024 and 4.4 10-7 dbar-1 respectively. This correction was applied to all CTD salinities. Comparison of the corrected CTDSAL with SALNTY gave a RMS for the difference of 0.0016 (figure 19). Figure 19. Plot of CTDSAL versus SALNTY for all samples with CTDSAL quality flags 2 and SALNTY quality flags 2 or 6. 3.5 Oxygen Measurements For the oxygen determination water samples were drawn in volume calibrated 120 ml pyrex glass bottles. Before drawing the sample each bottle was flushed with at least 3 times its volume. When the samples were drawn the temperature of the sample was determined. The determination of the volumetric dissolved oxygen concentration of water samples was carried out by means of a high precision automated oxygen Winkler titration system, based on an optical end point determination. For the conversion of the volumetric concentration O2vol to the densimetric concentration O2den the following conversion was used: O2den=O2vol / _ where _ is the density of sea water at the sample temperature, the salinity of the sample, and at zero pressure. At each cast duplicate samples were drawn from the deepest an shallowest water sampler, and at a number of stations also from an intermediate sampler (table 3). The difference between the duplicate samples had a RMS value of 0.26 _mol/kg. The available NOEX sampler bottles in use at NIOZ are equipped with flexible hollow ball formed lids, made of silicon rubber. Because of the known permeability of this material for gases and the high partial oxygen pressure in the remaining air in these balls which occurs when they are under pressure in sea, we suspected these balls to have an adverse effect on the quality of the oxygen samples, due to introduction of oxygen from the balls into the sampler bottle. To study this effect we had acquired a number of newly developed sampler lids, made of PETP, which is known to have a much lower gas Figure 20. Difference of the oxygen concentration from water sampled with the NOEX sampler fitted with the silicon rubber ball lids water sampled with NOEX samplers with PETP lids. Plotted versus the sample pressure. The line gives the linear regression. permeability. At a number of stations samples were taken with the NOEX sampler bottles with the suspected silicon lids and with the PETP lids at the same depth. At the final test station (#125) three Niskin sampler bottles were added to this procedure. The samples from the Niskin bottles and from the NOEX bottles with PETP lid did not show any significant difference in oxygen content. However the samples from the NOEX sampler bottles with silicon rubber ball lids clearly showed a pressure dependent excess in oxygen content, compared with the samples from the Niskin bottles and the NOEX bottles with PETP lid (figure 20). This dependence was modelled with a linear regression and appeared to amount to 1 _mol/kg per 1345 dbar. After correction with the resulting regression line the RMS value of the remaining differences between the bottles with the different lids had a RMS value of 0.8 _mol/kg. All oxygen samples taken with the NOEX samplers fitted with the ball lids have been corrected by subtracting the value of the regression line from the determined concentration. For each CTD/rosette cast also 1 to 3 samples were taken for the determination of the sea water blank value. In the surface layer (upper 50 dbar) the sea water blank amounted 0.58 (*0.05) _mol/kg, in the sub-surface layer (50 to 250 dbar) the sea water blanks had a value of 0.69 (*0.03) _mol/kg, deeper sea water blanks had a value of 0.74 (*0.03) _mol/kg. The final densimetric oxygen concentration, OXYGEN was calculated by subtracting the sea water blanks from the determined densimetric oxygen concentration. Figure 21. Plot of CTDOXY versus OXYGEN for all samples with quality flag 2 for CTDOXY and quality flags 2 or 6 for OXYGEN. The calibration of the oxygen sensor, fitted on the CTD system was determined by comparison of the raw CTDOXY values determined according to the manufacturers calibration with the OXYGEN values, taken at the same depth. On average the raw CTDOXY values were about 60 _mol/kg too low. It appeared that the calibration differed from station to station, and also between down-cast and up-cast. Therefore for each station, and for down-cast and up-cast separately the calibration of the oxygen sensor was determine with a multiple regression of OXYGEN versus the raw CTDOXY value, and the logarithms of CTDTMP and CTDPRS. The raw CTDOXY values for each cast were corrected according to the resulting calibration in order to get the final CTDOXY. The RMS value of the resulting difference for the up-casts amounted to 1.8 _mol/kg (figure 21). 3.6 Nutrient Measurements From al sampler bottles samples were drawn for the determination of the nutrients silica, nitrite, nitrate and phosphate. The samples were collected in polyethylene sample bottles after three times rinsing. The samples were stored dark and cool at 4_C. All samples were analysed for the nutrients silicate, phosphate, nitrate and nitrite within 10 hours with an autoanalyzer based on colorimetry. The lab container was equipped with a Technicon TRAACS 800 autoanalyzer. The different nutrients were measured colorimetrical as described by Grashoff (1983). The samples, taken from the refrigerator, were directly pored in open polyethylene vials (6ml) and put in the auto sampler-trays. A maximum of 60 samples in each run was analysed. Because of the large differences in nutrient content between the upper ocean and the deep water, the analyses were carried out in two different calibration ranges. A low concentration range for the samples from the upper 1500 m, and a high concentration range for the samples collected deeper than 1500 m. For the first ten stations on shallow- and deep-waters, the samples were filtered over a 0.45 _m filter and analysed, both filtered and unfiltered. Since no significant difference in nutrient-contribution from e.g. algae between the filtered and unfiltered samples was found, the analysis was continued without filtration. The different nutrients were measured colorimetrical as described by Grashoff (1983); _ Silicate reacts with ammoniummolybdate to a yellow complex, after reduction with ascorbic acid the obtained blue silica-molybdenum complex was measured at 800nm (oxalic acid was used to prevent formation of the blue phosphate-molybdenum). _ Phosphate reacts with ammoniummolybdate at pH 1.0, and potassiumantimonyltartrate was used as an inhibitor. The yellow phosphate-molybdenum complex was reduced by ascorbic acid to blue and measured at 880nm. _ Nitrate was mixed with a buffer imidazole at pH 7.5 and reduced by a copperized-cadmium coil (efficiency> 98%) to nitrite, and measured as nitrite (see nitrite). The reduction-efficiency of the cadmium-column was measured in each run. _ Nitrite was diazotated with sulphanilamide and naftylethylenediamine to a pink coloured complex and measured at 550nm. _ The difference of the last two measurements gave the nitrate content Standards were prepared by diluting stock solutions of the different nutrients in the same nutrient depleted surface ocean water as used for the baseline water. The standards were kept dark and cool in the same refrigerator as the samples. Standards were prepared fresh every two days. Each run of the system had a correlation coefficient for the standards off at least 0.9998. The samples were measured from the surface to the bottom to get the smallest possible carry-over-effects. In every run a mixed nutrient standard containing silicate, phosphate and nitrate in a constant and well known ratio, a so- called nutrient-cocktail, was measured in duplicate. This cocktail is used as a guide to check the performance of the analysis. The reduction-efficiency of the cadmium-column in the nitrate lane was measured in each run. The autoanalyzer determined the volumetric concentration at a standard temperature of 20_. In order to calculate the densimetric concentration in _mol/kg the volumetric concentrations were divided by the density of sea water at 20_C, sample salinity and zero pressure. For each CTD/rosette cast duplicate nutrient samples were measured in separate runs (tables 4 to 7) to assess the precision of the analysis. The resulting RMS value of the differences for silica (SILCAT), nitrite (NITRIT), nitrate (NITRAT), and phosphate (PHSPHT) amounted to 0.14, 0.02, 0.11, and 0.02 _mol/kg respectively. 3.6 Transmissometer Measurements The Sea Tech transmissometer was mounted in the rosette rack next to the CTD probe. During the cruise the instrument has been calibrated, following the manufacturers instructions. The zero output with a blocked light path has been measured as well as the output by transmission in air.. The zero output had not changed since the purchase of the instrument (December 1992), but the output with transmission in air was reduced with 8%, compared with the manufacturers calibration, probably due to ageing of the light source. After correction a 100% output should be equivalent to the transmission of clean pure water. From comparison of the transmission in the relatively clear deep water it however appeared that the calibration of the transmissometer differed from cast to cast causing differences in transmission in the deep water of several percent between successive casts. Thereupon it was decided to apply a shift in the individual transmission profiles in order to get matching transmission values in the clear deep water. The resulting transmission therefore contains an unknown scaling constant relative to the transmission of clear pure water. 3.7 CTD Data Collection and Processing For the data collection the Seasave software, produced by SBE, was used. The CTD data were recorded with a frequency of 24 data cycles per second. After each CTD cast the data were copied to a hard disk of the ship's computer network, and a back-up copy was made on another disk. At the end of the cruise back up copies were made on tape, and brought to NIOZ, together with the hard disk unit, containing all data. On board the up-cast data files were sub-sampled to produce files with CTD data corresponding to each water sample, taken with the rosette sampler. On board the CTD data were processed with the preliminary calibration data, and reduced to 1 dbar average ASCII files, which were used for the preliminary analysis of the data. Afterwards the raw CTD data from the down-casts were processed with the Seasoft software. Corrections were applied for the sampling time difference due to the forced flushing of the water along the different sensors, for the heating of the water in the flushing system between the temperature sensor and the conductivity sensor, and the different response times of the sensors. A time series of mean values of the readings were determined for 0.5 s intervals, equivalent with 0.5 to 0.75 dbar intervals. Consecutively the parameters were determined in physical units, using the calibration constants determined as described above. For the fluorometer data the manufacturers calibration was used, giving chlorophyll equivalent values in mg/m3. It appeared that in the very strong vertical gradients of the seasonal thermocline and below the Mediterranean Sea Water still salinity spikes were found which could not be removed by altering the constants in the Seasoft correction modules. Thereupon it was decided to apply a median filter over 5 consecutive time bins in order to remove these spikes. Consecutively the time series was filtered by means of a running mean over 5 consecutive time bins. Finally the time series was interpolated on equidistant 1 dbar intervals, only using the first downward crossing of the interpolation pressure by the time series. Since no pressure bin averaging was applied, the parameter NUMBER OF OBS. in the CTD files was set to 12, the number of individual data point used to obtain the time series 0.5 s averages which were used for the interpolation at equidistant pressure intervals. Appendix A Tables with duplicate samples Table 1. Readings of pairs of reversing electronic thermometers REVTMP1 REVTMP2 REVTMP1 REVTMP2 10.216 10.217 11.052 11.052 9.507 9.511 3.515 3.516 2.711 2.712 2.839 2.838 3.676 3.675 5.144 5.145 2.823 2.825 2.531 2.529 3.065 3.063 2.654 2.655 3.586 3.585 3.452 3.451 2.558 2.558 2.515 2.517 2.749 2.750 2.497 2.495 3.143 3.144 2.536 2.537 2.523 2.523 2.649 2.652 2.616 2.619 2.512 2.513 2.786 2.789 2.500 2.498 2.491 2.492 2.564 2.564 2.536 2.540 2.711 2.714 2.499 2.500 2.530 2.531 2.544 2.548 2.494 2.493 2.668 2.671 2.498 2.497 2.491 2.491 2.573 2.576 2.528 2.532 2.534 2.535 2.633 2.636 2.498 2.497 2.492 2.492 2.514 2.515 2.531 2.535 2.584 2.587 2.643 2.646 2.520 2.520 2.526 2.530 2.509 2.509 2.641 2.639 2.561 2.562 2.482 2.484 2.690 2.694 2.622 2.620 2.517 2.518 2.479 2.479 2.488 2.487 2.608 2.607 2.535 2.536 2.718 2.720 2.651 2.653 3.029 3.033 2.556 2.557 3.469 3.468 2.753 2.752 11.416 11.416 3.031 3.030 11.231 11.231 3.495 3.497 REVTMP1 REVTMP2 REVTMP1 REVTMP2 2.559 2.556 2.939 2.939 2.593 2.594 3.410 3.408 2.762 2.763 4.008 4.004 3.094 3.096 7.594 7.595 2.532 2.531 9.571 9.571 2.521 2.520 7.253 7.257 2.544 2.545 8.677 8.676 2.660 2.661 10.174 10.173 2.533 2.531 9.678 9.676 2.510 2.510 10.040 10.038 2.554 2.555 10.471 10.469 2.681 2.682 9.180 9.180 2.531 2.529 10.094 10.091 2.510 2.510 10.374 10.372 2.554 2.554 3.766 3.765 2.690 2.692 6.659 6.656 2.506 2.505 2.593 2.592 2.513 2.513 2.683 2.684 2.594 2.595 3.020 3.019 2.788 2.789 3.445 3.445 2.501 2.501 2.484 2.484 2.504 2.502 2.514 2.513 2.753 2.754 2.901 2.897 2.490 2.489 2.485 2.484 2.552 2.550 2.905 2.907 2.686 2.686 2.490 2.489 2.954 2.957 2.492 2.492 2.505 2.503 2.568 2.568 2.560 2.560 2.488 2.486 2.712 2.710 2.497 2.497 2.968 2.968 2.568 2.568 2.523 2.521 2.491 2.492 2.694 2.693 2.501 2.501 2.921 2.919 2.604 2.603 3.375 3.373 2.681 2.682 REVTMP1 REVTMP2 REVTMP1 REVTMP2 2.496 2.495 2.489 2.489 2.504 2.504 2.555 2.556 2.581 2.581 2.746 2.747 2.748 2.750 2.488 2.487 2.499 2.495 2.569 2.570 2.560 2.559 2.749 2.749 2.742 2.743 2.496 2.497 3.747 3.747 2.575 2.576 5.984 5.981 2.775 2.776 9.255 9.251 3.857 3.856 9.701 9.700 9.940 9.939 10.152 10.149 10.433 10.431 10.602 10.600 10.746 10.743 11.408 11.407 9.981 9.980 11.716 11.715 10.419 10.417 11.909 11.908 10.784 10.782 13.511 13.510 11.905 11.901 11.980 11.979 12.275 12.272 10.805 10.803 11.934 11.930 5.885 5.884 3.469 3.467 2.906 2.905 3.914 3.910 3.242 3.242 3.012 3.010 3.917 3.916 3.552 3.551 2.629 2.630 5.703 5.699 2.932 2.930 3.185 3.185 3.510 3.510 3.563 3.563 2.553 2.553 2.726 2.726 2.730 2.727 2.965 2.964 3.101 3.100 2.632 2.631 2.475 2.475 2.891 2.890 2.548 2.548 3.113 3.112 2.720 2.720 3.168 3.168 2.500 2.500 3.462 3.462 2.574 2.575 3.502 3.501 2.796 2.797 3.839 3.840 REVTMP1 REVTMP2 9.235 9.234 9.672 9.668 9.976 9.972 10.321 10.317 10.533 10.529 Table 2 Duplicates of sample salinity. SALNTY1 SALNTY2 SALNTY1 SALNTY2 35.4996 35.4992 34.9039 34.9037 35.5391 35.5395 34.9017 34.9022 35.6688 35.6691 34.9116 34.9113 35.3437 35.3442 34.9512 34.9515 34.9195 34.9196 34.9983 34.9984 34.9115 34.9116 35.0960 35.0962 34.9014 34.9020 35.4069 35.4072 34.9005 34.8997 35.6597 35.6598 34.9010 34.9007 35.5468 35.5472 34.8993 34.8992 35.5094 35.5104 34.8993 34.8996 35.5034 35.5032 34.8993 34.8993 35.5436 35.5435 34.8974 34.8984 35.6296 35.6298 34.8989 34.8991 35.6838 35.6839 34.8984 34.8976 35.5344 35.5348 34.9782 34.9789 34.9505 34.9508 35.7144 35.7153 34.9149 34.9154 35.6772 35.6773 34.9055 34.9060 36.0663 36.0661 34.9032 34.9033 34.9691 34.9694 34.9021 34.9024 34.9393 34.9396 34.9025 34.9032 34.9104 34.9103 34.9015 34.9023 34.8987 34.8989 34.9021 34.9025 34.8986 34.9001 34.9032 34.9035 34.8987 34.8991 34.9048 34.9053 34.8980 34.8985 34.9604 34.9605 34.8980 34.8973 35.3129 35.3134 34.9004 34.8996 35.6600 35.6611 34.9170 34.9168 35.5800 35.5806 34.9137 34.9134 35.5403 35.5399 34.9006 34.9000 35.5218 35.5217 34.8998 34.9003 35.5565 35.5570 34.9013 34.9014 35.5788 35.5788 34.9003 34.9001 35.6824 35.6825 34.9004 34.9006 34.9781 34.9780 SALNTY1 SALNTY2 34.9222 34.9224 34.9118 34.9118 34.9050 34.9053 34.9014 34.9014 34.9023 34.9034 34.9007 34.9013 34.9004 34.9013 34.9010 34.9010 34.9699 34.9700 35.7584 35.7587 35.7401 35.7408 35.5886 35.5885 35.5972 35.5974 35.5961 35.5969 35.1748 35.1751 34.9369 34.9375 34.9405 34.9412 34.9763 34.9757 34.9163 34.9168 34.9089 34.9095 34.9091 34.9098 34.9250 34.9264 34.9357 34.9357 Table 3 Duplicates of sample oxygen concentration OXYGEN1 OXYGEN2 OXYGEN1 OXYGEN2 229.64 229.48 217.51 217.54 251.01 251.33 238.17 238.05 246.92 246.93 214.01 214.23 231.30 231.64 228.41 228.39 245.43 245.22 206.23 206.17 196.63 196.52 206.65 206.65 245.08 244.73 251.64 251.90 241.47 241.67 187.43 187.39 236.36 236.28 242.38 241.99 239.95 240.12 250.06 250.09 242.62 242.60 241.73 241.59 240.34 239.95 246.77 246.63 238.59 238.60 241.32 241.76 240.43 240.21 242.89 243.01 239.06 239.13 242.86 242.91 238.96 238.47 245.32 245.50 240.98 240.91 243.72 243.50 233.18 233.31 236.88 236.72 242.58 242.48 243.33 243.33 242.29 242.07 236.56 236.68 242.63 242.35 243.18 242.79 236.06 236.09 233.70 233.94 242.04 241.83 243.12 243.01 234.39 234.29 252.59 252.64 243.88 243.64 233.53 233.27 238.38 238.56 242.04 242.31 250.88 250.96 251.86 251.78 201.02 201.00 237.31 237.23 237.35 237.56 242.41 242.87 198.90 198.41 254.39 254.66 237.82 237.82 241.79 242.01 OXYGEN1 OXYGEN2 OXYGEN1 OXYGEN2 264.50 264.71 246.13 246.20 242.92 243.04 249.91 250.01 264.57 264.70 216.97 217.18 239.44 239.53 255.06 254.93 254.38 254.79 197.07 197.13 242.74 242.79 255.07 255.18 240.67 240.77 234.70 234.52 267.88 267.98 233.17 233.96 241.09 241.00 233.23 233.44 252.96 252.89 201.21 201.35 234.95 234.64 261.46 261.54 241.41 241.37 195.17 195.31 261.01 260.91 256.32 256.06 240.32 240.63 207.73 207.93 239.55 239.40 256.93 256.88 255.90 255.95 250.24 250.38 239.40 239.59 243.56 243.74 240.01 240.12 250.53 250.36 268.63 268.56 241.40 241.16 241.26 241.50 247.91 247.85 248.89 248.12 242.33 242.48 266.54 266.66 237.03 237.12 240.21 240.30 242.21 242.19 241.34 241.34 233.31 233.24 243.55 243.56 236.18 236.01 245.02 245.39 240.71 241.46 233.60 233.64 250.46 250.48 254.18 253.49 241.54 241.38 248.91 248.92 236.99 236.96 234.09 234.07 240.69 240.42 241.64 241.79 247.95 248.37 OXYGEN1 OXYGEN2 OXYGEN1 OXYGEN2 227.56 227.31 243.15 243.21 242.37 242.42 226.12 226.07 233.30 233.24 241.48 241.36 240.64 241.09 231.09 230.78 242.15 241.54 241.47 241.33 240.49 240.24 241.97 242.07 247.91 248.49 229.98 230.22 230.24 230.18 243.19 243.17 245.89 245.90 232.31 232.21 233.90 233.83 230.13 229.85 238.30 238.06 242.29 242.11 197.78 198.01 244.47 244.41 244.84 245.58 228.55 228.55 226.53 226.79 251.07 250.61 231.08 230.69 192.91 192.80 228.23 228.09 229.70 229.52 231.74 231.74 193.05 193.05 236.46 236.51 193.88 194.26 192.89 192.84 226.13 226.57 247.24 247.55 223.23 223.15 190.43 190.78 227.42 226.70 229.70 229.30 212.44 211.91 243.78 243.55 231.73 231.68 188.76 188.69 237.60 237.86 224.16 224.11 233.60 233.88 241.82 241.68 247.00 247.02 223.75 223.48 221.72 221.57 241.97 241.62 248.33 248.99 205.98 205.96 197.04 197.05 224.33 224.01 229.10 229.18 240.35 240.25 243.89 244.05 OXYGEN1 OXYGEN2 246.45 246.74 243.32 243.15 243.45 243.25 203.42 203.39 222.47 222.37 245.50 244.94 246.32 246.03 231.15 230.33 217.77 217.98 221.30 221.38 190.61 190.47 222.30 222.44 233.90 233.69 221.32 220.95 246.55 246.46 247.18 247.26 246.39 246.32 231.40 231.25 232.41 232.22 231.70 231.67 190.96 191.11 195.66 195.06 191.82 191.41 228.20 228.13 228.67 228.93 230.40 229.95 230.80 230.96 Table 4 duplicates of dissolved silica samples SILCAT1 SILCAT2 SILCAT1 SILCAT2 3.22 3.11 4.40 4.42 3.08 3.09 3.76 3.77 2.99 3.08 2.90 2.99 0.65 0.68 2.14 2.12 2.77 2.63 0.67 0.62 2.89 2.91 43.92 43.85 1.70 1.70 44.18 44.17 0.64 0.68 44.29 44.51 3.36 3.20 44.28 44.64 3.37 3.37 44.48 44.23 2.62 2.64 44.31 44.26 2.22 2.24 44.27 44.17 1.80 1.81 44.18 44.15 0.69 0.74 44.15 44.41 14.44 14.67 44.02 43.88 39.81 39.98 40.11 40.11 41.39 41.26 26.42 26.46 39.34 39.38 10.34 10.29 38.14 38.03 4.76 4.64 34.34 34.30 4.85 4.73 32.90 32.96 2.22 2.29 30.42 30.50 4.71 4.80 27.52 27.55 5.90 6.06 24.03 24.04 9.29 9.55 21.04 20.97 27.78 27.56 16.60 16.75 34.07 33.94 15.15 15.21 44.21 44.18 12.99 13.03 43.77 43.62 11.36 11.29 43.81 43.73 9.56 9.59 43.92 44.01 8.88 8.89 43.56 43.65 8.31 8.36 40.24 40.18 7.62 7.58 41.67 41.57 6.57 6.58 44.07 43.81 5.48 5.45 43.89 43.94 SILCAT1 SILCAT2 SILCAT1 SILCAT2 44.17 44.14 43.39 43.33 44.59 44.28 44.81 44.47 42.06 41.98 44.46 44.34 34.44 34.33 44.48 44.36 25.63 25.85 44.07 44.07 15.98 15.95 43.88 44.20 12.76 12.88 28.00 28.27 10.01 10.06 9.68 9.97 3.62 3.83 9.99 10.05 2.72 2.75 4.59 4.64 2.71 2.66 4.86 4.83 3.38 3.28 3.27 3.24 8.00 7.96 15.95 15.73 9.02 9.10 34.98 34.91 11.82 11.85 34.26 34.34 34.34 34.33 27.64 27.70 40.96 41.12 40.06 40.20 44.20 44.25 41.95 41.72 44.42 44.29 37.63 37.64 44.46 44.41 35.69 35.89 44.06 44.05 12.74 12.70 43.94 44.23 9.98 9.98 44.01 44.36 3.21 3.25 43.22 43.53 31.68 31.85 14.66 14.80 10.92 11.06 4.29 4.40 2.77 2.92 2.87 2.96 2.59 2.68 2.92 3.02 8.27 8.12 39.26 39.45 41.57 41.47 Table 5 duplicate of dissolved nitrate samples NITRAT1 NITRAT2 NITRAT1 NITRAT2 8.24 8.19 13.40 13.28 7.90 7.86 11.81 11.82 7.81 7.91 10.90 10.81 0.09 0.07 8.98 9.00 7.54 7.54 7.02 7.04 7.64 7.74 0.04 0.03 5.02 5.04 22.37 22.59 0.25 0.05 22.32 22.54 9.14 8.97 22.48 22.47 9.13 9.13 22.23 22.35 7.62 7.59 22.15 22.11 6.41 6.45 22.08 22.15 4.92 5.01 22.27 22.28 0.02 0.00 22.23 22.14 16.50 16.65 21.91 21.75 18.41 18.37 19.63 19.79 21.88 21.91 17.14 16.90 22.01 22.03 12.06 11.93 21.83 21.90 11.42 11.37 21.79 21.67 7.02 7.24 21.03 21.13 11.09 11.26 21.03 20.90 13.58 13.66 20.53 20.68 15.69 15.78 20.22 20.12 19.59 19.46 19.65 19.67 20.63 20.55 19.26 19.16 22.01 22.11 18.58 18.61 22.28 22.16 18.55 18.47 22.27 22.12 18.22 18.24 22.42 22.34 17.72 17.64 22.23 22.17 16.87 16.97 22.05 22.22 16.64 16.70 21.65 21.73 16.18 16.24 21.86 21.96 15.63 15.61 22.56 22.31 14.51 14.54 22.23 22.30 NITRAT1 NITRAT2 NITRAT1 NITRAT2 22.58 22.33 21.70 21.59 22.21 22.25 22.07 21.89 22.29 22.30 22.25 22.07 22.06 22.23 22.44 22.35 22.27 22.38 22.47 22.47 21.88 22.01 22.41 22.26 20.87 20.66 22.20 22.03 19.60 19.73 19.92 19.87 18.41 18.25 16.80 16.88 17.93 17.84 16.89 16.96 16.74 16.76 11.77 11.82 9.81 9.70 10.61 10.63 7.22 7.18 9.20 9.25 7.11 7.11 18.65 18.46 9.01 8.82 21.01 21.02 15.70 15.35 20.93 20.89 16.26 16.19 19.90 19.90 17.43 17.47 21.78 21.75 20.86 20.64 21.72 21.62 22.29 22.12 21.82 21.71 22.03 22.09 21.21 21.19 22.17 22.38 21.02 20.84 22.15 22.28 17.99 17.94 22.23 22.28 17.00 17.02 22.07 22.21 9.51 9.50 20.49 20.57 18.30 18.20 17.32 17.35 11.30 11.34 7.59 7.53 7.50 7.47 7.17 7.21 8.63 8.68 15.97 15.90 20.13 20.10 Table 6 duplicates of dissolved nitrite samples NITRIT1 NITRIT2 NITRIT1 NITRIT2 0.05 0.14 0.02 0.03 0.01 0.05 0.01 0.01 0.04 0.06 0.02 0.03 0.01 0.03 0.01 0.01 0.04 0.09 0.03 0.01 0.07 0.05 0.00 0.01 0.10 0.10 0.01 0.04 0.00 0.00 0.01 0.03 0.04 0.05 0.02 0.03 0.05 0.10 0.08 0.04 0.07 0.09 0.01 0.04 0.07 0.07 0.00 0.03 0.10 0.10 0.04 0.04 0.00 0.02 0.02 0.02 0.01 0.03 0.02 0.05 0.00 0.05 0.03 0.02 0.00 0.02 0.04 0.04 0.04 0.03 0.03 0.03 0.01 0.02 0.02 0.00 0.02 0.03 0.05 0.03 0.00 0.01 0.06 0.04 0.02 0.02 0.11 0.14 0.00 0.02 0.02 0.03 0.02 0.03 0.02 0.03 0.00 0.03 0.02 0.02 0.01 0.03 0.01 0.03 0.01 0.03 0.01 0.02 0.02 0.02 0.00 0.02 0.00 0.02 0.02 0.03 0.01 0.02 0.00 0.04 0.00 0.03 0.02 0.04 0.02 0.03 0.05 0.03 0.01 0.02 0.02 0.02 0.02 0.02 0.03 0.03 0.01 0.02 0.02 0.02 NITRIT1 NITRIT2 NITRIT1 NITRIT2 0.05 0.01 0.05 0.09 0.03 0.01 0.04 0.03 0.04 0.04 0.04 0.02 0.02 0.05 0.04 0.03 0.02 0.04 0.02 0.03 0.02 0.02 0.04 0.02 0.01 0.02 0.02 0.04 0.02 0.02 0.03 0.05 0.00 0.02 0.01 0.06 0.00 0.01 0.00 0.05 0.00 0.01 0.02 0.05 0.02 0.02 0.05 0.04 0.02 0.01 0.01 0.02 0.01 0.01 0.01 0.03 0.05 0.05 0.05 0.02 0.04 0.05 0.04 0.00 0.04 0.04 0.04 0.04 0.03 0.03 0.04 0.06 0.04 0.04 0.07 0.04 0.02 0.02 0.01 0.00 0.03 0.02 0.01 0.02 0.03 0.01 0.02 0.01 0.01 0.01 0.02 0.00 0.03 0.01 0.01 0.02 0.02 0.01 0.05 0.06 0.01 0.00 0.02 0.04 0.03 0.01 0.01 0.03 0.03 0.02 0.02 0.01 0.01 0.02 0.01 0.04 0.02 0.01 0.02 0.01 0.02 0.01 0.01 0.05 0.02 0.06 0.04 0.05 0.02 0.03 0.07 0.08 Table 7 duplicates of dissolved phosphate samples PHSPHT1 PHSPHT2 PHSPHT1 PHSPHT2 0.53 0.51 0.63 0.63 0.49 0.51 0.52 0.52 0.49 0.52 0.41 0.41 0.03 0.04 0.01 0.01 0.49 0.49 1.51 1.54 0.50 0.51 1.55 1.54 0.35 0.36 1.53 1.57 0.05 0.06 1.55 1.53 0.59 0.57 1.51 1.51 0.50 0.51 1.51 1.54 0.42 0.44 1.51 1.54 0.33 0.34 1.51 1.52 0.04 0.05 1.58 1.54 1.07 1.02 1.53 1.50 1.17 1.16 1.49 1.48 1.48 1.49 1.32 1.34 1.47 1.49 1.09 1.08 1.47 1.43 0.76 0.76 1.42 1.39 0.75 0.74 1.39 1.41 0.46 0.47 1.37 1.35 0.72 0.71 1.34 1.34 0.86 0.86 1.31 1.27 0.99 0.97 1.26 1.27 1.33 1.31 1.21 1.19 1.41 1.41 1.18 1.18 1.52 1.51 1.15 1.12 1.51 1.51 1.09 1.08 1.52 1.52 1.03 1.01 1.51 1.53 1.00 1.03 1.52 1.51 0.98 0.97 1.52 1.50 0.94 0.94 1.48 1.47 0.87 0.86 1.51 1.49 0.81 0.79 1.55 1.52 0.69 0.69 1.50 1.52 PHSPHT1 PHSPHT2 PHSPHT1 PHSPHT2 1.52 1.49 1.00 1.00 1.51 1.50 1.36 1.37 1.53 1.52 1.48 1.49 1.51 1.50 1.49 1.50 1.52 1.52 1.52 1.53 1.49 1.50 1.55 1.54 1.43 1.41 1.53 1.55 1.31 1.26 1.53 1.54 1.22 1.21 1.53 1.53 1.16 1.16 1.51 1.53 1.07 1.07 1.36 1.36 0.61 0.62 1.02 1.03 0.47 0.47 1.05 1.05 0.47 0.48 0.76 0.73 0.98 0.97 0.69 0.68 1.02 1.03 0.58 0.58 1.12 1.12 1.21 1.21 1.41 1.39 1.41 1.42 1.49 1.46 1.40 1.40 1.51 1.49 1.32 1.34 1.51 1.51 1.47 1.48 1.52 1.50 1.48 1.49 1.49 1.50 1.49 1.50 1.52 1.49 1.44 1.44 1.52 1.50 1.43 1.43 1.51 1.50 1.15 1.12 1.52 1.50 1.06 1.05 1.38 1.37 0.57 0.55 1.19 1.18 1.10 1.10 0.70 0.71 0.48 0.49 0.47 0.48 0.45 0.46 0.53 0.55