A. Cruise Narrative: P24 A.1. Highlights WHP Cruise Summary Information WOCE section designation P24 Expedition designation (EXPOCODE) 49RY9511_2 Chief Scientist/affiliation Masahiko Fujimura, JMA/MD Dates 1995.11.15 - 1995.11.30 Ship RYOFU MARU Ports of call Nagoya, Japan to Naha, Japan Number of stations 26 31°15.48''N Geographic boundaries of the stations 131°28.19''E 137°04.41''E 23°57.99''N Floats and drifters deployed none Moorings deployed or recovered none Contributing Authors Y. Takatsuki (in order of appearance) H. Kamiya K. Nemoto I. Kaneko CRUISE REPORT OF RY9511, LEG-2 (WHP-P24) Oceanographical Division Climate and Marine Department Japan Meteorological Agency November 1999 1 CRUISE NARRATIVE 1.1 Highlights WOCE section designation: WOCE WHP P24 Expedition Designation (EXPOCODE): 49RY9511/2 (Ryofu Maru 95-11 cruise, leg 2) Ship: R/V Ryofu Maru Ports of Call: Nagoya, Japan to Naha, Japan Cruise Dates: November 15 to November 30,1995. Chief Scientist: Masahiko Fujimura1 Oceanographical Division Marine Department Japan Meteorological Agency 1-3-4 Otemachi, Chiyoda-ku, Tokyo 100, JAPAN E-mail: attention seadata@hq.kishou.go.jp 1.2 Cruise Summary CRUISE TRACK The station locations along the WHP P24 section are shown in *Figure 1. NUMBER OF STATIONS 26 stations of CTD/Rosette casts were completed and pre-and post-CTD/Rosette casts for CFC bottle blank measurements were also occupied. SAMPLING Measured parameters and numbers of samples are as follows: Numbers of water samples analyzed: salinity 815 samples at 26 stations oxygen 691 layers at 26 stations nutrients 691 layers at 26 stations CFCs 147 layers at 9 stations 1 - present affiliation: Maritime Meteorological Division, Climate and Marine Department, Japan Meteorological Agency Numbers of water samples collected for shore-based analysis: *Figure 1: WHP-P24 station locations. Contour level of the water depth: 200, 1000, 2000, 3000, 4000, 5000, 6000m. helium-3 (3He) 89 layers at 6 stations tritium (3H) 89 layers at 6 stations AMS radiocarbon 159 layers at 6 stations plus ca.160 samples for the forthcoming Pacific radiocarbon inter- comparison. FLOATS, DRIFTERS, AND MOORINGS No floats, drifters, or moorings were deployed on this leg of the cruise. 1.3 List of Principal Investigators The principal investigators responsible for the major parameters measured on the cruise and their E-mail address are listed in Table 1 and Table 2, respectively. 1.4 Scientific Programme and Methods NARRATIVE Primary goal of the cruise is to obtain a high-quality standard data set along P24 section, where the Kobe Marine Observatory of the Japan Meteorological Agency(JMA)will continue to carryout repeat hydrographic observations (PR17)and compare their data with the present standard data to detect long-term variations from sea surface to deep ocean. Another goal is to obtain detailed structure of deep circulation in the Shikoku and Northern Philippine Basins from deep density structure and property field along the section. Since most of the instruments and equipments worked properly and the weather during the casts was not so severe, CTD observations, measurements of sample water salinity, dissolved oxygen and nutrients were carried out as intended. We also measured CFCs and collected water samples for shore-based analysis for 3He/3H,radiocarbon. The cruise track is shown in *Figure 1. After leaving Nagoya, the section began at (31-15N, 131-28E) off the coast of Kyushu. The Ryofu Maru headed southeastward along WOCE WHP P24.The distances between the neighboring stations were around 30 NM over some Basin, less than 30 NM over steep bathymetry in the Daito Ridge, between 10 and 20 NM over the continental slope. The last station was settled at (25-00N, 137-00E) which is the station WOCE P9-31.This section was not from coast to coast, however, three revisited stations were occupied at (24-15N, 136-12E: P3- 322), (24-00N, 137-00E: P9-33), and (25-00N, 137-00E: P9-31) to confirm the trace ability of the measurements. PRELIMINARY RESULTS *Figure 2 shows the distribution of sample observations made on the P24 section. The preliminary results comparing the data this cruise and previous P3 and P9 cruises at three revisited stations showed in good agreements within the WOCE onetime standard of water samples. SALINITY We had three revisited stations on WHP P3 and P9. Salinity values interpolated with potential temperature below 1.6°C and differences are shown in Table 3. The deep water salinity values at the station P3-224 in 1985 are slightly lower (about 0.002 or 0.003) than those at the present station P24-24. While the salinity values at the stations P9-33 and P9-31 in 1994 are almost the same (almost within 0.002) with our P24-25 and P24-26. Table 1: List of the parameters to be measured, the sampling groups responsible for each, and the principal investigator for each. Chief Scientist: Masahiko Fujimura Parameter Sampling group Principal Investigator -------------------------------------------------------------- CTD/Rosette JMA/MD Yasushi Takatsuki Salinity JMA/MD Yasushi Takatsuki O2, NO3, NO2, PO4, SiO2 JMA/MD Hitomi Kamiya Chlorofluorocarbons JMA/MD Kazuhiro Nemoto 3H/3He JMA/MRI Michio Aoyama Radiocarbon JMA/MRI Michio Aoyama ADCP JMA/MD Masahiko Fujimura JMA/MD Marine Department, Japan Meteorological Agency JMA/MRI Meteorological Research Institute, JMA Table 2: List of E-mail address of each PI. Masahiko Fujimura fujimura.ma@met.kishou.go.jp Yasushi Takatsuki attention seadata@hq.kishou.go.jp Hitomi Kamiya attention seadata@hq.kishou.go.jp Kazuhiro Nemoto k-nemoto@met.kishou.go.jp Michio Aoyama maoyama@mri-jma.go.jp *Figure 2: Location of 12-liter water samples collected on P24. OXYGEN Accuracy was checked by comparison with P3 and P9 data. Data taken at stations 24, 25 and 26 were compared with P3 station 322, P9 stations 33 and 31 respectively. Our data agrees with the old data within 1% of reproducibility in all cases. Comparison with data of P24 and P9 (Stn.30 -34) is given in *Figure 4. Table 3: Salinity values and differences on isotherms of P24, P3 and P9. Potential Temp. 1.20 1.30 1.40 1.50 1.60 (Depth ca.) (4000m) (3400m) (3000m) (2750m) (2500m) -------------------------------------------------------------------------- 24-15N, 136-12E P24-24 - 34.672 34.662 34.652 34.640 P3-322 - 34.669 34.660 34.649 34.638 diff. - +0.003 +0.002 +0.003 +0.002 24-00N, 137-00E P24-25 - 34.671 34.663 34.653 34.642 P9-33 34.681 34.672 34.663 34.654 34.642 diff. - -0.001 0.000 -0.001 0.000 25-00N, 137-00E P24-26 34.681 34.671 34.662 34.652 34.643 P9-31 34.679 34.672 34.665 34.652 34.642 diff. +0.002 -0.001 -0.003 0.000 +0.001 *Figure 3: Salinity vs. potential temperature for P24 (+), P9 (Stn.30 -34; circle)and P3 (Stn. 322 -324; diamond) data. *Figure 4: Dissolved oxygen concentration vs. potential temperature for P24 (+), P9 (Stn.30 -34; circle)and P3 (Stn.322 -324; diamond)data. NUTRIENTS Accuracy was checked by comparison with P3 and P9 data. Data taken at stations 24, 25 and 26 were compared with P3 station 322, P9 stations 33 and 31 respectively. Some comparisons are given in *Figure 5. Our data agrees with the P9 data within 1% of reproducibility in all cases. On the other hand, our deep silicate concentrations were ca. 4.3 µmol/kg lower and deep phosphate data were ca. 0.1 µmol/kg higher on average than the P3 data. 1.5 Major Problems Encountered on the Cruise A major problem was the unstable cold welder for Helium samples. It caused 25 percent losses of the samples. 1.6 List of Cruise Participants The members of the scientific party are listed in Table 4, along with their responsibilities. Table 4: Cruise participants Name Affiliation and Responsibilities -------------------------------------------------------------- Masahiko Fujimura Chief Scientist (JMA/MD ADCP) Yasushi Takatsuki (JMA/MD CTD/Rosette, Salinity) Yoshiaki Kanno (JMA/MD CTD/Rosette, Salinity) Tetsuya Nakamura (JMA/MD CTD/Rosette, Salinity) Sinji Masuda (JMA/MD CTD/Rosette, Salinity, Oxygen) Ichiro Terashima (JMA/MD Oxygen) Hitomi Kamiya (JMA/MD Oxygen, Nutrients) Sonoki Iwano (JMA/MD Nutrients) Yoshisuke Takatani (JMA/MD Nutrients) Takafumi Umeda (JMA/MD Oxygen) Ikuo Kaneko (JMA/MD CFCs) Kazuhiro Nemoto (JMA/MD CFCs) Shu Saito (JMA/MD CFCs) Michio Aoyama (JMA/MRI Radiocarbon, 3H /3He) JMA/MD Marine Department, Japan Meteorological Agency JMA/MRI Meteorological Research Institute, JMA 2 HYDROGRAPHIC MEASUREMENT TECHNIQUES AND CALIBRATIONS 2.1 Sample Salinity Measurements by Y. Takatsuki (April 26,1999) EQUIPMENT AND TECHNIQUE Salinity samples were collected in 150 ml amber glass bottles with rubber caps and stored in an air-conditioned laboratory for more than 24 hours before salinity measurements. The salinities were measured with two Guildline TM Autosal TM Model 8400B salinometer (S/N 60,027 and 61,282)with an Ocean Scientific International peristaltic-type sample intake pump. The salinometer was standardized with IAPSO Standard Seawater (SSW) batch P124 (18 Jan. 1994, K 15 0.99990) everyday when it was used for sample measurements. The instruments were operated in the ship's separate laboratory at a bath temperature of 27°C with the laboratory temperature between 24°C and 26°C. We made efforts to keep the variation of laboratory temperature within 1°C between two standardizations before and after a series of salinity measurements, though the variation sometimes exceeded the limit and reached 2°C at the maximum. During the cruise, we regularly took a batch of deep water below 1000 m depth, sealed in a polyethylene rectangular bag and used as a sub-standard water to monitor instrument drifts. We kept a batch of sub-standard sea water being isolated from air and stirred with a magnet stirrer so as to maintain its constancy of salinity during salinity sample measurements. A batch of sub-standard sea water was replaced by new one when the bag decreased in volume by half. This is because salinity of the sub-standard sea water tended to increase by about 0.0004 when its volume decreased largely. 31 outputs of conductivity ratio from the Autosal were taken by a PC at each reading, and their median and standard deviation were calculated and recorded. There were 30 pairs of replicate samples drawn; and 40 pairs of duplicate samples. Of the duplicate pairs, 30 were from below 400m. The standard deviations of the three groups of sample pairs are given in Table 5 below. The precision of salinity measurements deeper than 400m depths is estimated at 0.0006. *Figure 5: Silicate (upper), phosphate (middle), and nitrate (bottom) concentration vs. potential temperature for P24 (+), P9 (Stn. 30-34; circle) and P3 (Stn. 322-324; diamond) data. Table 5: Salinity duplicate and replicate statistics Quantity Standard Deviation Number of pairs ------------------------------------------------- Replicates 0.0003 30 Duplicates (All) 0.0030 40 Duplicates (>400m) 0.0006 30 2.2 Sample Oxygen Measurements by H. Kamiya (March 11,1999) EQUIPMENT AND TECHNIQUE The dissolved oxygen samples were analyzed with an automated titration system. The titrator used in the P24 cruise, Model ART-3 TM, was a photometric type (372nm), which has been manufactured by Hirama Riken Inc. The volume of burette is 5 ml, and the resolution of titration is 0.0025 ml. The dissolved oxygen samples were collected in 120 ml borosilicate glass bottles immediately following the drawing of samples for CFCs. Our bottle has a collar on its mouth and its round glass stopper contains a long nipple, which is inserted into the bottle, displacing ca. 30 ml of sample water. The temperature of a sample was measured with a thermistor probe being inserted into seawater after adding reagents. The reagents were prepared according to the recipes by Carpenter (1965)and Culberson (1991) though normality of sodium thiosulfate for titration was selected about 0.05 in order that a titration for the highest oxygen concentration would be finished within a volume of the burette. Titration blank was measured during cruise, determined as -0.0075 ml, and subtracted from all of thiosulfate titers of the samples. PRECISION OF MEASUREMENTS During the cruise we monitored precision by analyzing duplicate samples taken from the samplers (Niskin bottles); both from the same sampler (replicate) and from two samplers tripped together at the same depth (duplicate). Replicate/duplicate samples were taken on every cast. The standard deviation of the difference were 0.81 (replicate) and 1.01 (duplicate) µmol/kg indicates the precision is about 0.4%. The results of comparisons between replicate/duplicate samples are shown in Table 6. Table 6: Statistics of duplicates and Replicate for dissolved oxygen Standard Deviation Case µmol/kg (%of F.S.) Number of data Replicates 0.81 (0.37) 80 Duplicates 1.01 (0.46) 32 Full Scale 220 REFERENCES Carpenter, J.H.(1965):The Chesapeake Bay Institute technique for the Winkler dissolved oxygen method. Limnol. Oceanogr. 10, 141 -143. Culberson, C.H.,(1991):Dissolved Oxygen. in WHP Operations and Methods -July 1991. 2.3 Nutrients by H. Kamiya (March 11,1999) EQUIPMENT AND TECHNIQUES The nutrient analyses were performed on a Technicon AutoAnalyzer-TM -II (AA-II). We prepared the regents and flow lines referred to the manual by L.I. Gordon et. al. (1993). However, as for phosphate and silicate analyses, we introduced the ascorbic acid method for convenience of reagent handling. Our system heated silicate and phosphate samples up to 37°C so as to keep coloration rate stable. The laboratory temperature was maintained from 23.5 to 25°C. Sampling of nutrients followed that for the trace gases and dissolved oxygen. Samples were drawn into 12 ml polymethylpentene test tubes with silicone caps which fit the AA-II sampler tray. Both the test tubes and caps were rinsed with 10% HCl and deionized water before sampling at every stations. The analysis routinely were started within half an hour after sampling on deck. Samples were introduced to the manifolds through the cycle of 80 seconds sampling and 45 seconds washing with artificial seawater of salinity ca. 34.7. CALIBRATIONS AND STANDARDS Nominal concentrations of standard are given in Table 7. All volumetric flasks and pipettors used on this work were calibrated before the cruise. Linearity was checked beginning of leg and again at the end of station work and 9 sets of data were taken. Standards concentrations (µmol/kg)were :silicate 160, 80, 40, 20, 0; nitrate 40, 30, 20, 10, 0; phosphate 3, 2.25, 1.5, 0.75, 0. The mean difference (µmol/kg) of the mid-scale offset from straight lines were silicate 0.57, nitrate 0.19, phosphate 0.004, the standard deviations (µmol/kg) were 0.25, 0.03, 0.010 respectively. For the reproducibility we measured 93 standards. The means (µmol/kg) were: silicate 82.45, nitrate 21.71, phosphate 1.57, the standard deviations (µmol/kg) were 0.74, 0.19, 0.033 respectively. During the cruise we monitored precision by analyzing replicate/duplicate samples taken from the Sampler. Replicate/duplicate samples were taken on every cast. The results of comparisons between replicate/duplicate samples are shown in Table 8. Table 7: Concentrations of nutrients standard (Unit: µmol/kg) Silicate Nitrate NO3+NO2 Nitrite Phosphate -------------------------------------------------------------------------------------- A standard 66454 25000 12500 1875 B standard 1993.6 500 500 37.5 C standard 159.5 40 41 1 3 Table 8: Statistics of duplicates and replicates for nutrients (Unit:upper:µmol/kg lower: %of full scale). Case Silicate Nitrate Nitrite Phosphate Number of data ------------------------------------------------------------------------------ Replicates 0.214 0.080 0.002 0.010 97 (0.13) (0.20) (0.18) (0.35) Duplicates 0.175 0.064 0.006 0.013 33 (0.11) (0.16) (0.65) (0.44) Full Scale 159 41 1 3 REFERENCES Gordon, L.I., J.C. Jennings, Jr., A.A. Ross, and J.M. Krest (1993): An Suggested Protocol for Continuous Flow Automated Analysis of Seawater Nutrients (Phosphate, Nitrate, Nitrite and Silicic Acid)in the WOCE Hydrographic Program and the Joint Global Ocean Fluxes Study. in WOCE Hydrographic Program Office, Method Manual, 91-1. 2.4 CFC-11 and CFC-12 measurements by K. Nemoto and I. Kaneko (March 18,1998) EQUIPMENT AND TECHNIQUE Concentrations of the dissolved chlorofluorocarbons (CFCs) F-11 and F-12 were measured by shipboard electron-capture (ECD) gas chromatography, according to the methods described by Bullister and Weiss (1988). Our extraction and analysis system was assembled by GL Science Corp. The ECD gas chromatograph is Hitachi Corp., Model 263-30. CFCs samples were analyzed at 153 layers of 9 stations along the WHP-P24 section. Replicate samples were drawn and analyzed at each station, except the first station (P24-01, RF-0069). WATER SAMPLING AND DATA PROCESSING We used a 12-liter (Niskin bottle) x 24 rosette system (General Oceanic Co. Ltd.) for water sampling. The inner walls of the Niskin bottles and stainless springs had been coated with epoxy. According to Bullister and Weiss (1988), the O-rings of the bottle caps were heated to 60°Celsius in a purged vacuum oven for two days to degas them, stored in a gas tight container and installed on the bottles just before the first station for CFCs sampling. CFCs samples were always drawn firstly by using 100 ml glass syringes. The samples were injected in the system and processed within 12 hours after sampling. Approximately 30 ml of samples was flushed, and 30 ml was transferred to the stripping chamber. The volumes of our gas sample loop and water sample cylinder were determined after the cruise by the method to fill the sample loop/cylinder with distilled water and measure its weight increase. The volumes of the gas sample loop and water sample cylinder were determined to 1.152 ml and 29.84 ml, respectively. Calibration curves used for converting output peak areas to CFCs concentrations are generated by multiple (up to seven, if necessary) injections of the known volume of standard gas. The coefficients of polynomial expressions used at each station are shown in Table 9. On the basis of several stripping test during the cruise, we determined the stripping efficiencies to 0.996 for F-11 and 0.990 for F-12. We divide output peak area by these factors to estimate total amounts of F-11/F-12 dissolved in seawater samples. SAMPLE BLANKS Sample blanks of F-11 and F-12 for each bottle were obtained before and after the observations along the P24 section, at 2500 m depth of Station RF-0068 (31-25N, 133- 03E; Nov.16, 1995) and RF-0095 (25-49N, 129-49E; Nov.27, 1995). The results are shown in Table 10. The mean and standard deviation of F-11/F-12 blanks are approximately 0.02±0.005 pmol/kg, and no bottle seriously contaminated was found. During the observation, samples drawn from the deepest bottle were analyzed to monitor contamination of the system. The results (Table 11) shows that the system was not seriously contaminated during the observation. Sample blanks which should be subtracted from measurement values are determined so that F-11/F-12 concentrations are zero below 2000 m depth at each station. The values are shown in Table 12. PRECISION The reproducibility was estimated from replicate analyses of 100-500m depths water at 8 stations (Table 13). It was approximately less than 2% for F-11 and F-12, but at two stations (RF-0085 and RF-0091) the F-12 differences showed extraordinary large values. AIR SAMPLING At 25-39N, 131-11E after the observations along the P24 section, on November 26 of 1995, we took marine air samples with a 300 ml syringe and injected them in the system to analyze CFCs. The results are shown in Table 6 with the CFCs concentration of the laboratory air simultaneously analyzed. STANDARD GAS A standard gas used in our cruise was made by Nippon Sanso Inc. Concentrations of F-11 and F-12 contained in our standard gas were calibrated by Dr. Yutaka Watanabe of National Research Institute for Resources (NIRE)on October 25, about twenty days before the WHP-P24 observations. F-11 and F-12 concentrations of our standard gas referred to a NIRE standard gas were 288.0±2.8 pptv and 482.4±5.7 pptv, respectively. We used these values to calculate the F-11 and F-12 concentrations of seawater/air samples obtained during the cruise. The NIRE standard gas has been scaled by a SIO standard gas used in the Hokkaido University. Therefore, our values determined via NIRE standard gas ought to have consistency with data scaled with SIO standards. Table 9: CFC scaling factors. CFC concentration = A + BX + CX2 + DX3, X: Area F12 RF-0070 RF-0072 RF-0074 RF-0078 RF-0082 P24-02 P24-04 P24-06 P24-10 P24-14 A -9.38E -15 -2.19E -15 8.48E -15 -6.64E -15 2.42E -15 B 1.29E -04 1.19E -04 1.22E -04 1.11E -04 1.18E -04 C -2.84E -10 6.10E -10 4.29E -10 1.24E -09 5.20E -10 D 2.58E -14 -1.68E -15 3.17E -15 -1.57E -14 -2.16E -15 F12 RF-0085 RF-0088 RF-0091 RF-0093 RF-0095 P24-17 P24-20 P24-23 P24-25 Blank test A -1.86E -14 7.48E -15 5.14E -16 6.10E -15 6.63E -17 B 1.19E -04 1.16E -04 1.20E -04 1.09E -04 1.08E -04 C 2.16E -10 6.57E -10 1.99E -10 1.26E -09 8.97E -10 D 7.27E -15 -4.75E -15 4.31E -15 -1.75E -14 0.00E+00 F11 RF-0070 RF-0072 RF-0074 RF-0078 RF-0082 P24-02 P24-04 P24-06 P24-10 P24-14 A -8.05E -15 2.25E -15 3.85E -15 1.22E -15 0.00E +00 B 1.91E -05 1.81E -05 1.87E -05 1.78E -05 1.95E -05 C -2.46E -11 6.66E -12 -1.38E -11 9.36E -14 -1.99E -11 D 1.38E -16 -5.66E -17 4.47E -17 -9.09E -18 9.87E -17 F11 RF-0085 RF-0088 RF-0091 RF-0093 RF-0095 P24-17 P24-20 P24-23 P24-25 Blank test A -2.98E -15 -6.85E -16 2.30E -15 -1.65E -15 1.11E -17 B 1.98E -05 2.11E -05 2.19E -05 1.81E -05 1.97E -05 C -3.75E -11 -3.79E -11 -6.19E -11 -1.59E -11 1.69E -11 D 1.71E -16 1.52E -16 2.72E -16 5.27E -17 0.00E+00 Table 10: Sample blanks at the test stations. (1)Before P24 section Station Bottle Syringe Depth(m) F12(pmol/kg) F11(pmol/kg) ---------------------------------------------------------------------------------------------- RF-0068 1 1 2500 0.030 0.028 Blank 2 2 2500 0.019 0.029 Test 3 3 2500 0.036 0.037 4 4 2500 0.023 0.025 5 5 2500 0.032 0.025 6 6 2500 0.014 0.028 7 7 2500 0.024 0.030 8 8 2500 0.025 0.030 9 9 2500 0.027 0.021 10 10 2500 0.027 0.028 18 18 2500 0.020 0.022 19 19 2500 0.021 0.024 11 11 2500 0.020 0.026 12 12 2500 0.021 0.031 13 13 2500 0.021 0.022 15 15 2500 0.019 0.023 14 14 2500 0.026 0.029 16 16 2500 0.015 0.023 17 17 2500 0.021 0.024 20 20 2500 0.014 0.022 21 21 2500 0.023 0.023 22 22 2500 0.011 0.023 23 23 2500 0.023 0.024 24 24 2500 0.018 0.038 MEAN 0.022 0.026 S.D. 0.006 0.005 (2) After P24 section Station Bottle Syringe Depth(m) F12(pmol/kg) F11(pmol/kg) --------------------------------------------------------------------------------------------- RF-0095 1 1 2500 0.017 0.014 Blank 2 2 2500 0.008 0.014 Test 3 3 2500 0.013 0.014 4 4 2500 0.014 0.019 5 5 2500 0.012 0.016 6 6 2500 0.013 0.016 7 7 2500 0.013 0.015 8 8 2500 0.011 0.014 9 9 2500 0.019* 0.024* 10 10 2500 0.013 0.016 11 11 2500 0.017 0.018 12 12 2500 0.015 0.018 13 13 2500 0.011 0.014 14 14 2500 0.010 0.012 15 15 2500 0.012 0.014 16 16 2500 0.010 0.014 17 17 2500 0.031 0.026 18 18 2500 0.016 0.014 19 19 2500 0.018 0.017 20 20 2500 0.014 0.015 21 21 2500 0.014 0.014 22 22 2500 0.013* 0.029* 23 23 2500 0.014 0.021 27 24 2500 0.023* 0.027* MEAN 0.015 0.017 S.D. 0.005 0.005 * : bad measurement Table 11: Sample blanks of the deepest bottles. Depth F12 F11 Station Cast Bottle (m) (pmol/kg) (pmol/kg) ------------------------------------------------------------------- RF-0072 (P24-04) 1 1 2058 0.019 0.038 RF-0074 (P24-06) 1 1 3909 0.017 0.030 1 3909 0.029 0.035 RF-0076 (P24-08) 1 1 4833 0.010 0.021 24 4834 0.017 0.023 1 4833 0.023 0.027 24 4834 0.016 0.023 RF-0077 (P24-09) 1 1 5009 0.023 0.026 1 5009 0.029 0.022 1 5009 0.026 0.025 1 5009 0.023 0.020 RF-0078 (P24-10) 1 1 4152 0.019 0.025 1 4152 0.022 0.022 RF-0082 (P24-14) 1 1 4290 0.017 0.022 RF-0084 (P24-16) 1 1 4881 0.022 0.029 1 4881 0.020 0.022 1 4881 0.018 0.017 RF-0085 (P24-17) 1 1 5164 0.020 0.025 RF-0091 (P24-23) 1 1 5376 0.027 0.034 RF-0093 (P24-25) 1 1 4170 0.018 0.024 1 4170 0.016 0.025 Table 12: Sample blanks determined at each station. F-12 F-11 Station (pmol/kg) (pmol/kg) -------------------------------------------- RF0070 (P24-02) 0.019 0.038 RF0072 (P24-04) 0.019 0.038 RF0074 (P24-06) 0.018 0.027 RF0078 (P24-10) 0.011 0.026 RF0082 (P24-14) 0.016 0.016 RF0085 (P24-17) 0.025 0.020 RF0088 (P24-20) 0.008 0.019 RF0091 (P24-23) 0.013 0.031 RF0093 (P24-25) 0.009 0.023 REFERENCES Bullister, J.L. and R.F. Weiss,1988:Determination of CCl3F and CCl2F2 in sea water and air. Deep Sea Research ,35, 839 -853. Table 13: Reproducibility estimated by replicate analyses. Depth F-12 F-11 F12 Diff F11 Diff Station Cast Bottle Syringe (m) (pmol/kg) (pmol/kg) (%) (%) ------------------------------------------------------------------------------------------- RF-0072 1 15 15 200 1.291 2.364 0.07 0.30 P24-04 15 15 200 1.292 2.357 20 20 49 1.061 1.886 3.41 0.83 20 20 49 1.098 1.901 RF-0074 1 6 14 204 1.292 2.385 0.53 0.36 P24-06 6 14 204 1.299 2.376 RF-0078 1 6 14 201 1.187 2.119 0.53 0.43 P24-10 6 14 201 1.180 2.110 8 16 101 1.090 1.791 2.30 1.88 8 16 101 1.066 1.758 RF-0082 1 6 14 203 1.359 2.486 0.97 0.79 P24-14 6 15 203 1.345 2.466 RF-0085 1 6 14 202 1.297 2.525 0.44 14.69 P24-17 6 15 202 1.291 2.179 RF-0088 1 6 14 203 1.365 2.458 0.71 2.68 P24-20 6 15 203 1.356 2.393 RF-0091 6 16 201 1.373 2.640 1.11 13.58 P24-23 6 17 201 1.358 2.304 3 12 504 0.941 1.708 2.00 1.84 3 13 504 0.922 1.676 RF-0093 1 19 13 504 1.069 2.048 0.00 1.68 P24-25 19 14 504 1.069 2.082 21 16 201 1.311 2.224 1.82 4.07 21 17 201 1.288 2.135 Table 14: Air measurements at 25-39 N, 131-11 E. F12 F11 Nov.26,1995 (ppt) (ppt) the open air 557.7 284.0 569.4 286.4 556.7 281.6 570.8 297.2 the air inside ship 582.2 426.1 (in the laboratory) 571.1 360.1 2.5 CTD measurements by Y. Takatsuki (April 30,1999) EQUIPMENT, CALIBRATIONS AND STANDARDS The CTD equipment used on this cruise was the property of JMA. The following equipment was deployed on the CTD/rosette underwater frame: 1. Falmouth Scientific, Inc. (FSI) Triton ICTD TM (#1316). 2. General Oceanics 12 liter 24 bottle rosette multi-bottle sampler Model 1015. 3. Benthos Altimeter Model 2110-1. 4. Preussag 10 kHz pinger Model TBB. 5. One SIS (Sensoren Instrumente Systeme) digital reversing thermometer (RTM) and two SIS digital reversing pressure meters (RPM). The shipboard equipment consisted of complete integral system for demodulating and displaying the CTD data as well as controlling the rosette multi-bottle sampler. The system included the following major units: 1. FSI deck terminal Model 1050. 2. Compaq Deskpro TM PC system with 128 Mbytes 3.5 inch Magneto-optical (MO) disk drive. 3. General Oceanics rosette firing module for Model 1015. Pre-cruise temperature and pressure calibrations for CTD #1316 was carried out by S.E.A. corporation in October/November, 1995. Correction on RTM and RPMs data were done according to the correction tables, which attached at shipping. Pre-and post-cruise calibrations of the conductivity sensors were not carried out, so the calibration constants were calculated from a fit to the salinities measured from the water samples collected at each station. CTD TEMPERATURE CALIBRATION CTD temperature was calibrated on 30 October 1995 in degrees Centigrade in the IPTS-68 scale at fifteen temperatures ranging from 0.99 to 30.1° by the S.E.A. corporation. The transfer standard had been calibrated on 20 October 1995 at the triple point of water. The following linear fit for CTD temperature was used, with a rms error of 0.3 millidegrees. T68 =0 .9999239 x T(raw) -0.0111757 CTD PRESSURE CALIBRATION CTD pressure was calibrated on 2 November 1995 with a dead-weight tester at ten point pressures ranging from 0.0 to 5878.2 dbar by the S.E.A. corporation. The following equations for CTD pressure for downcast and up-cast were used, with a rms error of 0.11 dbar and 0.08 dbar, respectively. P(down) = 0.219960 +1.000173 x P(raw) -1.174592E - 7 x P(raw)2 +1.68155E -11 x P(raw)3 (down cast ,full scale) P(up)' = -0.2453189 +0.9999456 x P(raw) -7.525608E -8 x P(raw)2 +1.860992E -11 x P(raw)3 (up cast ,full scale) Digital RTM calibration RTM was calibrated by SIS before shipping. Correction values for RTM are listed in Table 15. Table 15: Digital RTM correction value 'c'. T(cal) =T(raw) + c T777 (date of calibration:3 Nov.1993) Temperature -2 0 5 10 15 19.5 20 c 0.000 -0.001 -0.001 -0.001 -0.001 -0.001 -0.001 DIGITAL RPM CALIBRATION We used three RPMs, P6184, P6299H, and P6300H. Two of them were calibrated by SIS before shipping. P6184 has no calibration data, hence we have done no corrections on data from P6184. Correction values for RPMs are listed in Table 16. Table 16: Digital RPM correction value ''at 3°C. P(cal) =P(raw) + c P6299H (date of calibration:10 Sep.1993) Pressure -10 1000 2007 3008 4009 5005 5999 c +10 +1 -5 -5 -5 0 +6 P6300H (date of calibration:10 Sep.1993) Pressure -5 1001 2006 3008 4008 5007 6003 c +5 0 -4 -5 -4 -2 +2 CTD DATA COLLECTION AND PROCESSING The RS-232C signal from a FSI 1050-deck terminal was taken by a Compaq Deskpro-TM PC to log and process data. The CTD data at down-and up-casts were fully logged in real time to the RAM disk, and were copied to MO disks after CTD recovery. Data were processed on the PC with the software programmed by the members of Nagasaki Marine Observatory, according to the method by Millard and Yang (1993). A time-constant difference between the temperature and conductivity sensors, which is necessary for salinity de-spiking, was determined Tau =0 .250 seconds so as to minimize fluctuations of salinity profile (Kawabe and Kawasaki, 1993). The calibration for CTD #1316 was done according to the IPTS-68 scale, temperature was converted to the ITS-90 scale by following equation: T90 =0 .99976 x T68. Owing to pressure sensor hysteresis, pressure for up-cast (P up were calculated with following equations according to Millard and Yang (1993): P(up) =P(up)'(1 - W )+P(down)W W = exp ( - ( P(bottom) - P(down)) / Z0, where, P(bottom) is the maximum pressure for the cast, and Z0 is scaling factor, which is 300 dbar for ICTD. Table 17: Position on rosette of RTM and RPMs. Inst # position T777 3 P6184 3 P6300H 9 P6299H 13 Condition of the temperature and pressure sensors during the cruise were monitored to some extent through comparisons of CTD measurements with Digital RTM and Digital RPM at the time the water bottle was tripped. The position on rosette of RTM and RPMs were set are tabulated in Table 17. Any drift exceeding a nominal precision of RTM and RPM were not detected for the CTD (*Figure 6 and 7). *Figure 6: Temperature differences between CTD and Reversing Temperature Meter (RTM) *Figure 7: Pressure differences between CTD and Reversing Pressure Meter (RPM) Table 18: Correction coefficients for conductivity sensor of CTD #1316 C = A x C(raw)' +B Station A B P24-01 -P24-02 1.000626 -0.0110 P24-03 -P24-09 1.000700 -0.0110 P24-10 -P24-18 1.000687 -0.0110 P24-19 -P24-26 1.000701 -0.0110 As mentioned above, we could not carryout pre-and post-cruise calibrations of the conductivity sensors. The conductivity data were converted for cell material deformation correction at first: C(raw)' = (1 + alpha (P - P0) + beta (T -T0))C(raw) alpha = -3.0E -5 beta = 1.5E -8 T0 = 2.8 P0 = 0.0. The bias was assumed in advance, and then, the slope was determined from a linear- fit to the salinities measured from the water samples collected at each station. The coefficients for correction finally adopted for the data processing are listed in Table 18. Figure 8 shows the differences between CTD salinity and salinity of water samples. Statistical analysis of the difference between the CTD and water sample salinities deeper than 2000 m showed a standard deviation less than 0.0023 (all data) and less than 0.0008 (exclude three doubtful data, that is, 2275.8 dbar at P24-07, 2787.1 dbar and 2530.9 dbar at P24-09). *Figure 8: Differences between CTD salinity and salinity of water samples. Station number vs. salinity difference (deeper than 2000m; left), Pressure vs. salinity difference (right). REFERENCES Kawabe, and Kawasaki,1993:CTD Data Calibration. JODC manual guide JP013-93-1, 73 pp (in Japanese). Millard, R.C. and K. Yang,1993:CTD Calibration and Processing Methods used at Woods Hole Oceanographic Institution. WHOI Technical Report WHOI-93-44, 104 pp. *All figures shown in pdf file. FINAL CFC DATA QUALITY EVALUATION (DQE) COMMENTS ON P24. (David Wisegarver) Dec 2000 by Based on the data quality evaluation, this data set meets the relaxed WOCE standard (3% or 0.015 pmol/kg overall precision) for CFC's. Detailed comments on the DQE process have been sent to the PI and to the WHPO. The CFC concentrations have been adjusted to the SIO98 calibration Scale (Prinn et al. 2000) so that all of the Pacific WOCE CFC data will be on a common calibration scale. For further information, comments or questions, please, contact the CFC PI for this section I. Kaneko (ikuo-kaneko@met.kishou.go.jp, knemoto@mri-jma.go.jp) or David Wisegarver (wise@pmel.noaa.gov) More information may be available at www.pmel.noaa.gov/cfc. ******************************************************************************** Prinn, R. G., R. F. Weiss, P. J. Fraser, P. G. Simmonds, D. M. Cunnold, F. N. Alyea, S. O'Doherty, P. Salameh, B. R. Miller, J. Huang, R. H. J. Wang, D. E. Hartley, C. Harth, L. P. Steele, G. Sturrock, P. M. Midgley, and A. McCulloch, A history of chemically and radiatively important gases in air deduced from ALE/GAGE/AGAGE J. Geophys. Res., 105, 17,751-17,792, 2000. ******************************************************************************** WHPO CTD DATA CONSISTENCY CHECK 2002.JAN.15 The WHP-Exchange format bottle and/or CTD data from this cruise have been examined by a computer application for contents and consistency. The parameters found for the files are listed, a check is made to see if all CTD files for this cruise contain the same CTD parameters, a check is made to see if there is a one-to-one correspondence between bottle station numbers and CTD station numbers, a check is made to see that pressures increase through each file for each station, and a check is made to locate multiple casts for the same station number in the bottle data. Results of those checks are reported in this '_check.txt' file. When both bottle and CTD data are available, the CTD salinity data (and, if available, CTD oxygen data) reported in the bottle data file are subtracted from the corresponding bottle data and the differences are plotted for the entire cruise. Those plots are the' _sal.ps' and '_oxy.ps' files. Following parameters found for bottle file: EXPOCODE DEPTH SILCAT CFC-12_FLAG_W SECT_ID CTDPRS SILCAT_FLAG_W TRITUM STNNBR CTDTMP NITRAT TRITUM_FLAG_W CASTNO CTDSAL NITRAT_FLAG_W HELIUM SAMPNO CTDSAL_FLAG_W NITRIT HELIUM_FLAG_W BTLNBR SALNTY NITRIT_FLAG_W DELHE3 BTLNBR_FLAG_W SALNTY_FLAG_W PHSPHT DELHE3_FLAG_W DATE CTDOXY PHSPHT_FLAG_W DELC14 TIME CTDOXY_FLAG_W CFC-11 DELC14_FLAG_W LATITUDE OXYGEN CFC-11_FLAG_W LONGITUDE OXYGEN_FLAG_W CFC-12 - All ctd parameters match the parameters in the reference station. - All stations correspond among all given files. - No bottle pressure inversions found. - Bottle file pressures are increasing. p24_hy1.csv -> contains stations with multiple casts: station -> 10: | station -> 15: | station -> 20: | station -> 26: 2 casts. | 2 casts. | 2 casts. | 2 casts. station -> 11: | station -> 16: | station -> 21: | station -> 6: 2 casts. | 2 casts. | 2 casts. | 2 casts. station -> 12: | station -> 17: | station -> 22: | station -> 7: 2 casts. | 2 casts. | 2 casts. | 2 casts. station -> 13: | station -> 18: | station -> 23: | station -> 8: 2 casts. | 2 casts. | 2 casts. | 2 casts. station -> 14: | station -> 19: | station -> 24: | station -> 9: 2 casts. | 2 casts. | 2 casts. | 2 casts. WHPO DATA PROCESSING NOTES Date Contact Data Type Data Status Summary =============================================================================== 02/28/96 Fujimura DOC Cruise Rpt Rcvd @ WHPO 02/28/96 Fujimura SUM Submitted 10/16/97 Fujimura CTD/BTL Submitted for DQE 08/07/98 Diggs CTD Website Updated 12/06/99 Huynh CTD/BTL/SUM Data Update New data files received 12/06/99 Diggs DOC Submitted Hard copy only 04/20/00 Key DELC14 No Data Submitted See Note: Unfortunately, I can provide no new information on the C14 status for cruises P15N and P24. I do know that acquiring data from CS Wong (P15N) has been very difficult. I'll try to investigate. 07/07/00 Huynh DOC Website Updated; pdf, txt versions online 08/04/00 Saiki CTD/BTL Data Status changed to Public SALNTY, OXYGEN, NUT's, CFC's and CTD I am pleased to inform you that the PIs and participants of the one-time and repeat cruises conducted by the Japan Meteorological Agency's vessels agreed to change most of the data status to public. The only exception is the He/Tr of P09 and He/Tr, C-14 of P24. In this respect, a list of the cruises which we wish to change the status from non-public to public follows for confirmation. 08/08/00 Diggs CTD/BTL Website Updated; data unencryted JMA just released these data and Dave Muus and Jim Swift requested that the data be correctly pressure sorted. That is now done and the files are unencrypted and online. CTD files are now unencrypted and online as well. All tables and files associated with this cruise have been updated as well. 07/03/01 Wisegarver CFCs DQE Complete; precision outside original WOCE standards, meets 'relaxed' standard In regards to P24, the surface saturation of CFC-12 is about 100% while that of CFC-11 is about 90% at stations 2, 10, 20, 23, and 25. THis difference is greater than normally expected. Typically, an undersaturation of 10% can be associated with upwelling, deep mixing or convection, but even then, the two gasses are usually close in saturation. In light of this, CFC-11 QUALT1 flags of '2' (good) for stations 2 and 23 have been given QUALT2 flags if '3' (questionable) as well as the shallow low ratio values at stations 10, 17, 20 and 25. With these additional flags, P24 meets the 'relaxed' standard. We will forward our QUALT2 DQE flag recommendations to the WHP Office. We will not alter any of the original CFC data or flags sent by your group to the WOCE office for P24. 11/16/01 Bartolacci CFCs Updated CFCs ready to be merged I have placed the updated CFC data file sent by Wisegarver into the P24 original directory in a subdirectory called 2001.07.09_P24_CFC_UPDT_WISEGARVER This directory contains data, documentation and readme files. data are ready for merging 01/07/02 Uribe CTD Website Updated: CSV File Added CTD has been converted to exchange using the new code and put online. 01/17/02 Hajrasuliha CTD Internal DQE completed See Note: created .ps files, check with gs viewer. Created *check.txt file. 02/13/02 Swift He/Tr Data will not be processed; lack of funding Please update the records for P24 (49RY9511_2). He/Tr will not be processed due to lack of funds. Swift talked to Aoyama at the Ocean Sciences meeting yesterday and reminded him of that fact. 02/16/02 Diggs C14 Data ready to be merged I have recently located the Radiocarbons for P24 (Aoyama). They are in the following directory and are ready to merge: ... data/onetime/pacific/p24/original/20011129_P24_C14_AOYAMA I did some refomatting to get them into WOCE format and should merge without problems. 02/26/02 Muus DELC14 Data Merged into new online BTL & CSV files - Merged DELC14 and C14ERR into web bottle file. - Added QUALT2 same as QUALT1. - Put new woce format and exchange format bottle files on-line. Notes on P24 merging Feb 26, 2002 D.Muus 1. Merged DELC14 and C14ERR from: File p24hy.mao received from M. Aoyama Nov 29, 2001. into bottle file from web (20010327WHPOSIOKJU) 2. SUMMARY file has parameter code 12 (C14) on Stations 2/1, 6/1, 6/2, 14/1, 14/2, 17/1, 17/2, 23/1, 23/2, 26/1 and 26/2. New data file (p24hy.mao) has C14 data for Stations 17/1, 17/2, 23/1 and 23/2 only. Left SUMMARY file unchanged. 3. Changed all remaining quality code "1"s to "9"s and made QUALT2 word same as QUALT1. 4. Made new exchange file for Bottle data. 5. Checked new bottle file with Java Ocean Atlas. 06/25/02 Kappa DOC Cruise Report updated Added CFC DQE Report, CTD Data Consistency Check, and WHPO Data Processing Notes to both PDF and TXT documents.