A. CRUISE NARRATIVE WOCE P09 (RY9407) A.1. HIGHLIGHTS WHP CRUISE SUMMARY INFORMATION WOCE section designation P09 Expedition designation (EXPOCODE) 49RY9407_1-2 Chief Scientist(s) and their affiliation Ikuo KANEKO *, Satoshi KAWAE**/JMA Dates 1994.JUL.07 - 1994.AUG.25 Ship R/V Ryofu Maru Ports of call Leg-1: Tokyo - Palau, Leg-2: Palau - Guam Number of stations 105 34ƒ 15' N Geographic boundaries of the stations 137ƒ E 142ƒ E 15ƒ N Floats and drifters deployed none Moorings deployed or recovered none Contributing Authors I. Kaneko, H. Kamiya, M. Tamaki, Y. Takatsuki, T. Miyao, M. Ishii * Chief Scientist **Co-Chief Scientist Tel: +81-3-3212-8341 Ext.5127 Oceanographical Division Fax: +81-3-3211-3047 Marine Department Phone: 508-289-2530 Japan Meteorological Agency (JMA) Fax: 508-457-2181 1-3-4, Ohtemachi, Chiyoda-ku Internet: i_kaneko@umi.hq.kishou.go.jp Tokyo 100, Japan WHP CRUISE AND DATA INFORMATION Cruise Summary Information Hydrographic Measurements Description of scientific program CTD - general CTD - pressure Geographic boundaries of the survey CTD - temperature Cruise track (figure) CTD - conductivity/salinity Description of stations CTD - dissolved oxygen Description of parameters sampled Salinity Floats and drifters deployed Oxygen Moorings deployed or recovered Nutrients CFCs Principal Investigators for all measurements Helium Cruise Participants Tritium Radiocarbon Problems and goals not achieved CO2 system parameters References DQE Reports CTD S/O2/nutrients CFCs Data Processing Notes A.2 CRUISE SUMMARY INFORMATION A.2.a Geographic Boundaries The station locations along the P9 section are shown in Figure 1.1 and tabulated in Table 1.1. Table 1.1 includes the dates, times and water depths. The section was occupied from north toward south except two parts of the section, between Sta.37 and 40, and between Sta.54 and 61. These parts of the section were occupied from south toward north. The details on the cruise track is given in Section 1.4. Table 1.1 Station data of WHP-P9 (listed geographic sequentially) Leg Station Date Time Position(GPS) W.depth WHP-P9 Ry (JST: UTC+9h) Latitude Longitude (m) --------------------------------------------------------------------- 1 1 8633 07 09 94 0149 34 15.02 N 137 00.04 E 145 1 2 8634 07 09 94 0329 34 06.56 N 136 59.86 E 1220 1 3 8635 07 09 94 0608 34 00.03 N 136 59.37 E 1010 1 4 8636 07 09 94 1006 33 50.02 N 136 58.66 E 1850 1 5 8637 07 09 94 1227 33 39.91 N 136 59.73 E 2010 1 6 8638 07 09 94 1525 33 29.79 N 137 00.98 E 2055 1 7 8639 07 09 94 1836 33 20.19 N 137 00.06 E 2620 1 8 8640 07 09 94 2207 33 10.28 N 137 00.35 E 2870 1 9 8641 07 10 94 0122 33 00.04 N 136 59.60 E 4295 1 10 8642 07 10 94 1124 32 49.10 N 136 59.71 E 3885 1 11 8643 07 10 94 1653 32 40.52 N 137 00.38 E 4180 1 12 8644 07 10 94 2202 32 30.68 N 137 00.18 E 4095 1 13 8645 07 11 94 0217 32 20.08 N 136 59.95 E 4050 1 14 8646 07 11 94 0720 32 10.67 N 137 00.58 E 4000 1 15 8647 07 11 94 1111 31 59.84 N 136 59.66 E 4230 1 16 8648 07 11 94 1821 31 40.39 N 136 59.45 E 4170 1 17 8649 07 11 94 2338 31 20.11 N 136 59.87 E 4165 1 18 8650 07 12 94 0523 31 00.49 N 136 59.73 E 4170 1 19 8651 07 12 94 1248 30 39.87 N 136 59.90 E 4235 1 20 8652 07 12 94 1803 30 20.47 N 137 00.12 E 4420 1 21 8653 07 12 94 2323 30 00.36 N 137 00.02 E 4490 1 22 8654 07 13 94 0807 29 30.15 N 137 09.66 E 4530 1 23 8655 07 13 94 1448 28 59.87 N 136 59.68 E 4550 1 24 8656 07 13 94 2102 28 30.12 N 136 59.84 E 4515 1 25 8657 07 14 94 0351 28 00.33 N 136 59.98 E 4160 1 26 8658 07 14 94 1226 27 29.80 N 137 00.34 E 4350 1 27 8659 07 14 94 1922 26 59.86 N 136 59.90 E 4700 1 28 8660 07 15 94 0433 26 30.09 N 136 59.67 E 5020 1 29 8661 07 15 94 1137 25 59.56 N 137 00.07 E 5545 1 30 8662 07 15 94 2118 25 29.75 N 137 00.56 E 4920 1 31 8663 07 16 94 0413 25 00.41 N 137 00.14 E 5020 1 32 8664 07 16 94 1047 24 30.14 N 137 00.09 E 5310 1 33 8665 07 16 94 1812 23 59.81 N 136 59.87 E 3915 1 34 8666 07 17 94 0213 23 30.46 N 137 00.00 E 4220 1 35 8667 07 17 94 0942 23 00.27 N 137 19.61 E 4900 1 36 8668 07 17 94 1733 22 30.44 N 137 19.64 E 4580 1 37 8672 07 22 94 1352 22 00.12 N 137 20.23 E 4280 1 38 8671 07 22 94 0442 21 29.80 N 137 00.41 E 4370 1 39 8670 07 21 94 1806 20 59.63 N 137 00.11 E 4810 1 40 8669 07 21 94 0913 20 29.49 N 137 00.32 E 4465 --------------------------------------------------------------------- Leg Station Date Time Position(GPS) W.depth WHP-P9 Ry (JST: UTC+9h) Latitude Longitude (m) --------------------------------------------------------------------- 1 41 8673 07 23 94 0737 20 00.11 N 136 59.98 E 4750 1 42 8674 07 23 94 1657 19 30.27 N 136 59.85 E 4650 1 43 8675 07 23 94 2306 19 00.60 N 136 59.88 E 4690 1 44 8676 07 24 94 0542 18 30.63 N 137 00.05 E 4910 1 45 8677 07 24 94 1232 18 00.18 N 136 59.75 E 4920 1 46 8678 07 24 94 2117 17 29.88 N 136 59.78 E 4890 1 47 8679 07 25 94 0403 17 00.74 N 136 59.68 E 4775 1 48 8680 07 25 94 1042 16 30.21 N 137 00.05 E 5565 1 49 8681 07 25 94 1752 15 59.85 N 136 59.95 E 5200 1 50 8682 07 26 94 0239 15 30.27 N 136 59.96 E 5130 1 51 8683 07 26 94 0927 15 00.47 N 136 59.84 E 5290 1 52 8684 07 26 94 1643 14 30.58 N 136 59.64 E 4480 1 53 8685 07 26 94 2352 13 59.89 N 137 00.81 E 4810 2 54 8693 08 06 94 0836 13 29.30 N 136 59.75 E 5100 2 55 8692 08 06 94 0216 13 00.61 N 136 59.33 E 4815 2 56 8691 08 05 94 1752 12 30.13 N 137 00.06 E 4695 2 57 8690 08 05 94 0741 12 00.32 N 136 59.80 E 5150 2 58 8689 08 04 94 2318 11 30.20 N 136 59.78 E 4730 2 59 8688 08 04 94 0208 10 59.66 N 136 59.77 E 4895 2 60 8687 08 03 94 1921 10 30.55 N 136 59.89 E 5025 2 61 8686 08 03 94 1040 09 59.79 N 136 59.77 E 4860 2 62 8694 08 07 94 0934 09 29.99 N 136 59.85 E 4715 2 63 8695 08 07 94 1548 08 59.49 N 136 59.93 E 3160 2 64 8696 08 07 94 2026 08 40.29 N 137 00.95 E 2400 2 65 8697 08 07 94 2350 08 19.75 N 136 59.97 E 2270 2 66 8698 08 08 94 0306 08 00.52 N 137 02.00 E 2960 2 67 8699 08 08 94 0916 07 40.04 N 136 50.09 E 3175 2 68 8700 08 08 94 1304 07 30.56 N 136 50.09 E 2950 2 69 8701 08 08 94 1712 07 19.73 N 136 49.66 E 6560 2 70 8702 08 09 94 0224 07 00.12 N 136 59.89 E 4235 2 71 8703 08 09 94 0823 06 38.84 N 137 20.97 E 4110 2 72 8704 08 09 94 1428 06 17.09 N 137 43.42 E 4385 2 73 8705 08 09 94 2009 05 55.30 N 138 04.42 E 4210 2 74 8706 08 10 94 0352 05 33.29 N 138 26.19 E 4565 2 75 8707 08 10 94 1008 05 11.16 N 138 49.05 E 4210 2 76 8708 08 10 94 1603 04 49.13 N 139 10.75 E 4400 2 77 8709 08 10 94 2144 04 27.48 N 139 32.89 E 4090 2 78 8710 08 11 94 0518 04 05.24 N 139 55.54 E 4250 2 79 8711 08 11 94 1113 03 43.08 N 140 17.05 E 4280 2 80 8712 08 11 94 1913 03 21.20 N 140 39.50 E 3775 --------------------------------------------------------------------- Leg Station Date Time Position(GPS) W.depth WHP-P9 Ry (JST: UTC+9h) Latitude Longitude (m) --------------------------------------------------------------------- 2 81 8713 08 12 94 0023 03 00.76 N 140 59.67 E 3535 2 82 8714 08 12 94 0703 02 45.10 N 141 14.90 E 3030 2 83 8715 08 12 94 1131 02 30.08 N 141 29.64 E 2800 2 84 8716 08 12 94 1502 02 15.74 N 141 44.87 E 2615 2 85 8717 08 12 94 1838 02 00.52 N 141 59.74 E 2575 2 86 8718 08 13 94 0118 01 45.11 N 141 59.48 E 2750 2 87 8719 08 13 94 0524 01 30.64 N 142 00.18 E 2810 2 88 8720 08 13 94 0958 01 15.16 N 142 00.05 E 2940 2 89 8721 08 13 94 1442 01 00.48 N 142 00.10 E 3060 2 90 8722 08 13 94 2148 00 45.46 N 142 00.05 E 3140 2 91 8723 08 14 94 0224 00 30.14 N 141 59.96 E 3310 2 92 8724 08 14 94 0708 00 15.57 N 141 59.85 E 3420 2 93 8725 08 14 94 1230 00 00.07 S 141 59.83 E 3370 2 94 8726 08 15 94 0834 00 14.49 S 141 59.98 E 3285 2 95 8727 08 15 94 1333 00 30.03 S 142 00.01 E 3335 2 96 8728 08 15 94 1823 00 44.40 S 142 00.04 E 3140 2 97 8729 08 15 94 2323 00 59.63 S 142 00.03 E 3020 2 98 8730 08 16 94 0602 01 14.99 S 141 59.85 E 3195 2 99 8731 08 16 94 1053 01 30.21 S 141 59.93 E 3500 2 100 8732 08 16 94 1612 01 44.67 S 142 00.35 E 2855 2 101 8733 08 16 94 2045 01 59.46 S 142 00.05 E 3570 2 102 8734 08 17 94 0357 02 14.52 S 142 04.67 E 3910 2 103 8735 08 17 94 1027 02 29.22 S 142 09.86 E 4150 2 104 8736 08 17 94 1559 02 44.53 S 142 14.81 E 3040 2 105 8737 08 18 94 0718 02 52.16 S 142 16.92 E 1760 (Re-occupation) 2 92 8738 08 19 94 0004 00 15.09 N 141 59.97 E 3395 --------------------------------------------------------------------- A.2.b Total number of stations occupied Sampling Accomplished 105 stations of CTD casts were completed. Measured parameters and numbers of samples are as follows: Numbers of sampling bottles and layers bottles : triggered 3613 successfully closed 3592 sampling layers : triggered 3392 successfully sampled 3226 Numbers of water samples analyzed: salinity 105 stations 3224 layers oxygen 101 stations 3041 layers nutrients 101 stations 3102 layers CFCs 24 stations 351 layers Total Carbonate 23 stations 618 layers Numbers of water samples collected for shore-based analysis: helium-3 (3He) 25 stations 486 layers tritium (3H) 25 stations 389 layers AMS carbon-14 (14C) 23 stations 618 layers A.2.c Floats and drifters deployed None A.2.d Moorings Deployed or Recovered None A.3 LIST OF PRINICIPAL INVESTIGATORS FOR ALL MEASUREMENTS (TABLE 1.2) Table 1.2 Parameter Sampling group Principal Investigator ---------------------------------------------------------------------- CTDO/Rosette JMA/MD Yasushi Takatsuki Salinity JMA/MD Yasushi Takatsuki Oxygen, Nutrients JMA/MD Hitomi Kamiya CFC JMA/MD Ikuo Kaneko TU Mamoru Tamaki 3H/3HE JMA/MRI Katsumi Hirose L-DEO Peter Schlosser 14C JMA/MRI Katsumi Hirose Total carbonate JMA/MRI Masao Ishii ADCP JMA/MD Ikuo Kaneko ---------------------------------------------------------------------- JMA/MD: Marine Department, Japan Meteorological Agency JMA/MRI: Meteorological Research Inst., JMA TU: Tokai University L-DEO: Lamont-Doherty Earth Observatory of Columbia University A.4 SCIENTIFIC PROGRAMME AND METHODS Figures 1.2a-1.2f show the locations where water samples were collected for analyses of dissolved oxygen, nutrients, CFCs, 3H, 3He, and 14C. Figures 1.3a and 1.3b show preliminary vertical sections of potential temperature and salinity taken by the CTD. ADCP Measurements Continuous underway current measurements were made by ADCP (RD Instruments Inc., Model RD-VM0075TM) along the cruise track. The current was measured at 50 layers from the sea surface to 800m depth. 1.3 Lists of Principal Investigators and Cruise Participants The measured parameters, sampling groups, principal investi- gators (PIs) and participants in the cruise are listed in Tables 1.2 and 1.3. 1.4 Preliminary Results Cruise tracks Leg-1 (from Tokyo to Palau, Sta.1-53) Leg-1 consisted of 53 stations (Sta.1-53; Ry8633-8685). The P9 section was started at Sta.1 (34 15 N, 137 00 E) on July 9, 1994. From the start of the section to Sta.36(Ry8668; 22 30N), the observations were carried out from north to south according to the plan. Owing to the approach of the typhoon(T9407), after Sta. 36 on July 17, R/V Ryofu Maru sailed down to 20 N to wait till the typhoon(T9407) went through the P9 section at about 25 N. The observations resumed at July 21 from Sta.40 (Ry8669; 20 29 N) toward the northern stations to save shiptime because the sea condition recovered from south to north. A small rosette system(12 2.5-liter bottles) was used at Stas.40, 39 and 38(Ry8669-8671) owing to the unfavorable sea state due to high swell after the storm. After Sta.37 (Ry8672) at 22 00 N, R/V Ryofu Maru sailed down to Sta.41 (Ry8673) at 20 00 N and resumed the observation toward the southern stations. We cut short the first leg after Sta.53 (Ry8685) at 14 00 N on July 26 to enter the port of Palau as scheduled. Sta.53 is the last station of Leg-1. Leg-2 (from Palau to Guam, Sta.54-105) Owing to the typhoon, we had to cut Leg-1 leaving eight stations unoccupied, and Sta.54 at 13 30N was the northernmost site in Leg-2. These made Leg-2 schedule tight. We, therefore, decided to introduce a new track of shortcut from 7 00 N, 137 00 E toward 3 00 N, 142 00 E. The new Leg-2 contained 52 stations (Sta.54-105) from 13 30 N to the coast of Papua New Gunia. When R/V Ryofu Maru left Palau on Aug. 2 and began to sail back to the northernmost station of Leg-2 at 13 30 N (Sta.54), a weather forecast reported generation and approach of a typhoon (T9413). As stormy weather was predicted around the northern part of the Leg-2 section, we started Leg-2 from 10 00 N(Sta.61; Ry8686) toward the northern stations. The small rosette system (12 2.5-liter bottles) was used at Stas.58, 57 and 56 (Ry8689- 8691) to carry out the observation safely in the rough sea. R/V Ryofu Maru reached the northernmost station at 13 29 N (Sta.54; Ry8693) on August 6 and turned back to south in aiming at the station at 9 30 N (Sta.62; Ry8694). The observation pro- gressed on schedule from Sta.62 to the southernmost station(Sta.105; Ry8737), where we arrived on Aug. 18. On the way to Guam, R/V Ryofu Maru return to the station at 0 15 N(Sta.92) for re-occupation because mistrips of the rosette system had caused many data lacks at the station on the outward voyage. Sta.92 at 0 15 N has, therefore, the two serial station numbers, Ry8724 and RY8738. Some remarks on the hydrocast Because R/V Ryofu Maru, which was constructed in 1966, is not equipped with facilities to hover herself at a fixed posi- tion, hydrocasts had to be carried out while R/V Ryofu Maru was kept drifting. The CTD/rosette system was flowed far from the ship in case of swift current or high wind. A water depth meas- ured by sounding does not agree with one estimated from combina- tion of CTD depth and its altimeter height from the bottom in such a case. At Sta.36 (Ry8668), we had to deploy the CTD/ro- sette system under the condition that mean wind speed was over 17 m/s. The CTD/rosette system could not reach the bottom even payout of full length of the cable. The maximum CTD pressure was 4317 dbar while the water depth is 5075 m. Sta.69 (Ry8701) is above the western end of Yap Trench. Although the water depth was 6600 meters, we left off the cast at 6000 m depth, considering small power of our winch. Because mean water depths of the basins around Yap Trench never exceed 5500 m, the data lack in the deep trench will no seriously inconvenience for studies on the general circulations in this region. Owing to the limited capacity of the winch and thin cable, we had to choose small sampling bottles for our the CTD/rosette system, regardless off their vulnerability to CFCs contamination. As a countermeasure against the contamination, we introduced Bullister style 2.5-liter sampling bottles, which were designed so that sampled water is hard to contaminate with CFCs contained in materials of the bottles. They were made at the factory of NOAA/PMEL. The other countermeasure was a extra cast for CFCs sampling at stations for the tracers. At the stations, samples for oxygen and nutrients were completed in the first (shallow) and second (deep) cast. 14C and 3He samples below 1500 m depth were also drawn in the second cast. In the third extra cast, CFCs and 3H/3He samples above 1500 m depth were drawn. Salinity samples were also drawn from almost all bottles to determine true depths of bottle closings. In addition to copper tubes sampling for 3H/3He, 1 liter glass bottles filled with argon gas were used for 3H sampling at layers above 1500 m depth. A.5 MAJOR PROBLEMS AND GOALS NOT ACHIEVED Problems 1) Mistrip of the rosette system We were troubled with mistrips of the 24-bottles rosette system throughout the cruise. The mistrips occurred whenever the system was deployed below 1500 m depth. As the same number of double-trips always followed misfires, the number of closed bottles agreed with the one of trigger commands when the system was recovered on the deck. This agreement of the numbers delayed our discovery of the trouble. Mistrip was never reproduced at the trigger tests on the deck. Following the article of mistrip appeared in the report of Moana Wave Cruise 893 (in WHPO90-1 manual), we intended to adjust the tensions of lanyards and bolts fixing the upper plate of the pylon, on monitoring occurrence of mistrips. On the way of Leg- 1, we took out the pylon from the rosette frame, cooled it in a bath filled with ice water for two hours and repeated triggers under the condition that lanyards pulled the balls with high tension. But, this trial was in vain because the mistrip was not reproduced by the cooling. We speculated that this trouble was caused by high pressure and was a different phenomenon from the one occurred during Moana Wave Cruise 893. We cleaned up the trigger pins, loosened the bolts of upper plate, and mounted digital RTMs and RPMs on as many bottles as possible. Once we specified a bottle (or trigger pin) which tended to cause a misfire, we set the rosette so as to use it at the shallowest layer or not to use it if possible. However, this countermeasure has caused irregular misfires at other pins. After some trials and errors, we found a way to use a misfire bottle at the deepest layer and to send trigger command twice or more there. When a misfire was forced firstly at the deepest, a double-fire stably occurred at bottles around the opposite side of the rosette frame, and the occurrence of mistrips was kept under our control during several days. However, while we relaxed our attention, a misfire used to escape from the deepest layer to a shallower layer, and we had to change our sampling tactics. This vicious circle was continued until the last station. Owing to the mistrips, about 5% of total of the sampling layers were lost. As our rosette system was not an intelligent type, misfires and double-fires caused sampling layer shifts. We determined true sampling layers carefully from the data of RTMs, RPMs, salinity and the other chemical properties when we assem- bled the water sample data file, 49RY9407.SEA. 2) CTD break down and replacement at Sta.69 (Ry8701) At the second cast of Sta.69, the temperature sensor of our CTD ( FSI Triton ICTDTM ) broke down when the system descended below 3500 m depth. The CTD was replaced to the other Triton ICTD on the deck. However, a DO sensor prepared for the new CTD did not work on account of broken wires inside of plastics mold of the sensor unit. To repair the wires was impossible for us on the deck. The other DO sensor of the broken CTD did not work on the new CTD because its inside circuit did not adapt to the new CTD. We, therefore, had to give up measuring DO profiles by CTD system since the deep cast of Sta.69. According to the comparison of water temperatures between the RTMs and CTD, a drift of the CTD temperature was recognized from Sta.51(Ry8683) and reached at the maximum of 0.02ƒC before the CTD breakdown. CTD temperature was carefully corrected based on the RTM temperatures, but had to be flagged as 'Bad measure- ment' in our CTD record files at several stations. 3) A trouble of DO titrator We used a photometric automated titrator, Model ART-3TM manufactured by Hirama Riken Inc. During Leg-1, from Tokyo to Palau, the titrator often became unstable. The sensor circuit, bad focus of the lamp and large vibration of the table are specu- lated as the cause of bad titration. We could not repair the titrator until R/V Ryofu Maru reach Palau, where we replaced the bad optical unit with the one transported from Tokyo. In Leg-2, the titrator worked normally. 2. MEASUREMENT TECHNIQUES AND CALIBRATIONS 2.1 SALINITY MEASUREMENTS (I.Kaneko) Equipment and Technique Salinity samples were collected in 150 ml amber glass bot- tles with rubber caps and stored in an air-conditioned laboratory for more than 24 hours before salinity measurements. The salini- ties were measured with a GuildlineTM AutosalTM Model 8400B salinometer. The salinometer was standardized with IAPSO Standard Sea Water(SSW) every day when it was used for sample measure- ments. 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. We made efforts to keep the variation of laboratory tempera- ture within 1ƒC between two standardizations before and after a series of salinity measurements, though the variation sometimes exceeded the limit and reached 2ƒC at the maximum. Drifts of the laboratory and bath temperatures were monitored with a HPTM2804A Quartz Thermometer, of which temperature resolution was set to 0.0001ƒC. 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 with the labora- tory and bath temperatures measured simultaneously. Our results of inter-batch comparisons After all the observations along the P9 section were over, the IAPSO SSW batch used during the present cruise, P123 (Dated 10/6/1993), was compared with some older batches of IAPSO SSW (P88, 100, 110, 114, 118, 121) available, so as to obtain the correction value of salinity data based on the batch P123. The results of the inter-batch comparison is shown in Table 2.1.1. As for the batch P88, white precipitate was recognized on the glass walls of three ampoules, all of which salinity values measured were about 0.015 lower than the labeled value. The other ampoule contained suspended particles, but the salinity difference between measured and labeled was not large compared with the other three ampoules. Table 2.1.1 Differences of measured salinity(Smeas) and SSW label derived salinity(Slavel) referred to batch P123. ----------------------------------------------------------------- Batch Preparation K15 Slavel Smeas-Slabel Mean sS Date (sS: x103) (x103) ----------------------------------------------------------------- P88 1 Dec 1979 19.3760* 35.0037 -14.0,-16.7, -1.5** -1.5,-16.7 P100 29 Nov 1984 1.00003 35.0012 1.0 1.0** P110 20 Jul 1988 0.99999 34.9996 1.2 1.2** P114 30 Jul 1990 0.99986 34.9945 1.8 1.8** P118 12 Nov 1991 0.99994 34.9976 0.4,0.4,0.4,0.4 0.4 P121 8 Sep 1992 0.99985 34.9941 -0.2,-0.4,-0.4, -0.3 -0.2, P123 10 Jun 1993 0.99994 34.9976 0.0,0.0,0.2,0.0, 0.0 (Reference standard) 0.0,0.2 ----------------------------------------------------------------- *:Chlorinity **:Single datum Anyway, the number of ampoules for P88, P100, P110, and P114 is not enough to connect our results with the former studies(e.g., Mantyla,1987; Takatsuki et al.,1991). We hope to connect our result of inter-batch comparison with other similar works of WOCE which may contain P118 and P121, so as to determine the correction value of our salinity measurements referred to P123. Indexes of precision and accuracy Table 2.1.2 shows the results of salinity measurements made during the cruise from 261 replicate samples collected in differ- ent glass bottles from a 2.5-liter Niskin bottle. The precision of salinity measurements is estimated at 0.0007 in Leg-1 and 0.0005 in Leg-2. Table 2.1.2 Salinity measurements comparisons ----------------------------------------------------- Case Standard deviation Number of data PSS-78 ----------------------------------------------------- Leg 1 Replicate 0.00071 199 ----------------------------------------------------- Leg 2 Replicate 0.00045 62 ----------------------------------------------------- To provide the further estimate of data quality, scattering of property values at constant potential temperatures was in- spected in the deep ocean, after the example given in WOCE Opera- tions Manual(WHPO, 1991). Figures 2.1.1 and 2.1.2 shows meridi- onal distribution of salinity and oxygen concentration at con- stant potential temperatures of 1.2, 1.4, 1.6, 1.8 and 2.0ƒC. These plots indicate that meridional variation of the properties is almost linear at a constant potential temperature below 1.4ƒC, but not above 1.6ƒC. Considering characteristics of the bottom topography and property distributions in/around the Philippine Sea, we divided the whole P9 section into five regions. And, for each region, we calculated the standard deviations for the dif- ference of property concentrations at the constant potential temperatures from a least squares linear-fit to them (Table 2.1.3). From this method, precision of salinity measurements is estimated at about 0.001. The P9 section crosses with the P3(1989) and the P4(1989) sections. However, The station locations both of P3 and P4 sections around 137E does not agree with the ones of P9. We, therefore, averaged the data around the crossings as a function of potential temperature, and compared them each other to obtain the systematic biases in our data. This comparison was done by using the data in the deep ocean below 2000 meters, where short- term variability in the deep water may be small. The results (Table 2.1.4) suggest that our salinity data are 0.0025 higher than that of P3, and 0.0008 higher than that of P4. We hope to know whether these biases are ascribed to inter-batch variation of the IAPSO SSW used in P3, P4 and P9 cruises. A.6 OTHER INCIDENTS OF NOTE A.7 LIST OF CRUISE PARTICIPANTS (TABLE 1.3) Table 1.3 ------------------------------------------------------------ Name Role and affiliation ------------------------------------------------------------ Ikuo Kaneko Chief Scientist(JMA/MD ADCP) Satoshi Kawae Co-chief Scientist(JMA/MD Salinity) Yasushi Takatsuki (JMA/MD CTDO/Rosette, Salinity) Takashi Yamada (JMA/MD CTDO/Rosette) Satoshi Sugimoto (JMA/KMO CTDO2/rosette) Tatsushi Shiga (JMA/NMO Salinity) Hiroyuki Takano (JMA/HMO Salinity) Hitomi Kamiya (JMA/MD Oxygen, Nutrients) Toshiya Nakano (JMA/MD Oxygen) Tomoaki Nakamura (JMA/MD Oxygen) Takao Shimizu (JMA/MMO Oxygen) Sukeyoshi Takatani (JMA/MD Nutrients) Kazuhiko Hayashi (JMA/MD Nutrients) Kazuhiro Nemoto (JMA/MD CFCs) Shu Saitoh (JMA/MD CFCs) Mamoru Tamaki (TU CFCs) Masao Ishii (JMA/MRI 14C, 3H/3He, Total carbonate) Takashi Miyao (JMA/MRI 14C, 3H/3He) ------------------------------------------------------------- JMA/MD : Marine Department, Japan Meteorological Agency JMA/KMO: Kobe Marine Observatory, JMA 2.2 OXYGEN MEASUREMENTS (H. Kamiya and I. Kaneko) Sampling Procedure The dissolved oxygen samples were collected in 120 ml glass bottles, which were designed and manufactured being referred to WHPO 91-2 report(1991) on an intercomparison of oxygen measure- ment methods and a paper by Green and Carritt(1966). Our bottle has a collar on its mouth as a flan flask has, and its round glass stopper contains a long nipple, which extends into the flask and displaces enough volume of sample water so that titra- tion reagent do not overflow the flask. Both the bottles and stoppers had been washed and dried before they were used for seawater sampling on the deck. After a stopper was inserted into a bottle to seal seawater, temperature of a sample is measured with a thermistor probe being inserted into seawater remained in a collar. Equipment and Technique The reagents were prepared according to the recipes by Carpenter(1965) and Culberson(WHPO91-1 manual,1991) though nor- mality of sodium thiosulfate for titration was selected about 0.03 in order that a titration for the highest oxygen concentra- tion would finished within a volume of the burette. The titrator used in the P9 cruise, Model ART-3TM, was a photometric type (372 nm), which has been manufactured by Hirama Riken Inc. The volume of burette is 5 ml, and the resolution of titration is 0.0025 ml. Reagent blanks (expressed as Vblk,dw in WHPO91-1 manual) were measured during the cruise, determined as 0.0050 ml both for Leg-1 and Leg-2, and subtracted from all of thiosulfate titers of the samples. The reagent blank (Vblk,dw) of 0.0050 ml obtained with our oxygen flask, of which nominal volume is 118 ml, corre- sponds to a oxygen concentration of 0.0068 ml/l. Seawater blanks (Vblk,sw) were measured only at Sta.92 (Ry8724) in Leg-2 (Table 2.2.1). Considering the resolution of our titrator, 0.0025ml, this measurement did not detect vertical variability of Vblk,sw at Sta.92 from surface to deep ocean. Vblk,sw of 0.0150 ml corresponds to a oxygen concentration of 0.0204 ml/l, which is three times larger than Vblk,dw. According to the suggestion in WHPO91-1 manual, the value of Vblk,sw was recorded, but not used for the calculations of oxygen concentrations. Table 2.2.1 Measurements of seawater blanks Date 14/08/94 Stn.92(Ry8724) Lat. 00 16N Lon. 142 00E Water depth 3420m ------------------------------------------------------- Depth Vblk,sw Depth Vblk,sw Depth Vblk,sw (m) (ml) (m) (ml) (m) (ml) ------------------------------------------------------- 0 0.0150 300 0.0175 1750 0.0725* 10 0.0125 400 0.0175 2000 0.0075 25 0.0100 500 0.0125 2250 0.0150 50 0.0100 600 0.0125 2500 0.0150 75 0.0150 700 0.0225* 2750 0.0150 100 0.0125 800 0.0125 3000 0.0175 125 0.0100 900 0.0175 3250 0.0150 150 0.0150 1250 0.0175 3385 0.0150 200 0.0150 1500 0.0175 ------------------------------------------------------ *: bad measurement Indexes of precision and accuracy The results of comparisons between replicate/duplicate sam- ples are shown in Table 2.2.2. Owing to frequent misfires and double-fires of the rosette system, we often failed to obtain duplicate samples at purposed layers. We, therefore, had to make the best use of the samples from double-fired bottles as dupli- cate samples. Duplicate samples were classified two cases. 'Duplicate-A' is the case that samples were drawn from two bot- tles which had closed normally at adjacent depths. 'Duplicate-B' is the case that samples were drawn from two bottles which were judged that they had closed at the same depths owing to double- fires. Table 2.2.2 Oxygen analyses comparisons Case Standard deviation Number of data umol/kg (% of F.S.) -------------------------------------------------- Leg 1 Replicate 1.591 (0.68) 244 Duplicate-A 1.604 (0.69) 18 Duplicate-B 1.711 (0.73) 88 -------------------------------------------------- Leg 2 Replicate 0.595 (0.25) 252 Duplicate-A 1.133 (0.48) 70 Duplicate-B 0.576 (0.25) 85 -------------------------------------------------- F.S.: 234 umol/kg The precision during Leg-1 is not satisfactory. The sensor circuit, bad focus of the lamp and large vibration of the table are speculated as the cause of bad titration. The precision during the Leg-2 was improved since we replaced the titrator at Palau by new parts of optical unit. In Leg-2, mistrips frequent- ly occurred at the time of duplicate sampling in the deep ocean and made the depths of available 'Duplicate-A' data weighted to be shallow. We, therefore, interpreted that the low-precision in 'Duplicate-A' is ascribed to large gradient or fluctuation of vertical oxygen distribution in shallow layers. As is explained in the section of salinity measurements, scattering of oxygen concentrations at constant potential temper- atures (Figure 2.1.2) is used for another estimate of precision. Table 2.1.3 includes the standard deviations for the differences between the interpolated oxygen data and a least squares linear- fit to their values at each of the potential temperatures. The standard deviations at the deepest layer range from 0.4 to 0.9 umol/kg. Table 2.1.3 Standard deviation of water sample data Whole section(from 34 15 N to 02 52 S) Theta Press. Salinity Oxygen Silicate Nitrate Phosphate ƒC Points dbar PSS-78 umol/kg umol/kg umol/kg umol/kg ------------------------------------------------------------------ 1.2 50 101 0.0009 0.8518 0.8346 0.1771 0.0243 1.4 84 120 0.0012 0.8101 0.9432 0.2045 0.0259 1.6 92 63 0.0023 1.2691 1.1396 0.2152 0.0282 1.8 95 52 0.0042 1.4863 1.0212 0.2280 0.0254 2.0 95 53 0.0068 2.8115 1.0746 0.2520 0.0248 ------------------------------------------------------------------ Shikoku Basin(from 34 15 N to 26 00 N) Theta Press. Salinity Oxygen Silicate Nitrate Phosphate ƒC Points dbar PSS-78 umol/kg umol/kg umol/kg umol/kg ------------------------------------------------------------------ 1.2 7 135 0.0015 0.8268 0.5752 0.0810 0.0059 1.4 19 84 0.0011 0.5234 0.6193 0.1488 0.0094 1.6 20 73 0.0016 1.0444 0.6171 0.1430 0.0135 1.8 21 68 0.0015 1.0064 0.6370 0.2386 0.0186 2.0 21 64 0.0014 1.6617 0.6697 0.1610 0.0146 ------------------------------------------------------------------ Transient Area(from 26 00 N to 24 00 N) Theta Press. Salinity Oxygen Silicate Nitrate Phosphate ƒC Points dbar PSS-78 umol/kg umol/kg umol/kg umol/kg ------------------------------------------------------------------ 1.2 5 84 0.0014 0.3961 0.2042 0.0911 0.0042 1.4 5 37 0.0017 0.5051 0.4202 0.0874 0.0096 1.6 5 32 0.0005 1.6340 0.2598 0.0830 0.0086 1.8 5 34 0.0019 1.1954 0.6554 0.0591 0.0133 2.0 5 30 0.0036 2.1174 0.6255 0.0813 0.0123 ------------------------------------------------------------------ West Mariana Basin(from 24 00 N to 08 20 N) Theta Press. Salinity Oxygen Silicate Nitrate Phosphate ƒC Points dbar PSS-78 umol/kg umol/kg umol/kg umol/kg ------------------------------------------------------------------ 1.2 30 94 0.0006 0.6649 0.6934 0.1368 0.0185 1.4 31 81 0.0010 1.0329 0.9236 0.1668 0.0155 1.6 31 57 0.0011 1.5957 1.0965 0.1441 0.0196 1.8 33 45 0.0014 1.3663 1.0321 0.1503 0.0194 2.0 33 51 0.0025 1.5907 0.7925 0.1521 0.0162 ------------------------------------------------------------------ West Caroline Basin(from 08 20 N to 02 00 N) Theta Press. Salinity Oxygen Silicate Nitrate Phosphate ƒC Points dbar PSS-78 umol/kg umol/kg umol/kg umol/kg ------------------------------------------------------------------ 1.2 10 47 0.0008 0.5618 0.6337 0.1733 0.0236 1.4 15 35 0.0008 0.6066 0.6293 0.2133 0.0268 1.6 19 29 0.0008 0.5618 0.5614 0.2023 0.0282 1.8 20 27 0.0007 1.0387 0.9673 0.2439 0.0214 2.0 20 32 0.0008 1.4090 0.8063 0.2627 0.0198 ------------------------------------------------------------------ Eauripik Ridge(from 02 00 N to 02 52 S) Theta Press. Salinity Oxygen Silicate Nitrate Phosphate ƒC Points dbar PSS-78 umol/kg umol/kg umol/kg umol/kg ------------------------------------------------------------------ 1.2 0 - - - - - - 1.4 16 40 0.0007 0.4097 0.4273 0.1157 0.0197 1.6 20 34 0.0008 0.4800 0.4403 0.1459 0.0194 1.8 20 32 0.0010 0.4849 0.8089 0.1812 0.0234 2.0 20 33 0.0008 0.4649 0.4725 0.1392 0.0217 ------------------------------------------------------------------ The P9 section crosses with P3(1985) and P4(1989) sections. We compared our results with the data of these sections. Its procedure is explained in the section on salinity measure- ments (Sec.2.1), and the results are included in Table 2.1.4. Our deep oxygen concentrations seems to well agree with the ones of P3 section, but to be 2 or 3 % higher than those of P4 section. Table 2.1.4 Comparison of water sample data between P9 and P3/P4 Salinity Oxygen Silicate Nitrate Phosphate ------------------------------------------------------------------ Ratio(P9/P3) 1.0032 0.9843 0.9826 1.0245 Diff.(P9-P3) 0.0025 ------------------------------------------------------------------ P3 station : P3-320( 24 15.40N, 137 0.00E ) P9 stations: P9- 32( 24 30.14N, 137 0.09E ) P9- 33( 23 59.81N, 136 59.87E ) Salinity Oxygen Silicate Nitrate Phosphate ------------------------------------------------------------------ Ratio(P9/P4) 1.0267 0.9860 1.0023 0.9958 Diff.(P9-P4) 0.0008 ------------------------------------------------------------------ P4 stations: P3- 26( 8 59.70N, 136 40.10E ) P3- 27( 9 2.00N, 136 38.50E ) P3- 28( 9 0.10N, 137 14.90E ) P9 stations: P9- 62( 9 29.99N, 136 59.85E ) P9- 63( 8 59.49N, 136 59.93E ) P9- 64( 8 40.29N, 137 0.95E ) 2.3 NUTRIENT MEASUREMENTS (H. Kamiya and I. Kaneko) Sampling Procedure Nutrient samples were drawn into 10 ml polymethylpentene test tubes with screw caps. The tubes (bottles) were always handled with disposable polyethylene gloves. Each sample was collected in two bottles, one of which was immediately refriger- ated as a spare in case of questionable measurement or malfunc- tion of our analyzer. However in practice, we need not have used the spare samples throughout the P9 cruise. The Niskin bottles were filled with distilled water when we stopped observations for several days owing to bad weathers or a recess at Palau, and were washed with 0.1 molar NaOH before casts after the breaks. Equipment and Technique The nutrient analyses were performed using a Technicon AutoAnalyzerTM-II (AA-II). We prepared the reagents and flow lines referred to the manual by L.I. Gordon et al.(13 July 1992; Draft), entitled ' An Suggested Protocol for Continuous Flow Automated Analysis of Seawater Nutrients in the WOCE Hydrographic Program and the Joint Global Ocean Fluxes Study'. However, as for phosphate and silicate analyses, we introduced the ascorbic acid method for convenience of reagent preservability. The manifolds and reagent prescriptions are shown in Figures 2.3.1- 2.3.4 for silicate, nitrate, nitrite and phosphate. Our system heated silicate and phosphate samples up to 37ƒC so as to keep coloration rate stable. The analyses routinely were started within one hour after water 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. Nominal concen- trations of A, B and working standards are listed in Table 2.3.1. Output from the AA-II was taken at each second by a microcomput- er. For each sample, six output values were selected from ten highest values around a peak, by rejecting the two highest and lowest values, and they are averaged to yield a peak-hold value. Table 2.3.1 Nominal concentrations of standards A-standard B-standard Working-standard (umol/l) (umol/l) (umol/l) -------------------------------------------------------------------- Silicate 99840* 1996.8 159.74 Nitrate 25000 500 40 + 1 Nitrite 12500 250 1 Phosphate 1875 37.5 3 -------------------------------------------------------------------- * Three ampoules of Silica, 1000 ppm StandardTM by J.T.Baker Inc. were together diluted with 500ml water and preserved as A-stand- ard. Indexes of precision and accuracy The results of comparison between duplicate/replicate sam- ples are shown in Table 2.3.2. In the same manner as oxygen, duplicate samples were classified into two cases. 'Duplicate-A' is the case that samples were drawn from two bottles which had closed normally at adjacent depths. 'Duplicate-B' is the case that samples were drawn from two bottles judged that they had closed at the same depths owing to double-fires. The result of low-precision in 'Duplicate-A' during Leg-2 is similar to the one in oxygen. This supports our interpretation given in the section of oxygen measurements; i.e. owing to the mistrips, the data available for 'Duplicate-A' had been weighted to shallow layers, where gradients or fluctuations of vertical nutrient distribu- tions are relatively large compared to the ones in the deep ocean. Table 2.3.2 Nutrient analyses comparisons (Unit: upper: umol/kg lower: % of full scale). Case Silicate Nitrate Nitrite Phosphate Num. of data ------------------------------------------------------------------- Leg 1 Replicate 0.227 0.102 0.004 0.008 260 (0.16) (0.24) (0.42) (0.27) Duplicate-A 0.244 0.075 0.003 0.005 19 (0.17) (0.18) (0.28) (0.17) Duplicate-B 0.292 0.100 0.003 0.009 94 (0.20) (0.24) (0.29) (0.30) ------------------------------------------------------------------- Leg 2 Replicate 0.370 0.137 0.005 0.011 295 (0.25) (0.33) (0.45) (0.38) Duplicate-A 0.559 0.165 0.005 0.017 66 (0.38) (0.38) (0.48) (0.56) Duplicate-B 0.413 0.098 0.005 0.013 89 (0.28) (0.23) (0.47) (0.45) ------------------------------------------------------------------- Full Scale 146 42 1 3 (umol/kg) ------------------------------------------------------------------- As is explained in the section of salinity measurements, scattering of nutrient concentrations at the constant potential temperatures is used for another estimate of precision. Table 2.1.3 includes the standard deviations for the difference between nutrient concentrations interpolated at the potential tempera- tures and a least squares linear-fit to their values. Table 2.3.3 Nutrient laboratory temperatures for each station. -------------------------------------------------------------------- Leg Station Date Time Temp. Leg Station Date Time Temp. P9 Ry ddmmyy (UT) (C) P9 Ry ddmmyy(UT) (C) -------------------------------------------------------------------- 1 1 8633 080794 1740 28.2 2 61 8686 030894 0633 27.5 1 2 8634 080794 2034 28.3 2 60 8687 030894 1200 28.0 1 3 8635 080794 2246 27.8 2 59 8688 030894 1823 27.0 1 5 8637 090794 0435 28.3 2 58 8689 030894 1935 26.7 1 7 8639 090794 1230 28.5 2 57 8690 050894 0541 26.9 1 9 8641 090794 2126 28.0 2 56 8691 050894 1330 27.5 1 10 8642 100794 0515 29.5 2 55 8692 050894 1825 27.4 1 11 8643 100794 1230 29.8 2 54 8693 060894 0250 29.3 1 13 8645 100794 2117 27.3 2 62 8694 070894 0200 28.0 1 15 8647 110794 0505 28.5 2 63 8695 070894 0740 29.0 1 16 8648 110794 1350 28.5 2 64 8696 070894 1400 28.5 1 17 8649 110794 1745 27.9 2 65 8697 070894 1656 27.5 1 18 8650 120794 0120 27.8 2 66 8698 070894 2100 28.6 1 19 8651 120794 0805 27.8 2 67 8699 080894 0256 28.9 1 20 8652 120794 1325 26.8 2 68 8700 080894 0505 29.3 1 21 8653 120794 1937 27.7 2 69 8701 080894 1300 28.5 1 22 8654 130794 0400 29.0 2 70 8702 080894 1941 28.5 1 23 8655 130794 1005 29.0 2 71 8703 090894 0030 28.8 1 24 8656 130794 1640 28.5 2 72 8704 090894 0930 28.8 1 25 8657 130794 2156 27.8 2 73 8705 090894 1502 28.1 1 26 8658 140794 0821 29.1 2 74 8706 100894 0750 28.3 1 27 8659 140794 1700 29.2 2 75 8707 100894 0509 28.2 1 28 8660 150794 0040 28.5 2 76 8708 100894 0750 29.1 1 29 8661 150794 0710 28.5 2 77 8709 100894 1638 28.1 1 30 8662 150794 1800 28.2 2 78 8710 100894 2130 28.5 1 31 8663 150794 2248 28.4 2 79 8711 110894 0910 29.0 1 32 8664 160794 0745 28.9 2 80 8712 110894 1300 28.5 1 33 8665 160794 1320 29.8 2 81 8713 110894 1630 28.5 1 34 8666 160794 2146 27.7 2 82 8714 120894 0130 28.9 1 35 8667 170794 0600 29.0 2 83 8715 120894 0502 28.7 1 36 8668 170794 1430 28.8 2 84 8716 120894 0850 28.9 1 40 8669 210794 0412 28.2 2 85 8717 120894 1230 28.3 1 39 8670 210794 1700 28.8 2 86 8718 120894 1920 28.3 1 38 8671 220794 0100 27.8 2 87 8719 130894 0000 28.8 1 37 8672 220794 0940 26.6 2 88 8720 130894 0400 28.5 1 41 8673 230794 0410 29.9 2 89 8721 130894 0805 28.7 1 42 8674 230794 1300 29.4 2 90 8722 130894 1500 28.0 1 43 8675 230794 1846 28.9 2 91 8723 130894 1811 27.6 1 44 8676 240794 0130 28.5 2 92 8724 140894 0200 28.9 1 45 8677 240794 0803 27.8 2 93 8725 140894 0416 28.4 1 46 8678 240794 1705 28.8 2 94 8726 150894 0230 28.0 1 47 8679 240794 2300 29.2 2 95 8727 150894 0830 29.0 1 48 8680 250794 0710 29.3 2 96 8728 150894 1000 28.8 1 49 8681 250794 1400 28.8 2 97 8729 150894 2000 28.8 1 50 8682 250794 2223 27.6 2 98 8730 150894 2230 28.9 1 51 8683 260794 0600 28.0 2 99 8731 160894 0400 28.0 1 52 8684 260794 1230 29.3 2 100 8732 160894 0800 29.0 1 53 8685 260794 2050 27.3 2 101 8733 160894 1430 29.0 2 102 8734 160894 2000 28.9 2 103 8735 170894 0230 29.2 2 104 8736 170894 0800 29.5 2 105 8737 180894 0045 28.3 2 92 8738 180894 1827 28.0 -------------------------------------------------------------------- The P9 section crosses with P3(1985) and P4(1989) sections. We compared our results with the data of these sections. Its procedure is explained in the section of salinity measure- ments(Sec.2.1), and the results are included in Table 2.1.4. Our silicate and nitrate concentrations are ca. 2 % lower than the P3 data, while our phosphate concentrations are 2 % higher. As for the comparison with the P4 data, our nitrate and phosphate con- centrations well agree with them, but the silicate concentrations are 1 or 2 % lower, which level is close to the one obtained in the comparison with the P3 silicate data. Laboratory temperatures at the measurements are indispens- able for the concentration conversion from volumetric units to mass units. They are given in Table 2.3.3. 2.4 CFC-11 AND CFC-12 MEASUREMENTS (M. Tamaki and I. Kaneko) 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 Bullis- ter and Weiss (1988). Our extraction and analysis system was assembled by GL Science Corp. The ECD Gas chromatograph is Hitachi Corp., Model 263-30. The CFC measurements were carried out as a collaboration between the Japan Meteorological Agency and Tokai University. A total of 351 water samples were analyzed for CFCs. Replicate samples were taken at 200 m depth of nine stations. Sampling Procedure and Data Processing We used a 2.5Lx24 rosette system for water sampling. The rosette bottles were designed by Dr. J. Bullister so that sampled water is hard to be contaminated with CFCs contained in materials of the bottles, and were made at the factory of NOAA/PMEL. On board sampling for the CFCs were usually carried out in the third cast. CFC samples were always drawn firstly by using 50 ml glass syringes. The samples were injected in the system and processed within 12 hours after sampling. Approximately 20 ml of samples was flushed, and 30 ml was transferred to the stripping chamber. Calibration curves used for determining CFC concentrations are generated by multiple injections of known volumes of standard gas. However, at Stas. 9 (Ry8641) and 15 (Ry8647) in the begin- ning of the first leg, the volume of standard gas sample loop included in our system was so large that the amounts of F-11 and F-12 injected in one aliquot of standard exceed those contained in 30 ml surface seawater samples. As linear regressions to only two data, system blank and one aliquot of standard, had to used for determining CFC concentrations at these stations, quality of the concentration data is not high, especially for the sample at deep layers. Before the third CFC station, Sta.18 (Ry8650), we replaced the gas sample loop with a smaller one. For the sta- tions south of Sta.18 at 31 00N, the curves were adequately obtained by least-square fittings of quadratic polynomials to five calibration data, from system blank to four aliquots of standard. The data at these two stations are, therefore, as- signed a value of 3 for the quality bytes in our .SEA file, even in the case of good sampling and analysis. Sample blanks At the factory of NOAA/PMEL, the bottles were tested indi- vidually for CFC contamination. They generally had F-11 and F-12 blanks of about 0.005 pmol/liter/hour for water stored inside (J. Bullister, 1994; personal communication). The bottles were wrapped with blank paper, stored in a box of plain wood, and sent by air from Seattle to Tokyo. Owing to many circumstances, we had no chance to measure the sample blank of F-11 and F-12 for each bottle in the beginning of the cruise. The sample blank for each bottle were finally meas- ured at Sta. 79 (Ry8711; 3 43N, 140 17E) during the second leg, by sampling deep water at 1500m depth. No bottle seriously contaminated was found for F-11 and the mean and standard devia- tion of sample blanks were 0.015+0.003 pmol/kg. However, as for F-12, very high concentrations, of which mean and standard devia- tion were 0.167+0.095 pmol/kg, were obtained. The values of F-12 measurements sampled in the deepest layer had varied largely from station to station and often exceeded the level of 0.1 pmol/kg. A o-ring used in the connection of the glass stripping chamber was suspected of being a contamination source, but we could not replace it with other materials during the cruise. As the other estimates of the blanks, the mean concentra- tions of CFCs measured south of 10N in the layers deeper than 1250m were calculated. The mean and standard deviation of the F- 11 measurements was 0.014+0.006 pmol/kg, which is close to the result at Sta. 79. Those of F-12 measurements, 0.112+0.042 pmol/kg, were considerably large. After all, we adopted these mean values as the sample blanks throughout the cruise. These blanks were subtracted from the measurement values of F-11 and F- 12. Judging from the unacceptable large value and fluctuation of F-12 measurements in the deep ocean, all of the F-12 data are assigned a value of 3 or 4 for the quality byte in our 49RY9407.SEA file. Precision The reproducibility was estimated from replicate analyses of 200m-depth water at nine stations. It is about 1.3% for F-11 and 5.8% for F-12. Quality of the F-12 data is far from that of the WHP requirements. 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 with the standard of University of Tokyo(UT) on Nov. 1 of 1994, about two month after the P9 cruise. F-11 and F-12 concentrations of our standard gas were 288.5+1.8 pptv and 485.3+3.0 pptv, respectively. We used these values to calculate the F-11 and F-12 concentrations of seawater sample obtained in the P9 cruise. Both UT and SIO calibration scales were compared with the scale employed in the ALE/GAGE program. According to the result(Table 1.2.1 in the report ed. by J.A.Kaye et al., 1994), our data can be converted to the level of data referred to SIO scale by multiplying our data by 1.02 for F-11, 1.01 for F-12. 2.5 CTD/O MEASUREMENTS (Y. TAKATSUKI) Calibration and Standards The CTDs used during Ry9407 cruise are Triton ICTDsTM, which are manufactured by Falmouth Scientific Instruments Inc.(FSI). CTD #1316 was used at the hydrographic stations from Sta.1 (Ry8633) to Sta.69 (Ry8701), till its temperature circuit broke down at the second cast of Sta.69. We replaced CTD #1316 with CTD #1318 and used it until the last cast of the cruise at Sta.92 (re-occupation; Ry8738). All of temperature, conductivity and pressure sensors are manufactured by FSI while the oxygen sensor by Beckman Inc. As CTD #1318 was a new device delivered to JMA several days before the departure, we had no chance for pre-cruise calibration of its sensors. We had to regard CTD #1318 as being adequately adjusted by FSI. Fortunately, a Triton ICTD is the type that the sensor outputs are corrected by calibration tables written in a PROM of internal circuit. On the basis of the results of post- cruise calibrations and on-board check of the sensors by using the RTMs and RPMs, we determined reasonable processing methods of the data obtained by CTD #1318. FSI claims a resolution of 0.0001ƒC and an accuracy of +0.003ƒC for the platinum temperature sensors. Post-cruise calibrations of CTD #1318 at FSI showed a trivial difference of CTD temperature from the standard, 0.00038ƒC at 0.5ƒC and 0.00111ƒC at 29ƒC (Figure 2.5.4). However, as for CTD #1316, the post-cruise temperature calibrations after the temporary repairs showed an extraordinary drift, of which values were no longer available for the data processing. The situation and correction method of this temperature drift are described in the section for CTD calibration constants. The CTD pressure sensors, of which type is the one consists of titanium diaphragm and strain-gage, have a resolution of 0.1 dbar and an accuracy of +0.03% of full scale, according to the manual by FSI. Pre- and post- cruise calibrations for CTD #1316 and a post-cruise calibration for CTD #1318 were carried out in JMA by using a BudenbergTM Model 380D dead-weight tester with 'class-A' certificated weights. The pair of calibrations detect- ed a minute drift about 0.2 dbar in average for CTD #1316 (Fig- ures 2.5.1a and 2.5.1b). Condition of the pressure sensors during the cruise can be monitored to some extent through com- parisons of CTD pressures with RPM pressures at the time the water bottle is tripped. Any drift exceeding a nominal precision of RPM was not detected for the two CTDs. Pre- and post- cruise calibrations of the conductivity sen- sors were not carried out because we could not find the facility in Japan. The calibration constants used were calculated from a fit to the salinities measured from the water samples collected at each station. Statistical analysis of the difference between the CTD and water-sample salinities showed a standard deviation less than 0.0014 in the deep water (>2000 m; Table 2.5.1). Table 2.5.1 Standard deviation of salinity difference between CTD and water sampling. Station: Sta.1(Ry8633) - Sta.69(Ry8701),Cast-1 All data Not flagged data Layer S.Dev. Num. of data S.Dev. Num. of data ------------------------------------------------------------- all 0.0176 2272 0.0175 2257 >1000m 0.0038 1024 0.0017 1010 >2000m 0.0038 700 0.0014 691 >3000m 0.0047 450 0.0014 442 >4000m 0.0065 210 0.0013 206 ------------------------------------------------------------- Station: Sta.69(Ry8701),Cast-2 - Sta.92(Ry8738) All data Not flagged data Layer S.Dev. Num. of data S.Dev. Num. of data ------------------------------------------------------------- all 0.0224 1243 0.0214 1238 >1000m 0.0105 526 0.0018 522 >2000m 0.0130 330 0.0013 326 >3000m 0.0174 152 0.0011 150 >4000m 0.0115 36 0.0009 35 ------------------------------------------------------------- The oxygen sensor mounted on CTD #1316 was also calibrated with shipboard oxygen measurements from the water samples col- lected at each station. Oxygen measurements by CTD have been discontinued at Sta.69, where CTD #1316 was replaced by the other CTD, #1318. The oxygen sensor used on CTD #1316 did not work on CTD #1318 because its inside circuit did not adapt to the new CTD. CTD Data Collection and Processing The RS-232C signal from a FSI 1050 deck terminal was taken by a Compaq DeskproTM 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 Compaq Deskpro with the software programmed by the members of Nagasaki Marine Observatory, according to the method by Millard (1993). A time-constant difference between the temperature and conductivity sensors, which is necessary for salinity despiking, was determined so as to minimize fluctuations of salinity profile (Kawabe and Kawasaki, 1993). CTD Calibration Constants Pressure The results of pre-/post- cruise calibrations for CTD #1316 and a post-cruise calibration for CTD #1318 are shown in Figures 2.5.1 and 2.5.2, respectively. The comparison between the pre- cruise and post-cruise calibrations for CTD #1316 indicated that its pressure drift was about 0.2 dbar, of which effect on salini- ty error is negligible. Hence, so as to obtain the calibration constants for CTD #1316, the pre-cruise calibration data was used for a polynomial fit. For the data obtained by CTD #1318, a polynomial fit to the post-cruise calibration was applied because of the lack of pre-cruise calibration data. Any serious pressure drift of CTD #1318 had not been detected with the bottle-mounted RPMs though their precision is lower than that of CTDs. The calibration constants are tabulated in Table 2.5.2. Al- though the pressure differences between the increasing and de- creasing curves owing to sensor hysteresis are not more than 1 dbar for both the CTDs, a technique known as exponential decay feathering (Millard, 1991) is introduced to adjust between the two curves. Table 2.5.2 Pressure calibration constants CTD #1316, Pre-cruise, 0-6000 dbar range Increasing Decreasing (Linear fit) (Cubic fit) -------------------------------------------------------------- Bias 0.101671 0.030432 Slope 0.999808 0.999893 Coef. 1 0 -1.06871E-7 Coef. 2 0 1.65002E-11 -------------------------------------------------------------- CTD #1318, Post-cruise, 0-6000 dbar range Increasing Decreasing (Cubic fit) (Cubic fit) -------------------------------------------------------------- Bias 0.118827 -0.360069 Slope 0.999365 0.999221 Coef. 1 9.79631E-8 9.982900E-8 Coef. 2 -1.60597E-11 -1.014070E-11 -------------------------------------------------------------- Temperature The results of the pre-cruise calibration for CTD #1316 and the post-cruise calibration for CTD #1318 are shown in Figures 2.5.3 and 2.5.4, respectively. The calibration constants are listed in Table 2.5.3. Table 2.5.3 Temperature calibration constants CTD #1316, Pre-cruise, 0-30ƒC range Quadratic fit ---------------------------------------------- Bias -0.0108521 Slope 0.999385 Coef. 1 1.33467E-5 ---------------------------------------------- CTD #1318, Post-cruise, 0-30ƒC range Quadratic fit ---------------------------------------------- Bias -0.000325853 Slope 1.00014 Coef. 1 -5.66299E-6 ---------------------------------------------- A temperature drift of CTD #1316 before its breakdown had been detected with seven RTMs mounted on the Niskin bottles. As an example, Figure 2.5.5 shows a time-series of temperature dif- ference between CTD #1316 and RTM #T759. The drift began at Ry8686 (Sta.61) and reached -0.02ƒC at Ry8700 (Sta.68), one sta- tion before the breakdown. The mean of drift during this period is estimated at -0.008ƒC from the comparison between the CTD and seven RTMs. We, therefore, processed the CTD temperature as follows: (1) The constants obtained from the pre-cruise calibration for CTD #1316 is applied to correct the data of Leg-1, because any so large drift as to exceed 'WHP standards for CTD sensors' was not recognized through the monitoring with RTMs from Ry8633 to Ry8685 (Sta.1-53). (2) The data at the stations from Ry8686 to the first cast of Ry8701 (Sta.61-54 & Sta.62-69) were processed in the same way as the data of Leg-1, and then, they were added by a constant value of +0.008ƒC. (3) Despite of the data correction above, a flag '3' (Question- able measurement) was assigned to the data at the stations from RY8696 to the first cast of Ry8701(Sta.64-69). This is because the drift at these station was so large that we could not cor- rected it adequately. (4) The constants obtaine from the post-cruise calibration for CTD #1318 was applied to correct the data at the stations from the second cast of Ry8701 to Ry8738(Sta.69-105 & the re-occupa- tion of Sta.92). The level of temperature differences between RTMs and CTDs is classified in three categories, CTD #1316 in Leg-1, CTD #1316 in Leg-2 and CTD #1318, and are compared in Table 2.5.4. The table indicates that the level of CTD temperature hardly changed before and after the replacement from CTD #1316 to CTD #1318 (see Figure 2.5.5). Table 2.5.4 Difference between CTD and RTM temperatures obtained below 2000m depth Leg-1 Sta. 1- 53(Ry8633-8685) CTD #1316 RTM # T662 T710 T754 T755 T759 T760 T777 ---------------------------------------------------------------- Mean(1) -0.0029 -0.0021 -0.0038 -0.0032 -0.0045 -0.0036 0.0044 S.Dev. 0.0015 0.0022 0.0017 0.0023 0.0039 0.0015 0.0027 N.D. 38 31 38 23 39 41 31 ---------------------------------------------------------------- Leg-2a Sta.61- 68(Ry8686-8700) CTD #1316 RTM # T662 T710 T754 T755 T759 T760 T777 ---------------------------------------------------------------- Mean(2a) 0.0061 0.0035 0.0037 0.0033 0.0035 0.0039 0.0123 S.Dev. 0.0038 0.0016 0.0020 0.0005 0.0039 0.0014 0.0027 N.D. 16 13 15 7 16 10 13 ---------------------------------------------------------------- Diff. (2a)-(1) 0.0090 0.0056 0.0075 0.0065 0.0079 0.0075 0.0079 ---------------------------------------------------------------- Leg-2b Sta.69- 105,92(Ry8701-8738) CTD #1318 RTM # T662 T710 T754 T755 T759 T760 T777 ---------------------------------------------------------------- Mean(2b) -0.0012 -0.0070 -0.0088 -0.0029 -0.0044 -0.0029 0.0051 S.Dev. 0.0020 0.0020 0.0029 0.0013 0.0026 0.0034 0.0019 N.D. 35 31 33 25 34 20 30 ---------------------------------------------------------------- Diff. (2b)-(1) 0.0017 -0.0049 -0.0050 0.0003 0.0001 0.0007 0.0007 ---------------------------------------------------------------- Conductivity As mentioned above, we could not carry out pre- and post- cruise calibrations of the conductivity sensors. 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 scaling factors finally adopted for the data processing are listed in Table 2.5.5. Table 2.5.5 Conductivity scaling factors Station CTD No. Bias Slope ---------------------------------------------------------------- 1 - 4 (Ry8633-8636) #1316 0.0150 0.999852 5 - 11 (Ry8637-8643) #1316 0.0150 0.999690 12 - 21 (Ry8644-8653) #1316 0.0150 0.999533 22 - 36 (Ry8654-8668) #1316 0.0150 0.999520 40 (Ry8669) #1316 0.0150 0.999422 39, 38 (Ry8670,8671) #1316 0.0150 0.999497 37, 41 (Ry8672,8673) #1316 0.0150 0.999596 42 - 53 (Ry8674-8685) #1316 0.0150 0.999546 61 - 59 (Ry8686-8688) #1316 0.0500 0.998507 58 - 56 (Ry8689-8691) #1316 0.0500 0.998349 55,54,62 (Ry8692-8694) #1316 0.0500 0.998440 63 - 65 (Ry8695-8697) #1316 0.0500 0.998364 66 - 68 (Ry8698-8700) #1316 0.0500 0.998343 69 Cast1 (Ry8701 Cast1) #1316 0.0500 0.998508 69 Cast2 (Ry8701 Cast2 -70 -8702) #1318 -0.0100 1.000700 71 - 93 (Ry8703-8725) #1318 -0.0100 1.000659 94 -105,92(Ry8726-8738) #1318 -0.0100 1.000641 ---------------------------------------------------------------- Oxygen The scaling factors were determined according to the method developed by Millard (WHPO91-1 manual, 1991). The values of parameters used for each station groups are listed in Table 2.5.6. Table 2.5.6 Oxygen scaling factors (for CTD #1316) Station Bias Slope Pcor Tcor Wt Lag ---------------------------------------------------------------- 1- 6 0.142 1.828 2.507E-4 -2.129E-2 0.911 5.712 (Ry8633-8638) 7- 21 0.154 1.756 1.938E-4 -2.080E-2 0.841 2.597 (Ry8639-8653) 22- 36 0.164 1.968 1.578E-4 -2.462E-2 0.893 1.051 (Ry8654-8668) 40- 37 0.164 1.968 1.578E-4 -2.462E-2 0.893 1.051 (Ry8669-8672) 41- 53 0.165 2.450 1.471E-4 -2.974E-2 0.943 0.734 (Ry8673-8685) 61- 59 0.158 2.294 1.508E-4 -2.992E-2 0.932 0.724 (Ry8686-8688) 58- 54 0.172 2.229 1.475E-4 -3.003E-2 0.676 0.715 (Ry8689-8693) 62- 69 0.181 2.247 1.461E-4 -2.764E-2 0.931 1.057 (Ry8694-8701) ---------------------------------------------------------------- 2.6 HELIUM AND TRITIUM SAMPLING (T. Miyao) Samples for Helium Isotopes Measurement Soft annealed, refrigeration-grade 5/8" copper tubing coils were used to collect crimped tube helium samples. The copper tubing was cut into 2' lengths and immediately placed plastic caps on both ends. Each tube was marked at the center and 2" from each end. Consequently, each 10" section between the center mark and the end mark was partially flattened. The sampling tubes were prepared by each arrival at sampling station. Helium sampling always followed that for CFC's which started just after the rosette is on deck. To draw a sample, a pair of Tygon tube with pinch clamp was attached to the both ends of a sampling tube and one end was connected to the spigot on the Niskin bottle. Then the valve was opened to establish sample flow. The sampling tube was pounded during the flushing period to eliminate air bubbles. After purging air bubbles, the downstream clamp was closed first, and then the upstream one. Immediately, the sample tube was crimped first at the end mark on one side, then at the center mark, finally at another end mark. Thus, two replicate crimped samples were taken. Each sample was re-rounded so that the inner pressure can be reduced. The crimped samples were carefully rinsed with fresh water. After towel drying, the samples were stored in foam-lined cardboard boxes. A total of 521 pairs of samples were taken from seasurface to deep layer at 25 stations. It was found, however, that 9 sample tubes might contain some air bubbles. Thus, 512 pairs of complete samples might be successfully obtained during Ryofu-maru WOCE P9 cruise. Samples were sent to the laboratory of Dr. John Lupton, NOAA MRRD. They will then be shipped in flame-sealed glass ampoules to L-DEO for mass spectrometric measurement. The He-3/He-4 ratio with a precision of about +/-0.2 percent or better and the He-4 concentration with a precision of about +/-0.5 percent will be reported in two years or so. Samples for Tritium Measurement The 1 liter tape-sealed flint glass bottles, pre-baked for a few hours at about 180 deg.C in an argon-atmosphere and put screw caps with polyethylene cones on, were used for tritium sampling. Tritium sampling followed that for another elements but salin- ity. The sealed bottles were untaped and opened just before sample drawing. Sample was carefully led into the bottle with pre-soaked plastic tubing, not to . Each sample bottle was filled to within a cm or two of the top without rinse procedure. The sample bottle was immediately replaced with a cap, then tape- sealed, wrapped up with cushion sheet and stored in wooden box. A total of 425 samples were taken from upper 1500m layer at 25 stations. However, sample volume was small for 4 bottles, and 2 bottles were overflowed. Samples were sent to the laboratory of Dr. Peter Schlosser, Lamont-Doherty Earth Observatory of Columbia University. Then the samples for He-3 ingrowth from tritium decay will be flame-sealed after gas extraction. After a storage time of 6 to 9 months, the tritium concentration will be determined by mass spectrometric measurement of the tritiogenic He-3. Precision of these measure- ments will be approximately +/-1 to +/-2 percent and the detec- tion limit will be below 0.01TU. The results will be reported in two years or so. 2.7 CARBON-14 OF THE TOTAL DISSOLVED INORGANIC CARBON (M. Ishii) 16 June 1995 Equipment and Technique Carbon-14 isotopic ratio of the total dissolved inorganic carbon was analyzed using the AMS facility at the Institute of Geological and Nuclear Sciences Limited at Lower Hutt, New Zea- land, which is based on a 6MV EN tandem Van de Graaff accelerator and uses a Chapman-type inverted sputter source with graphite targets produced by direct deposition (G. Wallace et al. 1987) Sampling Procedure Subsamples for carbon-14 of the total dissolved inorganic carbon analyses were collected after those for the concentration of the total dissolved inorganic carbon. Subsamples were drawn into 120 cm3 glass bottles carefully (i.e., no bubbles, low turbulence) after the bottles had been rinsed three times with approximately one forth of their volume and overflowed with at least half their volume. Then 0.2 cm3 of saturated HgCl2 solu- tion was added and rubber cap lubricated with Apiezon H grease was clamped with aluminum cap. These samples were stored at room temperature. In the laboratory on land, CO2 was extracted from the sea- water samples using a vacuum line. A 300 cm3 flask in which 2 cm3 of conc. phosphoric acid and a magnetic stirring bar were put was attached to the vacuum line and evacuated. Then a seawater sample was sucked into the flask. The evolved CO2 was purified by the cryogenic distillation using electric cooler of -65 degree C and liquid nitrogen, and sealed in a 9 mm o.d. glass break-seal-tube. Those CO2 samples were sent to the Institute of the Geologi- cal and Nuclear Sciences Limited, where graphite targets for AMS were prepared using excess H2 and an iron catalyst (D.C.Lowe et al., 1987). Status Delta-C14 analyses for 140 samples have been finished so far and their mean uncertainty is +/- 7.9 per mille. 2.8 TOTAL DISSOLVED INORGANIC CARBON ANALYSES (M. Ishii) Equipment and Technique Total dissolved inorganic carbon analyses were performed using a commercially available coulometer (UIC Inc., Model 5012) and hand-made automated CO2 extraction unit. Sample bottles to be analyzed were placed in a temperature-controlled water bath (20.0 +/- 0.1 degree C ) at least 30 minutes before analysis. Seawater subsamples were delivered to the carefully pre-calibrat- ed pipette bulb with water jacket on the CO2 extraction unit at 20.0 +/- 0.1degree C by pressurizing the sample with nitrogen gas. The pipette was flushed with approximately 2 volumes of sample. Approximately 3 cm3 of 10% phosphoric acid was poured into the stripping chamber and was purged for 2 minutes with CO2- free nitrogen gas treated with Ascarite before the coulometer reading was reset and the sample in the pipette was loaded into the stripping chamber. The carrier nitrogen gas containing the evolved CO2 was dried with an electric desiccant unit, magnesium perchlorate and silica gel before entering the titration cell of the coulometer. The acidified sample was allowed to purge for 12 minutes. The coulometer blank was determined once every 2 or 3 hours by allowing approximately 3 cm3 of pre-purged phosphoric acid to be purged with CO2-free nitrogen gas for 12 minutes. It was 0.49 +/- 0.28 ugC/12 minutes (n=115). Concentrations of the total dissolved inorganic carbon were calculated according to DOE(1994). Sampling Procedure Subsamples for total dissolved inorganic carbon analyses were collected immediately after those for dissolved oxygen as soon as the rosette arrived on deck. Subsamples were drawn into 300 cm3 borosilicate glass reagent bottles carefully (i.e., no bubbles, low turbulence) after the bottles had been rinsed three times with approximately one fourth of their volume and over flowed with at least half their volume. Samples were stored in boxes at room temperature and analyses were completed within 15 hours after the rosette reached the deck. Calibrations and Standards We used sodium carbonate solutions in order to calibrate the extraction/coulometric system. Anhydrous sodium carbonate (primary standard grade, 99.97%, Asahi glass Co.) dried at 600 degree C for 1 hour was carefully weighed in 3 cm3 vials in the laboratory on land and stored in 20 cm3 screw-capped vials with silica gel. The standard solutions were prepared in 1 dm3 volu- metric flasks under CO2-free nitrogen at 20.0 +/- 0.1degree C using deionized water prepared by a MILLI-Q.SP.TOC. (Millipore Co.) system. These standards were run immediately in order to avoid errors due to the absorption of atmospheric CO2. Recovery (calibration factor) was calculated as 99.244 %. We assessed accuracy by analyzing Certified Reference Mate- rials for total dissolved inorganic carbon provided by Dr. A. G. Dickson at Scripps Institution of Oceanography (batch #20;1983.40 +/- 1.59(1s) umol/kg (n=13)) once every run. The mean of the results for the CRM analyses during this cruise was 1982.3 +/- 1.3(1s) umol/kg (n=23). The means agreed at the 98% confidence level but disagreed at the 95% confidence level. Data presented are not corrected for the probable systematic error. We monitored precision by analyzing duplicate samples taken from the same Niskin bottle and by taking duplicate samples from Niskin bottles tripped at the same depths. The mean of the absolute difference of duplicate analyses from the same Niskin bottle, shown in Table 2.8.1, was 1.2 umol/kg near surface and increased to 2.2 umol/kg in deep layers. The standard deviation estimated for the 10m - 75m layer and that for the 3250m - 4750m layer are significantly different at the 95% confidence level. The mean of the absolute difference of duplicate analyses from the different Niskin bottles was 2.0 umol/kg. All data for duplicate analyses from the same bottle and from different bot- tles are tabulated in Tables 2.8.2 and 2.8.3, respectively. Table 2.8.1: Mean of the absolute value of the difference between duplicate analyses from the same Niskin bottle. ---------------------------------------------------------------- Layer Mean of the absolute Estimate of the Number of difference in umol/kg standard deviation analyses ---------------------------------------------------------------- 10m - 75m 1.2 1.0 20 500m - 700m 1.5 1.2 6 1000m - 2250m 1.7 1.4 18 3250m - 4750m 2.2 1.8 11 Total 1.6 1.4 55 ---------------------------------------------------------------- Table 2.8.2: All data for duplicate analyses from the same Niskin bottle. ------------------------------------------------------- STN Cast BTL Depth TCARBN average difference m umol/kg umol/kg umol/kg ------------------------------------------------------- RY-8642 1 23 75 1965.9 1964.8 2.0 1963.8 RY-8642 2 13 1249 2345.0 2346.1 2.2 2347.2 RY-8647 1 3 75 1969.0 1969.9 1.7 1970.7 RY-8647 2 21 1249 2342.3 2343.5 2.4 2344.6 RY-8653 1 8 25 1944.1 1944.1 0.2 1944.0 RY-8653 2 15 999 2317.4 2317.9 1.0 2318.3 RY-8653 2 4 3749 2323.6 2325.4 3.6 2327.1 RY-8658 2 15 1248 2346.6 2346.1 1.1 2345.5 RY-8663 1 16 50 1959.6 1959.6 0.0 1959.6 RY-8663 2 1 1249 2350.0 2350.4 0.8 2350.9 RY-8663 2 13 4000 2321.6 2320.9 1.5 2320.1 RY-8668 1 19 10 1908.5 1908.3 0.4 1908.1 RY-8668 2 23 1249 2339.5 2340.4 1.9 2341.4 RY-8673 1 16 50 1925.1 1924.6 0.9 1924.2 RY-8673 2 24 1501 2340.1 2340.8 1.4 2341.5 RY-8673 2 12 4001 2316.6 2317.5 1.7 2318.3 RY-8678 1 21 25 1892.8 1892.7 0.2 1892.6 RY-8678 2 2 1500 2338.0 2339.4 2.9 2340.9 RY-8678 2 14 4252 2318.9 2320.4 2.9 2321.9 RY-8683 1 22 25 1891.1 1891.6 1.1 1892.2 RY-8683 2 5 1500 2328.3 2327.8 0.9 2327.3 RY-8683 2 16 4502 2311.4 2311.0 0.8 2310.6 RY-8691 3 5 49 1883.5 1882.3 2.5 1881.0 RY-8691 2 2 1502 2329.6 2329.7 0.1 2329.7 RY-8691 1 2 4504 2311.2 2311.3 0.2 2311.4 RY-8686 1 21 9 1872.0 1872.7 1.2 1873.3 RY-8686 2 3 1250 2319.9 2318.6 2.5 2317.4 RY-8686 2 15 4003 2317.0 2316.4 1.2 2315.8 RY-8698 2 6 50 1890.4 1889.2 2.4 1887.9 RY-8698 1 3 500 2248.8 2249.5 1.4 2250.2 RY-8702 1 17 50 1904.9 1904.5 0.8 1904.1 RY-8702 2 22 2001 2336.0 2335.1 1.8 2334.1 RY-8702 2 14 3754 2319.8 2321.8 3.9 2323.7 RY-8707 1 18 26 1866.6 1866.0 1.2 1865.5 RY-8710 1 18 25 1887.4 1888.6 2.4 1889.8 RY-8710 2 21 2252 2336.7 2338.9 4.4 2341.2 RY-8710 2 14 3753 2325.2 2326.8 3.1 2328.3 RY-8717 1 10 25 1905.6 1905.4 0.4 1905.2 RY-8717 1 1 500 2239.4 2238.1 2.5 2236.9 RY-8717 1 15 2001 2334.6 2334.7 0.1 2334.8 RY-8721 1 17 51 1939.2 1939.4 0.4 1939.7 RY-8721 2 2 701 2248.5 2248.1 0.7 2247.7 RY-8725 1 17 50 1899.5 1898.6 2.0 1897.6 RY-8725 2 19 2001 2331.0 2330.5 1.0 2330.0 RY-8725 2 15 3002 2327.6 2329.1 3.0 2330.6 RY-8729 1 19 25 1892.8 1891.8 2.0 1890.8 RY-8729 2 3 700 2255.3 2255.6 0.7 2256.0 RY-8733 1 19 25 1889.6 1889.8 0.5 1890.1 RY-8733 2 4 700 2232.8 2233.9 2.2 2235.0 RY-8733 2 20 2001 2332.8 2333.5 1.4 2334.2 RY-8735 2 23 2251 2331.1 2332.6 3.0 2334.1 RY-8735 2 15 3753 2328.5 2330.0 2.9 2331.5 RY-8737 1 9 25 1911.8 1912.3 1.0 1912.8 RY-8737 1 21 699 2206.5 2207.4 1.7 2208.3 RY-8737 1 15 1251 2307.5 2308.4 1.7 2309.3 ------------------------------------------------- Table 2.8.3: All data for duplicate analyses from different Niskin bottles tripped at the same depth. ------------------------------------------------------ STN Cast BTL Depth TCARBN average difference m umol/kg umol/kg umol/kg ------------------------------------------------------ RY-8642 1 20 149 2003.0 2003.3 0.7 19 149 2003.7 RY-8642 2 22 298 2037.5 2036.0 3.0 21 298 2034.5 RY-8642 2 20 499 2166.7 2167.9 2.3 19 499 2169.1 RY-8642 2 12 1749 2342.3 2343.1 1.6 11 1749 2343.9 RY-8642 2 10 2249 2337.1 2335.9 2.3 9 2249 2334.7 RY-8647 2 21 1249 2343.5 2342.5 2.0 20 1249 2341.5 RY-8653 2 21 500 2070.7 2071.5 1.6 20 500 2072.3 RY-8653 2 7 3249 2325.0 2326.0 2.1 6 3249 2327.0 RY-8658 2 21 600 2107.3 2107.0 0.5 20 600 2106.8 RY-8658 2 12 2249 2336.5 2338.8 4.6 11 2249 2341.1 RY-8658 2 6 3749 2323.6 2323.6 0.1 5 3749 2323.6 RY-8658 2 3 4409 2321.0 2321.3 0.7 2 4409 2321.7 RY-8663 2 8 499 2131.5 2132.6 2.3 7 499 2133.8 RY-8663 2 22 1999 2342.7 2344.1 2.7 21 1999 2345.4 RY-8668 2 23 1249 2340.4 2340.8 0.7 22 1249 2341.2 RY-8678 1 13 399 2130.8 2131.9 2.3 12 399 2133.0 RY-8678 2 22 2501 2336.3 2338.9 5.3 21 2501 2341.5 RY-8683 1 13 500 2241.8 2242.3 0.9 12 500 2242.8 RY-8683 2 20 3753 2322.2 2323.0 1.7 19 3753 2323.9 RY-8686 1 16 124 2021.4 2019.8 3.3 15 124 2018.1 RY-8686 2 7 699 2259.6 2259.7 0.2 6 699 2259.8 RY-8702 2 7 499 2242.3 2243.2 1.9 6 499 2244.2 RY-8702 2 22 2001 2335.0 2336.1 2.2 21 2001 2337.2 RY-8710 2 7 502 2232.8 2232.3 1.0 6 502 2231.8 RY-8710 2 21 2252 2339.0 2337.8 2.3 20 2252 2336.7 RY-8717 1 20 1000 2300.4 2302.2 3.7 19 1000 2304.1 RY-8729 2 7 401 2199.2 2198.8 0.8 6 401 2198.4 RY-8733 2 7 500 2186.2 2186.7 1.0 6 500 2187.2 RY-8735 2 20 3003 2333.6 2333.3 0.6 19 3003 2333.0 RY-8735 2 16 3753 2332.5 2330.5 4.0 15 3753 2328.5 RY-8737 1 20 800 2228.0 2228.6 1.1 19 800 2229.1 RY-8737 1 17 1000 2270.6 2268.1 4.9 16 1000 2265.7 RY-8737 1 14 1500 2321.3 2322.0 1.4 13 1501 2322.7 ------------------------------------------------------ REFERENCES Bullister, J.L. and R.F. 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Ormond(1994): Report on Concentrations, Lifetimes, and Trends of CFCs, Halons, and Related Species. NASA Reference Publication 1339, NASA Office of Mission to Planet Earth Science Division, Washington, D.C. Lowe, D.C., G.Wallace and R.J.Sparks (1987): Applications of AMS in the atmospheric and oceanographic sciences. Nuclear instruments and methods in physics Research B29, 291-296. Mantyla, A.W.(1987): Standard seawater comparisons updated. J. Phys. Oceanogr., 17, 543-548. Millard, R.C. and K. Yang(1993): CTD Calibration and Processing Methods used at Woods Hole Oceanographic Institution. WHOI-93- 44, Technical Report, Woods Hole, MA., USA. Takatsuki, Y., M. Aoyama, T. Nakano, H. Miyagi, T. Ishihara and T. Tsutsumida(1991): Standard Seawater Comparisons of Some Recent Batches. J. Atmos. Oceanic. Tech., 8, 895-897. Wallace, G., R.J.Sparks, D.C.Lowe and K.P.Pohl (1987): The New Zealand accelerator mass spectrometry facility. Nuclear instruments and methods in physics Research B29, 124-128. WHPO(1991): WOCE Operations Manual. Part 3.1.2:Requirements for WHP Data Reporting. WHP Office Report WHPO90-1. July 1991, Rev.1. WHPO(1911): WOCE Operations Manual. Part 3.1.3:WHP Operations and Methods. WHP Office Report WHPO91-1. Nov.1994, Rev.1. WHPO(1991): A Comparison of Methods for the Determination of Dissolved Oxygen in Seawater. WHP Office Report WHPO91-2. FIGURE CAPTIONS (Figures available in PDF file) Figure 1.1 WHP-P09 station locations Figure 1.2a Location of oxygen samples collected on WHP-P09 Figure 1.2b Location of nutrient samples collected on WHP-P09 Figure 1.2c Location of CFCs samples collected on WHP-P09 Figure 1.2d Location of tritium samples collected on WHP-P09 Figure 1.2e Location of helium-3 samples collected on WHP-P09 Figure 1.2f Location of carbon-14 samples collected on WHP-P09 Figure 1.3a Potential temperature section by the CTD Figure 1.3b Salinity section by the CTD Figure 2.1.1 Meridional distribution of salinity Figure 2.1.2 Meridional distribution of oxygen concentration Figure 2.3.1 Reagents and flow diagram for the silicate determination Figure 2.3.2 Reagents and flow diagram for the nitrate determination Figure 2.3.3 Reagents and flow diagram for the nitrite determination Figure 2.3.4 Reagents and flow, diagram, for the phosphate determination Figure 2.5.1a Pressure sensor difference (CTD #1316, pre-cruise) Figure 2.5.lb Pressure sensor difference (CTD #1316, post-cruise) Figure 2.5.2 Pressure sensor difference (CTD #1318, post-cruise) Figure 2.5.3 Temperature sensor difference (CTD #1316, pre-cruise) Figure 2.5.4 Temperature sensor difference (CTD #1318, post-cruise) Figure 2.5.5 Drift of CTD temperature referred to RTM temperature COMMENTS ON DQ EVALUATION OF WOCE P09 CTD DATA (Michio AOYAMA) 29 March 1996 General: The data quality of WOCE P09 CTD data (EXPOCODE: 49RY9407_1 & 49RY9407_2) and the CTD salinity and oxygen found in dot sea file are examined. The individual 2 dbar profiles were observed in temperature, salinity and oxygen by comparing the profiles obtained in the same basin. The 105 profiles of P09 CTD data were divided into five groups described in the cruise report as listed below; Station number Corresponding basin name ----------------------------------------- from 1 to 28 Shikoku Basin from 29 to 33 from 33 to 65 West Mariana Basin from 65 to 85 West Caroline basin from 85 to 105 Eauripik Ridge The CTD salinity and oxygen calibrations are examined using the water sample data file p1 0.mka. DQE used the original water sample data flagged "2" only for the DOE work. Details: 1. CTD profiles CTD temperature, salinity and oxygen look good in general. CTD salinity profiles look a little bit noisy even in the deeper layers among the first 68 stations, while the quality of CTD salinity profiles becomes better among the stations from 69 to 105. DQE guesses that the first CTD unit used on the P09 cruise might have a problem from the beginning of the cruise. DOE also observed clear salinity spikes in a few CTD files obtained by both first CTD unit and second CTD unit. DOE also observed spikes and unreasonable values in the oxygen profile for a few stations. Details for each problem are listed in Sec. 3. 2 Evaluation of CTD calibrations to water samples 2.1 Salinity calibration; Standard deviation of Ds, Ds = CTD salinity in dot sea file - bottle salinity, is 0.0186 psu for all data and 0.00806 psu for deeper than 2000 dbar, respectively. These values are fairly large considering the required accuracy of CTD salinity and sample water salinity. The histogram of Ds for all depths shows a non-symmetric distribution having a bias of negative Ds (fig.1). For the deep salinity fit, DQE also observed the non-symmetric distribution having a bias of positive Ds (fig. 2). Ds vs. pressure plot shows the strong pressure dependency of Ds (fig. 3). This pressure dependency can explain the non-symmetric distributions and opposite sign of biases in the histograms of Ds for all depth and deep. Since the deep water sample salinity data among the first 60 stations bounced toward fresher values and pressure dependency mentioned above, standard deviation of Ds might account for a larger value of 0.00806 psu than one would expect from good salinometer operation and CTD salinity calibration. After flagged out the fresher values as suggested by DQE, standard deviation of Ds becomes 0.00115 psu for deeper than 2000 dbar. Although this smaller value of0.00115 psu is well enough, the histogram of Ds for deeper than 2000 dbar still shows a non-symmetric distribution (fig. 4), DQE suggests that further/additional correction will improve the quality of CTD salinity. 2.2 Oxygen calibration; Although the Dox, Dox = CTD oxygen in dot sea file - bottle oxygen, histogram for all depths (fig. 5) looks symmetric, Dox has a strong pressure dependency as shown in fig. 6. DQE also observed that this pressure dependency of Dox was unquestionable at the beginning of the cruise but settled down as the cruise progressed. Dox vs. pressure plots for the stations 1 to 10 (fig. 7), 21 to 30 (fig. 8), 41 to 50 (fig. 9) and 60 to 69 (fig. 10) show the gradual transition of the pressure dependency of CTD oxygen sensor. DQE strongly suggest further correction for CTD oxygen calibration considering the characteristics of the pressure dependency using several station groupings. 3. The following are some specific problems that should be looked at: stn. 11 Theta-salinity plot for stn. 11 does not overlay the theta-salinity plots for nearby stations. It may have originated from higher salinity and/or higher temperature. Check the conductivity scaling factor and/or temperature profile. stn. 37 from ca. 3230 dbar to 3427 dbar; oxygen shows extremely high. Suggest flag "4". stn. 53 from 3100 dbar to 3200 dbar: Oxygen spikes of 4 - 5 µmol/kg were observed among these depths. Suggest flag "4". stn. 56 Many oxygen spikes were observed in the deep. Suggest flag "3" or "4". stn. 58 Many oxygen spikes were observed in the deep. Suggest flag "3" or "4". stn. 58 at 4140 dbar, 4213 dbar and 4315 dbar: Salinity spikes were observed at these depths. Suggest flag "4". stn. 62 within deepest 60 dbar: Noisy salinity profile. Suggest flag "T. stn. 69 at 2833 dbar: Salinity shift of 0.004 pss was observed clearly. Suggest check the whole profile. stn. 78 between 3700 dbar and 4200 dbar: Salinity profile looks noisy. Suggest flag "3". stn. 92 at 3379 dbar: Salinity spike/noise observed. Suggest flag "4". stn. 103 at 2333 dbar: Salinity spike/noise observed. Suggest flag "4". COMMENTS ON DQ EVALUATION OF WOCE P9 HYDROGRAPHIC DATA (EXPOCODE: 49RY9407/1 & 49RY9407/2). Michio AOYAMA 29 March 1996 The data quality of the hydrographic data of the WOCE P9 cruise (EXPOCODE: 49RY9407/1 & 49RY9407/2) are examined. The data files for this DQE work were P9.sum and P9.mka ( this P9.mka file is created for DQE, then it has a new column of quality 2 word) provided by WHPO. General; The station spacing ranged from ca. 7 to ca. 38 nautical miles. Aside from suffering some lost data due to the trip malfunctions on the Rosette samplers throughout the cruise, the sampling layer spacing was kept ca. 250 dbar in the deeper layers during this P9 cruise. The ctd lowerings were made to within 20 meters to the sea bottom except several stations. The data originators have done a good job in evaluating the data and in solving trip problems. DQE, however, observed a few unreasonable values among the data flagged "good" by the data originators. Aside from these small problems mentioned above, the Ryofu maru P9 cruise at 137Ewill improve our knowledge on the western North Pacific and update the deep water data set at this area. DQE used the data flagged "2" by the data originators for this DQE work. DQE examined 6 profiles and 7 property vs. property plots as listed below: salinity, oxygen, silicate, nitrate, nitrite and phosphate profiles 1 theta vs. salinity plot 2 theta vs. oxygen plot 3 salinity vs. oxygen plot 4 nitrate vs. phosphate plot 5 salinity vs. silicate plot 6 theta vs. silicate plot 7 silicate vs. nitrate plot 1. Salinity; The deep water salinity data bounced mostly toward fresher among the first 40 stations. This tendency observed among the stations between 54 and 60 again, but settled down as the cruise progressed. Since the data originator had not flagged out these bounced values, DS, DS=CTD salinity - bottle salinity in dot sea file, vs. station # plot for the deeper layer (deeper than 2000 dbar) shows a larger variability of salinity difference among the stations up to 60 (fig. 1) 2. Oxygen; Bottle oxygen profile looks good. Salinity vs. oxygen and theta vs. oxygen plots also looks reasonable. DQE thinks that the flags of the bottle oxygen data are reliable. 3. Nutrients; The profiles of nitrate, nitrite and phosphate look well. Nitrate vs. phosphate plot also looks pretty reasonable. Although DQE observes that silicate concentration seems to be slightly fluctuating station by station and higher as already stated in the cruise report (2.3 Nutrient measurements and Table 2.1.4), P9 silicate overlays pre-woce (P3 and P4) silicate data within the accuracy of 1-3 %. 4. The following are some specific problems that should be looked at: STNNBR XX/ CASTNO X/ SAMPNO XX at XXXX dbar: 4/1/3 at 1515 dbar: Bottle salinity looks low. Suggest flag "3". 10/2/17 at 2276 dbar: Bottle salinity looks low. Suggest fig. "3". 11/2/19 at 2022 dbar: Nitrate and phosphate concentrations look low and observed almost identical with the values at 2275 dbar. 13/2/11 at 3550 dbar: Bottle oxygen looks high. Suggest flag "3". 14/1/1 at 3806 dbar: Bottle salinity looks like high. Suggest flag "3". 14/1/4 at 3296 dbar: Bottle salinity looks like low. Suggest flag "3". 15/2/12 at 4063 dbar: Bottle oxygen looks high. Suggest flag "3". 15/3/34 at 1006 dbar: Bottle salinity looks low. Suggest flag "3". 17/2/10 at 4064 dbar: Bottle oxygen looks high. Suggest flag "3". 19/2/14 at 3298 dbar: Bottle salinity looks like low. Suggest flag "3". 20/2/12 at 4063 dbar: Bottle salinity looks low. Suggest flag "3". 20/2/13 at 3087 dbar: Bottle salinity looks like low. Suggest flag "3". 20/2/17 at 3040 dbar: Bottle salinity looks like low. Suggest flag "3". 21/2/14 at 3296 dbar: Bottle salinity looks like low. Suggest flag "3". 21/2/15 at 3296 dbar: Bottle salinity looks like low. Suggest flag "3". 21/2/16 at 3550 dbar: Bottle salinity looks like low. Suggest flag "3". 21/2/18 at 2529 dbar: Bottle salinity looks like low. Suggest flag "3". 24/2/15 at 3550 dbar: Bottle salinity and oxygen look low. Suggest flag "3". 24/2/16 at 3550 dbar: Bottle salinity looks like low. Suggest flag "3". 25/2/17 at 2783 dbar: Bottle oxygen looks high. Suggest flag "3". 26/2/12 at 4320 dbar: Bottle salinity looks like high. Suggest flag "3". 26/2/14 at 3807 dbar: Bottle salinity looks like high. Suggest flag "3". 28/ */ at all depths: Silicate seems to be shifted toward lower considering the silicate concentrations at nearby stations. Suggest flag "3". 29/1/2 at 402 dbar: Bottle salinity looks very high. Suggest flag "4". 29/2/13 at 5683 dbar: Bottle salinity looks like low. Suggest flag "3". 29/2/16 at 5092 dbar: Bottle salinity looks like low. Suggest flag "3". 35/2/29 at 1512 dbar: Bottle salinity looks low. Suggest flag "3". 36/2/25 at 1513 dbar: Bottle salinity looks low. Suggest flag "3". 37/1/7 at 50 dbar: Bottle oxygen looks high. Suggest flag "3". 37/2/18 at 3039 dbar: Bottle salinity looks like low. Suggest flag "3". 38/11/8 at 2780 dbar: Bottle salinity looks like low. Suggest flag "3". 42/2/20 at 3038 dbar: Bottle salinity looks like low. Suggest flag "3". 43/2/13 at 4576 dbar: Bottle salinity, oxygen and nutrients should be at shallower layer. Suggest flag "4". 43/2/16 at 3806 dbar: Silicate concentration looks low. Suggest flag "3". 43/2/34 at 402 dbar: Bottle salinity looks like low. Suggest flag "3". 48/2/14 at 5697 dbar: Bottle salinity looks like very low. Suggest flag "4". 51/2/19 at 4320 dbar: Phosphate concentration looks high. Suggest flag "3". 54/*/* to 77/*/* at all depths: BTLNBRs for the stations 54 to 77 were blank or zero. Put correct BTLNBR 54/2/15 at 5091 dbar: Bottle salinity looks like low. Suggest flag "3". 55/2/20 at 3042 dbar: Bottle salinity looks like low. Suggest flag "3". 55/2/22 at 2531 dbar: Bottle salinity looks low. Suggest flag "3". 56/1/4 at 4063 dbar: Bottle salinity looks like low. Suggest flag "3". 60/2/17 at 4320 dbar: Phosphate concentration looks high. Suggest flag "3". 60/2/20 at 3808 dbar: Bottle salinity looks like low. Suggest flag "3". 61/2/16 at 3807 dbar: Bottle oxygen looks high. Suggest flag "3". 61/2/18 at 3295 dbar: Bottle oxygen looks high. Suggest flag "3". 61/2/20 at 2785 dbar: Phosphate concentration looks high. Suggest flag "3". 62/2/22 at 4319 dbar: Bottle salinity looks like high. Suggest flag "3". 62/2/34 at 1515 dbar: Bottle salinity looks low. Suggest flag "3". 69/2/29 at 3294 dbar: Phosphate concentration looks low . Suggest flag "3". 69/2/32 at 2530 dbar: Phosphate concentration looks low. Suggest flag "3". 69/2/37 at 1260 dbar: Bottle salinity looks low. Suggest flag "3". 69/2/39 at 907 dbar: Phosphate concentration looks low. Suggest flag "3". 70/2/12 at 3807 dbar: Bottle salinity looks like high. Suggest flag "3". 70/2/13 at 3552 dbar: Bottle salinity looks like high. Suggest flag "3". 71/2/12 at 4151 dbar: Bottle salinity looks low. Suggest flag "3". 73/2/13 at 4064 dbar: Bottle salinity looks low. Suggest flag "3". 75/2/20 at 2276 dbar: Bottle salinity looks like low. Suggest flag "3". 77/2/19 at 2022 dbar: Bottle salinity, oxygen and nutrients should be at shallower layer. Suggest flag "4". 79/2/ 10-33 at 1517-1518 dbar: Although the sampling depths are almost same for these layers, bottle oxygen varied from 155 µmol/kg to 70 µmol/kg. Put correct values with appropriate flags. 75/2/14 at 3552 dbar: Bottle salinity looks low. Suggest flag "3". 79/3/35 at 4061 dbar: Bottle salinity looks like low. Suggest flag "4". 89/3/30 at 1513 dbar: Bottle salinity looks low. And this salinity seems similar with the salinity at one layer shallower. Suggest flag "4". 90/2/19 at 1512 dbar: Bottle oxygen and nutrients should be at shallower layer. Suggest flag "4". 92/2/12 at 3296 dbar: Bottle salinity, oxygen and nutrients should be at shallower. Suggest flag "4". 92/4/ 14-17, 24-26, 28 and 31-37: Although the depth ranged from 152 dbar to 3433 dbar, phosphate concentrations are zero. Put correct values with appropriate flags. 92/4/22 at 2275 dbar: Bottle oxygen looks high. Suggest flag "3". 100/2/18 at 2276 dbar. Bottle salinity looks low. Suggest flag "3". 103/2/15 at 4225 dbar: Bottle oxygen looks very high. Suggest flag "4". 105/1/5 at 1008 dbar: Phosphate looks low. Suggest flag "3". 105/1/12 at 502 dbar: Phosphate looks low. Suggest flag "3". DATA QUALITY EVALUATION OF HYDROGRAPHIC DATA FOR P09 (George C. Anderson) October 25, 1998 and updated several times since Notes on the DQ Evaluation of Cruise P09, a Japanese cruise along 137E and 142E from about 35 deg N to 3 deg South EXPOCODE: 49RY9407_1 & 49RY9407_2 PI: Dr. Hiroki Kondo DQE of the discrete data listing for: temperature, salinity (CTD and bottle data), oxygen (CTD and bottle data), silicate, nitrate, nitrite, and phosphate. After completing the DQE work on this cruise, it was discovered that this cruise had already been DQE'd, a report written, corrections made, and an updated file submitted. The initial DQ evaluation had been done by Michio Aoyama and was dated 29 March 1996. Unfortunately the file I examined was not the most recent, so many of the items I would have flagged had already been discovered and corrected. The processing scheme consisted of preparing plots of the parameters to be investigated. All parameters were plotted versus pressure. As necessary, supplementary plots of theta-salinity and salinity-silicate were prepared for individual stations or groups of stations. In addition, plots of phosphate (x-axis) versus nitrate (y-axis) were prepared for each station. From these data, plots of the N03/PO4 ratio, and y-intercept were prepared plotting these values versus station number (copy attached). Positions from the sum file were plotted and appear to be correct. Cast times and dates were checked for consistency. No errors were found. The work of Dr. Hiroki Kondo is to be commended in resolving bottle tripping problems. These are described in the Cruise Report. Results: Overall the data look quite good. There are some "bad" bottle salts; excluding the surface levels (1st and 2nd bottles) CTD-oxygens look very reasonable. There are some "bad" nutrient samples, mostly phosphate, and a few leaky bottles. The phosphate values on stations 104 and 105 are not of the quality of the rest of the cruise. On a few stations it appeared as though there were some key entry errors, double sampling from the same Niskin bottle, or data for two levels reversed. At station 69 the CTD-02 sensor. failed and the back-up sensor was found to be faulty. As a result CTD-02 data were not available for the remainder of the cruise. This has been pointed out in the Cruise Report. On four stations, numbers 55, 66, 68 and 70, some to all the silicates had been flagged uncertain. There does appear to be somewhat more scatter in the data than on other stations, but calling the data uncertain may be a bit harsh. I am recommending that the flags be changed back to "2". The values of the N03/PO4 ratio change during the course of the cruise from about 14.2 at the beginning to about 14.8 at the end. At the same time, the value of the y-intercept changes from about 0 to ~ -1. These negative intercepts are quite reasonable and to be expected. The reason(s) for the change in the ratio over the duration of the cruise should be checked. There may have been a problem with one of the phosphate standards (See the attached report on the comparison of nitrate and phosphate data for Cruises P09 and P10). Data from this cruise were compared with data from the following: P09 Station No. Cruise Date Station No. -------------------------------------------------------------------- 11 Geosecs (Pacific) (October of 1973) 224 32 TPS 24 [WOCE P03] (May of 1985) 320 63 P04 (March of 1989) 28 81 WEPOC II (February of 1986) 93 The data for TPS 24 and WEPOC 11 had oxygen concentrations listed in units of ml/l and nutrient values in units of µMoles. These were converted to the WHPO units of µmoles/kg using approximate conversion factors. For oxygen, the values in ml/l were divided by 43.50; for nutrients, the µM units were divided by a density value of 1.0236, based on an approximate lab temperature of 25 degrees Celsius and a salinity of 35 p.s.u. Salinities from P09 compare very well with the data from P04, but are typically 0.002 to 0.004 p.s.u. higher than reported on the other cruises. This is consistent with the observations recorded in the Cruise Report (pages 7 & 8). Part of this offset may be the result of the batch of Wormley water used in standardizing the salinometer (Aoyama, WOCE Newsletter, No. 32, Sept. 1998). Oxygen values are comparable to those reported on the other cruises. The nutrients below 3000 meters show the following: excluding the data from Geosecs, P09 silicates are lower than those reported on the other cruises by 2 to 3 µmoles/kg [at a conc. of 141.0, 2.5 µmoles/kg is 1.8%]; nitrates are within ±1 µmoles/kg of those reported on the other cruises [at a conc. of 36.5 µmoles/kg, this is ~ 2.7% ]; excluding the data for WEPOCII where the phosphates are 0.05 µmoles/kg lower, phosphates are higher than those reported on the other cruises by approximately 0.05 µmoles/kg [at a conc. of 2.55 µmoles/kg, this is ~ 2.0%]. These observations are similar to those described in the Cruise Report (page 13). Except for nitrate, all observations have met the "data quality goals" specified in WOCE Report No. 67/91, Rev. 2, May 1994, page 20). A philosophical question that has no bearing on the quality of the data for this cruise has to do with the use of quality flags when calibration data are not available for a cast. As an example when the CTD oxygen sensor was operational, there were casts made for water samples which did not include discrete samples for oxygen. One could make an argument that without these calibration data, one's confidence in the data is somewhat less than if discrete samples had been collected and analyzed. To this extent at best flag "3" should be used. However, since previous casts at this station and casts on adjacent stations had calibration data, quality flags should be assigned based on this information and normally would be "2". As stated above, this is a philosophical question whose answer goes beyond the scope of this DQE work. George C. Anderson DQE, WHPO CRUISE P09 DQE DATA SUMMARY The following are some specific problems that should be checked: Station Cast Bottle Pressure Notes Number Number (dbars) ----------------------------------------------------------------------------- 2 1 13 100.3 CTD salinity appears to be low; suggest flag it 3 1 13 Bottle salinity appears to be okay; suggest change flag from 3 to 2 4 1 5 1009.7 Bottle salinity is low; suggest flag it 3 1 2 1515.2 Bottle data look okay; suggest change the bottle flag from 4 to 2 1 3 1515.2 Bottle appears to have leaked; suggest flag 4 for bottle 11 1 6 50.1 CTD salinity is high; suspect a salinity spike or a key entry error 2 1 4235.4 Phosphate value is low; suggest flag 3 13 2 7 3550.2 Bottle oxygen appears to be okay; suggest change flag to 2 2 6 3805.6 Bottle oxygen low; suggest flag 3 15 2 9 4063.3 Bottle oxygen appears to be okay; suggest change flag to 2 2 7 4306.8 Bottle oxygen low; suggest flag 3 16 2 10 2783.8 Bottle oxygen low; suggest flag 3 18 2 18 906.6 CTD oxygen looks okay; suggest change flag to 2 19 2 12 2274.9 Bottle oxygen high; suggest flag 3 23 1 7 49.9 CTD salinity spike; suggest flag 4 24 2 2 4577.1 Bottle oxygen low; suggest flag 3 27 2 11 2531.0 Phosphate value is low; suggest flag 3 30 2 7 3807.6 Oxygen and nutrient values low; suggest flag 3 for both parameters 2 4 4834.0 Bottle oxygen low; suggest flag 3 31 2 22 2021.2 Phosphate value is low; suggest flag 3 2 10 4834.5 Bottle oxygen low; suggest flag 3 32 1 15 125.8 CTD salinity high; suggest flag 3 2 4 1008.7 CTD salinity is high; suggest flag 3 2 4 Bottle salinity looks okay; suggest change flag from 3 to 2 2 15 4064.7 Phosphate value is low; suggest flag 3 33 1 16 24.9 CTD salinity spike; suggest flag 3 36 2 13 3547.8 Bottle salinity is low; suggest flag it 3 2 14 3547.8 Bottle salinity is low; suggest flag it 3 2 12 3805.5 Bottle salt looks okay; suggest change flag from 3 to 2 2 9 4307.5 Bottle salinity is low; suggest flag it 3 39 2 1 2015.4 Bottle salinity is low; suggest flag it 3 41 2 3 907.9 CTD oxygen looks okay; suggest change flag from 3 to 2 2 11 4320.0 CTD oxygen high; suggest flag 3 43 2 21 2020.9 Nutrient values look okay; suggest change flags from 4 to 2 2 14 3806.5 Silicate value is suspect but not bad; suggest change flag from 4 to 3 47 2 21 3040.1 Silicate value is low; suggest flag 3 Cruise P09 DQE data summary (continued) The following are some specific problems that should be checked: Station Cast Bottle Pressure Notes Number Number (dbars) ----------------------------------------------------------------------------- 50 1 18 100.5 CTD oxygen looks okay; suggest change flag to 2 1 18 100.5 Bottle oxygen looks very low; suggest flag 4 2 22 3040.1 Bottle salinity is low; suggest flag it 3 2 16 4318.3 CTD oxygen value is high; suggest flag 3 52 2 12 4513.6 Bottle data appear to be okay; suggest change bottle flag from 3 to 2 55 2 10 503.8 Silicates from here to bottom flagged 3; data a bit noisy but okay; suggest change flags to 2 2 20 3041.8 Bottle oxygen looks okay; suggest change flag from 3 to 2 61 2 17 3551.8 Bottle salinity is low; suggest flag it 3 60 2 13 5098.6 CTD salinity is low; suggest flag 3 57 2 3 1767.5 Bottle salinity is low; suggest flag it 3 56 2 8 604.6 CTD salinity is low; suggest flag 3 62 2 16 3805.0 Phosphate value high; suggest flag 3 63 2 19 2276.4 CTD salinity is low; suggest flag 3 66 2 all depths Silicates flagged 3; data a bit ragged but okay; suggest change flags to 2 68 2 15 2529.6 Phosphate value is low; suggest flag 3 2 7 150.2 Silicates at all depths between 150.2 and 3261.3 flagged 3; 2 12 3261.3 data a bit noisy but okay; suggest change flags to 2 69 2 8 1260.6 CTD salinity is high; suggest flag 3 2 8 Bottle salinity appears to be okay; suggest change bottle flag from 3 to 2 2 12 6122.6 Bottle salinity is low; suggest flag it 3 70 all depths Silicates flagged 3 but appear to be okay; suggest change flags to 2 72 2 17 3294.0 Bottle salinity is low; suggest flag it 3 75 2 22 2275.6 Bottle oxygen is suspect; suggest flag 3 2 22 Phosphate value is low; suggest flag 3 78 2 20 2275.9 Phosphate value is low; suggest flag 3 80 2 19 2022.5 Phosphate value is low; suggest flag 3 2 13 3552.2 CTD salinity is high; suggest flag 3 93 2 15 3038.4 Bottle salinity is okay; suggest change flag from 3 to 2 2 15 Bottle oxygen is suspect; flag it 3 2 14 3295.9 Bottle oxygen low; suggest flag 3 101 2 6 503.9 CTD salinity is low; suggest flag 3 2 19 2275.6 Phosphate value is low; suggest flag 3 103 1 16 301.7 Phosphate value is low; suggest flag 3 104 3 15 907.2 CTD salinity is high; suggest flag 3 92 The second occupation of this station 3 16 127.0 The phosphates at these depths appear to be 3 15 151.6 low; suggest all be flagged 3. 3 13 302.2 many missing or suspect phosphates on this 3 14 302.2 station 3 11 404.5 3 12 404.5 Review of the Nitrate and Phosphate Data from Selected Stations WOCE Cruises P09 and P10 As part of the repeat DQE of WOCE Cruise P09, the nitrate and phosphate data from a station were plotted against each other. A least squares fit was used to determine the N03/PO4 ratio and intercept. Subsequently, plots were made of the slope and intercept values at each station versus the station number. There appeared to be a transition zone in the curves between stations 44 and 60. Between these stations the N03/PO4 ratio increased from ~ 14.3 to ~ 14.7 while the intercept changed from ~ -0. 15 to ~ -1.0. Initially it was thought that this might have been the result of changes in the primary phosphate standards being used on the cruise. To investigate this, data from WOCE Cruise P10, stations 29-31 and 70-72, were treated similarly as those from P09. The two groups of stations from P10 were at similar northern latitudes as those of P09 but were 12 degrees of longitude to the east at the northern stations and ~6 degrees of longitude to the east at the southern stations. The N03/PO4 ratios from P09 & P10 are similar and increase towards the equator. At the northern stations the values are 14.27 and 14.44 respectively for P09 and P10. At the southern stations the values are 14.74 and 14.66 respectively. There is also an increase in the value of the intercepts in moving towards the equator. At the northern stations the values are -0.08 and -0.29 respectively for P09 and P10. At the southern stations the values are -0.74 and -1.30 respectively. These data would suggest that the changes in the values of the N03/PO4 ratio and intercept seen on Cruise P09 are real. They are related to changes in the surface phosphate and nitrate values as one moves south rather than to problems with one of the standards used during the cruise. As a second approach in examining, this phenomenon, the N03/PO4 ratio was calculated for each bottle deeper than 3000 decibars at all stations from both cruises. The mean was determined for all values within each group of stations. At the northern part of the pattern, the mean of the P09 station data is ~14.45, for P10, the mean is ~14.44, almost identical. At the southern part of the pattern, the mean of the P09 station data is ~ 14.6, for P10, the mean is ~ 14.2, so P09 is ~ 0.4 units higher than P10. In going from the northern to the southern groups of stations, the P09 value increases by ~ 0. 15 units while the P10 value decreases by ~ 0.24 units. From these data, it would appear that there has been a shift in the deep data. Other sections need to be reviewed before resolving this. It should be noted that station depths on P10 were ~1000 decibars deeper than on P09. As a result a few more values were included in the averages at each P10 location. FINAL CFC DATA QUALITY EVALUATION (DQE) COMMENTS ON P09. (David Wisegarver) Dec 2000 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 (Dr. I. Kaneko, ikuo-kaneko@met.kishou.go.jp, or Y. Takatsui, yasushit@jamstec.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. ******************************************************************************** DATA PROCESSING HISTORY DATE CONTACT DATA TYPE DATA STATUS SUMMARY ----------------------------------------------------------------------------- 3/29/96 Aoyama CTD/S/O DQE Report rcvd @ WHPO 8/15/97 Uribe DOC Submitted 2000.12.11 KJU File contained here is a CRUISE SUMMARY and NOT sumfile. Documentation is online. 2000.10.11 KJU Files were found in incoming directory under whp_reports. This directory was zipped, files were separated and placed under proper cruise. All of them are sum files. Received 1997 August 15th. 9/15/98 Talley SUM/BTL Website Updated SUM, S/O, NUTs, CFCs online 10/30/98 Anderson NUTs/S/O DQE nearly complete 5/5/99 Anderson NUTs/S/O Letter from DQE to Chief Scientist: Enclosed is a DQE report on the hydrographic data submitted to the WHPO for onetime line P9 (49RY9407/1 &2). As it turns out, this is the second review of the data for this cruise, and I think you deserve an explanation. I have recently been employed to do DQE work for the WHPO. Originally this work was coordinated through the WHPO office at the Woods Hole Oceanographic Institution located in Woods Hole, Massachusetts. About two years ago, the WHPO office was moved to the Scripps Institution of Oceanography. Unfortunately, during the transition, some records were misplaced including the original DQE evaluation of these data by M. Aoyama. It wasn't until after I completed my evaluation, the end of 1998, that his report and related records were discovered. This included a copy of correspondence sent to you by Terrence M. Joyce, Director, WHPO, dated 12 June, 1996, with M. Aoyama's DQE report. When the error was discovered, there was some discussion as to whether I should continue my efforts on this cruise. It was decided that since I had done as much work as I had, I should complete this task. Many of the items that I flagged had already been flagged by M. Aoyama, had been reviewed by your personnel, and differences in Q I and Q2 flags had been resolved. These items will not be found in my listing. There are a few other items that I have flagged, only a few of which would affect the use of or interpretation of these data by other users. I found the nitrate/phosphate data plots of particular interest. As a result I went well beyond what might normally be done by a DQ Evaluator in examining the patterns in these plots. I have not resolved the question of the deep nitrate data discrepancies, but this is something that I will be looking at as I evaluate other cruises. 5/10/99 Anderson NUTs/S/O DQE Report rcvd @ WHPO 12/6/99 Huynh CTD/BTL/SUM Data Update New data files received 4/14/00 Key DELC14 Data are Public As of 3/2000 the 2 year clock expired on the last of the Pacific Ocean C14 data (P10). All Pacific Ocean WOCE C-14 data should be made public. 4/19/00 Bartolacci DELC14 Website Updated P09 Changed to indicate WHPO has data. 6/7/00 Schlosser HELIUM/DELHE3/NEON Submitted 8/4/00 Saiki CTD/BTL Data are Public: 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. P09 Salinity, Oxygen, Nutrients, CFCs, C-14 and CTD 9/26/00 Schlosser TRITUM No Data Submitted; See Note: Tritium data will be submitted later (after intercalibration). We hold tritium data for a subset of our He lines only. WHP lines with tritium: S04P. S04I (East). I08S, I09S, P09 9/29/00 Talley He/Tr Schlosser responsible for all He/Tr There will be one data set submitted from L-DEO. It covers the shallow water column for tritium and He and the deep water column for He only. - P. Schlosser 1/5/01 Kappa DOC Doc Update txt version created 1/8/01 Huynh DOC Website Updated; txt version online 2/16/01 Schlosser HELIUM/DELHE3 Data NonPublic final calibration not yet done Thanks for your message. The reason that the he data are classified non- public is probably due to the fact that the final calibration has not yet been carried out. If there is a way to make them public with the note of caution that a small correction might be applied later, we should move the data into the public domain. we probably wanted to look at a 'funny' feature of elevated tritium concentrations that seem to fall along a certain isopycnal. We will transmit the tritium data within a short time (I would like to have another look at this feature and correlate it with some other properties). 2/26/01 Schlosser HELIUM/DELHE3 Data are Public Minor corrections may be needed post-intercal. Effort. Following up on bill Jenkins's message, I would like to ask you to make public all ldeo woce tritium/he data that have been submitted to you. Because the tritium/he community has not yet finished the final calibration of the data, I might have to apply minor corrections to these data once the intercal. effort has been completed. Our acce work was funded over a 5-year period that ended in 2000. Consequently, this data set is further behind in quality control before submission, but I expect that we will get these data ready soon. SR3 was never funded in a 'regular' fashion, but I used NOA corc funds to keep the measurements of this sample set moving. I expect to finish the analyses this summer and submit them in fall. 3/29/01 Kaneko CFCs/NUTs/C14/CO2 Update Needed; See Note: Through DQE of P9-CFCs, we found considerable amount of errors in CFCs sampling layers at Stas.15, 33, 66, 73. These errors were occurred when CFC data were merged with the other property data. For the second cast at Sta. 66, three sampling bottles and layers of oxygen, nutrients, radio-carbon and total carbon were wrong. Oxygen value drawn from bottle 5 should be re-calculated because density used for the conversion from µmol/l to µmol/kg is changed. Mr. Takatsuki (yasushit@jamstec.go.jp) is now reconstructing new data set of water sampling. He will send it to WHPO/SIO via FTP, as soon as possible. 4/9/01 Takatsuki CFCs/NUTs/C14/CO2 DQE Issues Resolved The Bottle File has the following parameters: OXYGEN,SILCAT,NITRAT,NITRIT,PHSPHT,CFC-11,CFC-12,DELC14,TCARBN. The Bottle File contains: CastNumber StationNumber BottleNumber SampleNumber TAKATSUKI, YASUSHI would like the data PUBLIC. And would like the following done to the data: correct errors in CFCs (Stn.15,33,66,73) and Nutrients /Total Carbon /C-14 (Stn.66) 6/22/01 Muus HELIUM Submitted/not on web Helium received June 7, 2000: /usr/export/html-public/data/onetime/pacific /p09/ original/2000.06.07_P9_DOC_SEA/P9HeNe.SEA/P9HeNe.SEA and made public by P Schlosser Feb 26, 2001, are not yet on web bottle file. (19980914WHPOSIOSA) 6/22/01 Uribe CTD/BTL Website Updated; CSV File Added CTD and Bottle files in exchange format have been put online. 9/14/01 Muus CFCs Data Merged into BTL file Notes on P09 CFC merging Sept 14, 2001. D. Muus 1 New CFC-11 and CFC-12 from: /usr/export/html-public/data/onetime/pacific/p09/original/20010907_P09_CFC _UPDT_WISEGARVER/20010907.121249_WISEGARVER_P09/20010907. 121249_WISEGARVER_P09_CFC_DQE.dat merged into SEA file received from web, Sept 7, 2001 (19980914WHPOSIOSA) No SEA file QUALT2 words so added QUALT2 identical to QUALT1 prior to merging. .SEA file name changed from p09hy.txt to p09_hy.txt. .SUM file name p09su.txt and text left unchanged. 2 Exchange file checked using Java Ocean Atlas. 9/18/01 Muus BTL/DOC Website Updated New CSV file w/ updated CFCs now online. Created directory in p09/orignal for new files and moved new file to p09 directory. New bottle and exchange files are now on line 9/18/01 Muus CFCs Website Updated New btl file w/ updated CFCs now online 11/9/01 Kappa DOC Doc Update added PDF version w/ figs, cfc/ctd/btl dqe reports in both versions