Shore-based Reference Analyses
The replicate samples from 11 Niskin bottles at 4 stations were collected for shore-based reference analyses at the laboratory of C. D. Keeling of SIO. The TCO2 measurements were produced by vacuum extraction/manometric analysis and the TALK values by potentiometric titration. Both measurements were performed in controlled laboratory conditions using standards. Samples were collected from the same Niskin bottles used to collect samples for shipboard analyses of TCO2. The shore laboratory analyses of TCO2 and TALK employed a precise and proven methodology to provide information on the quality of the shipboard analyses (Guenther et al. 1994). For all shore-based analyses, a replicate s of 1.43 µ mol/kg for eleven unflagged pairs was calculated, with no deltas greater than 3s. The average difference for eleven comparisons of single replicate samples comparing ship and shore TCO2 values was -3.5 ± 2.0 µ mol/kg. Only two surface water and two deep water comparisons exist for the TUNES-2 Expedition. These represent too few data points for meaningful comparative analysis.
Figure 3 displays the one set of profile differences from Station 180 of the TUNES-2 Expedition. There are eight comparisons from Niskin bottles at 300 m and deeper. After the one shallowest comparison (a replicate singlet) was omitted, the remaining seven are characterized by an average difference of -4.3 ± 1.6 µ mol/kg. The consistency of the four deeper comparisons, all with excellent bottle pair agreement, is striking. Tables 1 and 2 summarize the replicate shore-based measurements of TCO2 and TALK.
THE CARBON DIOXIDE PROJECT OF THE SCRIPPS INSTITUTION OF OCEANOGRAPHY
TUNES Leg 2 1991 Pacific WOCE Lines P17S/P16S
-----------------------------------------------
S.I.O. RUN BOTTLE BOTTLE "NISKIN" LDEO LDEO
LEG LAT. CAST DEPTH SAMPLE EXTRAC ANALYSIS MANO SAMPLE RUN DELTA TCO2 DELTA AVG TCO2 -S.I.O.
STN LONG. NISK (M) DATE DATE DATE TYPE BOTTLE RUN FLAG ----------------- (µMOLES/KG SW) ---------------------
2 23-43S 1 19 909 01AUG91 11DEC91 11DEC91 M S4158 001 2208.25 2208.25
160 132-33W 11DEC91 20DEC91 S S4158 001 2208.73 2208.73
11DEC91 12DEC91 M S4159 001 2207.96 2207.96 -0.29 2208.10 2206.1 -2.00
11DEC91 20DEC91 S S4159 001 2208.23 2208.23 -0.50 2208.48 2206.1 -2.38
2 30-32S 1 61 4 06AUG91 03DEC91 04DEC91 M R4548 001 2023.46 2023.46
174 134-20W 03DEC91 09DEC91 S R4548 001 2022.97 2022.97
03DEC91 04DEC91 M R4549 001 2023.77 2023.77 +0.31 2023.61 2024.2 0.59
03DEC91 09DEC91 S R4549 001 2024.61 2024.61 +1.64 2023.79 2024.2 0.41
1 33 3081 03DEC91 03DEC91 M R4546 001 2301.42 2301.42
03DEC91 06DEC91 S R4546 001 2303.27 2303.27
03DEC91 03DEC91 M R4547 001 2302.64 2302.64 +1.22 2302.03 2299.0 -3.03
03DEC91 06DEC91 S R4547 001 2302.94 2302.94 -0.33 2303.10 2299.0 -4.10
2 37-30S 2 69 315 12AUG91 04DEC91 06DEC91 S R4565 001 2121.42 2121.42 2121.42 2125.5 4.08
180 150-30W
2 11 469 11DEC91 11DEC91 M R4562 001 2134.64 2134.64
11DEC91 19DEC91 S R4562 001 2133.70 2133.70
11DEC91 11DEC91 M R4563 001 2130.68 2130.68 -3.96 2132.66 2126.2 -6.46
11DEC91 19DEC91 S R4563 001 2129.14 2129.14 -4.56 2131.42 2126.2 -5.22
2 13 622 16DEC91 17DEC91 M R4560 001 2138.07 2138.07
16DEC91 20DEC91 S R4560 001 2137.74 2137.74
16DEC91 17DEC91 M R4561 001 2133.80 2133.80 -4.27 2135.94 2132.5 -3.44
16DEC91 20DEC91 S R4561 001 2134.91 2134.91 -2.83 2136.32 2132.5 -3.82
2 16 931 06MAY92 17JUL92 E R4558 001 2169.51
06MAY92 17JUL92 E R4558 002 2168.19 -1.32 2168.85
06MAY92 17JUL92 E R4559 001 2168.22
06MAY92 17JUL92 E R4559 002 2168.53 +0.31 2168.38 -0.47 2168.61 2167.2 -1.41
2 18 1188 05MAY92 17JUL92 E R4556 001 2207.85
05MAY92 17JUL92 E R4556 002 2207.82 -0.03 2207.84
05MAY92 17JUL92 E R4557 001 2207.12
05MAY92 17JUL92 E R4557 002 2206.20 -0.92 2206.66 -1.18 2207.25 2202.9 -4.35
2 20 1543 04DEC91 04DEC91 M R4554 001 2258.59 2258.59
04DEC91 09DEC91 S R4554 001 2259.74 2259.74
04DEC91 05DEC91 M R4555 001 2258.58 2258.58 -0.01 2258.59 2253.9 -4.69
04DEC91 09DEC91 S R4555 001 2257.71 2257.71 -2.03 2258.73 2253.9 -4.83
2 37-30S 2 22 2052 12AUG91 05MAY92 10JUL92 E R4552 001 EX 2299.71
180 150-30W 05MAY92 10JUL92 E R4552 002 2294.57 2294.57
05MAY92 10JUL92 E R4553 001 2295.61
05MAY92 10JUL92 E R4553 002 2295.46 -0.15 2295.54 +0.97 2295.06 2290.4 -4.66
2 26 3051 04MAY92 10JUL92 E R4550 001 2309.37
04MAY92 10JUL92 E R4550 002 2309.74 +0.37 2309.56
04MAY92 10JUL92 E R4551 001 2308.23
04MAY92 10JUL92 E R4551 002 EX 2299.35 2308.23 -1.33 2308.90 2303.7 -5.20
2 21- 0S 1 3 62 23AUG91 12DEC91 13DEC91 M S4118 001 1997.57 1997.57
213 150-30W 12DEC91 19DEC91 S S4118 001 1998.22 1998.22
12DEC91 13DEC91 M S4119 001 1995.37 1995.37 -2.20 1996.47 1992.9 -3.57
12DEC91 20DEC91 S S4119 001 1995.98 1995.98 -2.24 1997.10 1992.9 -4.20
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MANOMETER TYPE: FLAGS:
M = CONSTANT VOLUME MERCURY MANOMETER DATUM F: No Hg found in bottle
S = QUARTZ SPIRAL MANOMETER DATUM G: Severe bottle leak
E = ELECTRONIC CONSTANT-VOLUME MANOMETER DATUM EX: Data excluded from analysis
BOTTLE TYPE:
R = RODAVISS S = S TYPE
NOTE: Dilution factor of 1.000170 has been applied.
Table 2. Summary of total alkalinity replicate data collected during R/V Thomas Washington TUNES-2 Expedition
THE CARBON DIOXIDE PROJECT OF THE SCRIPPS INSTITUTION OF OCEANOGRAPHY
TUNES Leg 2 1991 WOCE Pacific Line P17S/P16S
----------------------------------------------
S.I.O. TRIAL BOTTLE BOTTLE "NISKIN"
LEG LAT. CAST DEPTH SAMPLE ANALYSIS TITR SAMPLE FLAG TRIAL DELTA ALK DELTA AVG
STN LONG. NISK (M) DATE DATE SYST BOTTLE TRIAL ----------------- (µEQUIV/KG SW) ------
2 23-43S 1 19 909 01AUG91 20JAN92 V S4158 1 2300.18 2300.18
160 132-33W 20JAN92 V S4159 1 2302.05 2302.05 +1.87 2301.11
2 30-32S 1 61 4 06AUG91 10JAN92 V R4548 1 2318.15 2318.15
174 134-20W 10JAN92 V R4549 1 2324.19 2324.19 +6.04 2321.17
1 33 3081 10JAN92 V R4546 1 2395.78 2395.78
10JAN92 V R4547 1 2396.62 2396.62 +0.84 2396.20
2 37-30S 2 69 315 12AUG91 14JAN92 V R4564 1 2277.74 2277.74
180 150-30W 14JAN92 V R4565 1 2280.79 2280.79 +3.05 2279.27
2 11 469 14JAN92 V R4562 1 2275.55 2275.55
14JAN92 V R4563 1 2273.45 2273.45 -2.10 2274.50
2 13 622 17JAN92 V R4560 1 2275.23 2275.23
17JAN92 V R4561 1 2281.82 2281.82 +6.59 2278.53
2 16 931 22JUN92 V R4558 1 2290.65 2290.65
22JUN92 V R4559 1 2285.23 2285.23 -5.42 2287.94
2 18 1188 22JUN92 V R4556 1 2304.57 2304.57
22JUN92 V R4557 1 2304.45 2304.45 -0.12 2304.51
2 20 1543 13JAN92 V R4554 1 2343.31 2343.31
13JAN92 V R4555 1 2343.93 2343.93 +0.62 2343.62
2 22 2052 18JUN92 V R4552 1 2380.77 2380.77
18JUN92 V R4553 1 2382.52 2382.52 +1.75 2381.65
2 26 3051 18JUN92 V R4550 1 2403.47 2403.47
18JUN92 V R4551 1 2404.50 2404.50 +1.03 2403.99
2 21- 0S 1 3 62 23AUG91 20JAN92 V S4118 1 2365.81 2365.81
213 150-30W 20JAN92 V S4119 1 2366.34 2366.34 +0.53 2366.08
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TITRATION SYSTEM: FLAGS:
G = GRAVIMETRIC F: No Hg found in bottle
V = VOLUMETRIC X: Titrator malfunction
BOTTLE TYPE: EX: Data excluded from analysis
R = RODAVISS S = S TYPE
NOTE: Dilution factor of 1.000170 has been applied.
