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.

Table 1. Summary of total CO2 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 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  
---------------------------------------------------------------------------------------------------------------------------------- 
   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               
--------------------------------------------------------------------------------------------------------------------
     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.

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