US JGOFS Antarctic Environments Southern Ocean Process Study (AESOPS) Palmer Leg 96-04; Sept. 1996 Documentation file for: THE HYDROGRAPHIC BOTTLE DATA L.A. Codispoti (lou@ccpo.odu.edu) Old Dominion University, January, 1997 General Comments: This "readme" file pertains to the salinity, dissolved oxygen, and nutrient data taken from sampling bottles with the hydrographic rosette that was equipped with 24 ~10-liter "Niskin-like" Bullister Bottles made mostly of PVC and equipped with orange silicone o-rings during Palmer leg 96-04 (Sept. 1996). Dr. Robert Anderson of the Lamont Dougherty Observatory was the chief scientist during this leg (boba@ldeo.columbia.edu). This cruise was the first AESOPS Leg, and its main purpose was to do site surveys for the emplacement of moorings, but a few hydrocasts were taken. Several casts with a Trace Metal clean rosette equipped with 8, 30-l Go-Flo bottles were also taken during this leg, but they are not reported here because this system was not designed to produce hydrographic data of "WOCE quality". For example, the CTD system on this rosette was not capable of the precision obtained from the system on the hydrographic rosette, and Go-Flo bottles, while superior for obtaining trace metal clean samples, are not the bottles of choice for dissolved oxygen values. In addition, the handling system for the Trace Metal rosette was cumbersome and there is the possibility that freezing occurred in the water in the Go-Flo bottles while this rosette was being "wrestled" into its wet lab. Some questionable data are not included in this report. These data together with data from the trace metal casts are retained in files at Old Dominion University and are available upon request. No units are given for salinity in this report because the most recent definitions of salinity define it as a dimensionless number. To accommodate every preference, Winkler oxygen values are reported in ml/l, micromolar, and micromoles per kg. The latter values can only be calculated with a knowledge of the oxygen sample temperatures when the samples were drawn. These "draw temperatures" are not reported here, but can be obtained by contacting lou@ccpo.odu.edu. Nutrient values are reported in micromolar. They can be converted to micromoles per kg, by combining laboratory temperature on the Palmer (approx. 20 deg C during this leg) and the salinity of the sample to compute density and then dividing the value in micromolar by this number. Methods: In general, the methods employed for the bottle salinity, Winkler dissolved oxygen, and nutrient analyses did not differ significantly from those described in the JGOFS protocols that were distributed in 1994 (UNESCO, IOC Manual and Guide #29). Minor differences included the following: 1) Sea Bird CTD systems and bottle carousels were employed (SBE-9+ underwater units, SBE-11 deck units, SBE-32 carousels). These units represent a newer generation of equipment than the units described in the JGOFS protocols. 2) The weights of the salts used for primary standards for dissolved oxygen were not adjusted to an "in vacuo" basis as suggested in the protocols. It is unlikely that this departure from procedure would cause significant errors. Our calculations suggest that the maximum differences arising from our decision to not correct to an "in vacuo" basis would be 0.02% 3) The protocols give one a choice of adjusting nutrient methods so that calibration curves are strictly linear, or opting for more response and taking into account non-linearities. We choose the former method. 4) No corrections were made for "carryover" between nutrient samples run on the Technicon Autoanalyzer. Carryover effects in our nutrient analyses are generally less than ~2% of the concentration difference between adjacent samples, and were minimized by arranging samples in depth order and by running duplicate samples in some cases. 5) Calibration and re-calibration of volumetric ware were not exactly as described in the JGOFS protocols, but this was largely compensated for by comparing independent standards. 6)Duplicate oxygen samples were not routinely drawn. Temperature: The temperature data associated with each bottle depth were taken by the CTD system during the bottle tripping process. Consult the companion CTD data report for this cruise to learn more about the CTD system. Sampling: The samples in this report were taken from ~10 liter Bullister bottles. Because there is little or no lag time between triggering a bottle and bottle closure with the new SeaBird rosette systems, bottles were generally held at the sampling depth for at least 30 seconds before tripping or until the deck read-outs stabilized if this took more than 30 seconds. NOTE THAT THE MID-POINT OF THE SAMPLING BOTTLES WAS 0.8 METER ABOVE THE CTD SENSORS. THE DATA HAVE NOT BEEN CORRECTED FOR THIS OFFSET. Salinity: Salinities were determined with Guildline Autosal salinometers. New vials of standard sea-water were used to standardize before and at the end of every run. Agreement between bottle salinities and the recently calibrated sensors on the Sea Bird CTD systems was usually better than 0.01 (except in regions of strong gradients) before post-cruise data processing which employs the bottle salinities to correct the CTD salinities. More information on the quality of the salinity data are given in the companion CTD report. Both the CTD salinity data at the time of bottle tripping and the salinities run on the Niskin bottle samples with an Autosal salinometer are reported here. NOTE THAT TEMPERATURE CONTROL AND POWER PROBLEMS IN THE AUTOSAL ROOM MAY HAVE SLIGHTLY DEGRADED THE AUTOSAL SALINITY DATA FROM THIS CRUISE AND THAT IT IS POSSIBLE THAT THE ERRORS MAY HAVE, AT TIMES, EXCEEDED THE WOCE STANDARD OF 0.002 FOR AUTOSAL ACCURACY BY A FACTOR OF ~2. Dissolved oxygen: The Winkler dissolved oxygen set-up was built and supplied by the SIO/ODF group. This system is computer controlled and detects the end-point photometrically. Temperature of the thiosulfate and standard solutions is automatically monitored by this system. Nutrients: Note that the terminology used to describe nutrients has become somewhat loose over the years and that silicate=silicic acid or reactive silicate, and phosphate=reactive phosphorus. Nutrient analyses were performed on a 5-channel Technicon II AA system that was modified and provided by Dr. Lou Gordon of Oregon State University. The nutrient standards provided by Dr. Gordon's group were compared with standards from the Ocean Data Facility Group at Scripps and with standards purhased from Ocean Scientific International (OSI). The results of these comparisons were good. Interested users may contact Dr. Louis I. Gordon (lgordon@oce.orst.edu) if they are interested in the details of these intercomparisons. The only notable differences were a tendency for the OSI silicate values to be ~1% high relative to the OSU standards, and 4% low relative to OSU nitrite standards. We believe that the OSI nitrite standards may be in error, but in any event nitrite values in the data reported from this leg were always less than 0.25 micromolar, so the error would be <0.01 micromolar even if the OSI nitrite standards were correct. No ammonium standards were available from OSI for intercomparison, but the ammonium concentrations in the data reported from this leg are all quite low (<0.25 micromolar), so it is unlikely that there will be any significant systematic errors in excess of ~0.01 micromolar. The salinity of the low nutrient sea water used for making standards was monitored during this leg, as were cadmium column efficiences which did not appear to fall below 97.5%. Questions about these data may be addressed to: Dr. L.A. Codispoti CCPO Old Dominion University Norfolk, VA 23529 lou@ccpo.odu.edu