ĐĎॹá>ţ˙ y{ţ˙˙˙x˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙ěĽÁ3 đżSbjbj}+}+ &~AAO˙˙˙˙˙˙l*`+`+`+`+ l+”*nK> , , , , , , , ,ËJÍJÍJÍJÍJÍJÍJ$ŹL ĚNÄńJ , , , , ,ńJ¨7 , ,K,¨7¨7¨7 ,ň , ,ËJ¨7 ,ËJ¨7¨7Ŕ>ŽIhËJ ,, `Ř,”VrČ*6*`+ţ.Ş÷IËJ2K<nKJĐO¨7OËJ¨7**Ů R/V Ronald H. Brown METADATA - 1997 Class of Data: Surface ocean and atmospheric carbon dioxide concentrations Dataset Identifier: R/V Ronald H. Brown One File: RHB1997 Statement of how to cite dataset: Ron Brown website: http://www.aoml.noaa.gov/ocd/gcc/rvbrown_data1997.php These data are made freely available to the public and the scientific community in the belief that their wide dissemination will lead to greater understanding and new scientific insights. The availability of these data does not constitute publication of the data. We rely on the ethics and integrity of the user to assure that AOML receives fair credit for our work. Please send manuscripts using this data to AOML for review before they are submitted for publication so we can insure that the quality and limitations of the data are accurately represented. Measurement platform identifier: NOAA research vessel Ronald H. Brown (R104) Cruise Information: The Ron Brown was commissioned in July, 1997 and conducted 2 research cruises in the eastern Pacific. Also included is data from the transit from the Pacific to the ship’s home port of Charleston, S.C. Project Information: The system was permanently installed on the Ron Brown before the ship was commissioned and has in most cases been operated by ship’s personnel. The work was sponsored by the Underway pCO2 on Ships project of the NOAA climate program. Scientist responsible for technical quality of dataset: Rik Wanninkhof NOAA/AOML/Ocean Chemistry Division 4301 Rickenbacker Causeway Miami, Florida 33149 Rik.Wanninkhof@noaa.gov Contact person for this dataset: Bob Castle NOAA/AOML/Ocean Chemistry Division 4301 Rickenbacker Causeway Miami, Florida 33149 Robert.Castle@noaa.gov Timestamp for initial submission of dataset: 02/15/08 Timestamp for the most recent update of dataset: 02/18/08 Timestamp period the dataset refers to: 7/28/1997 – 11/14/1997 Geographic area the dataset refers to: 6 N to 47 N 131 W to 79 W 1997 Cruises: RB199701 – PACS Leg 1 Panama Canal to San Diego, CA July 28, 1997 to August 28, 1997 Chief Scientist – Sandra Yuter Operator – Bob Castle RB199702 - PACS Leg 2 San Diego, CA to San Diego, CA August 29, 1997 to September 6, 1997 Chief Scientist – Sandra Yuter Operator – Bob Castle RB199703 - VENTS Leg 1 San Diego, CA to Newport, OR September 12, 1997 to September 16, 1997 Chief Scientist – Christopher Fox Operator – Marilyn Roberts RB1997094 - VENTS Leg 2 Newport, OR to Newport, OR September 20, 1997 to October 5, 1997 Chief Scientist – Christopher Fox Operator – Dana Greeley RB199705 - VENTS Leg 3 Newport, OR to San Francisco, CA October 11, 1997 to October 25, 1997 Chief Scientist – Gary Massoth Operator – Marilyn Roberts RB199706 - Transit Leg 1 San Francisco, CA to San Diego, CA October 29, 1997 to October 31, 1997 Chief Scientist – None Operator – Jonathan Shannahoff RB199707 - Transit Leg 2 San Diego, CA to Panama Canal November 1, 1997 to November 10, 1997 Chief Scientist – None Operator – Jonathan Shannahoff RB199707 - Transit Leg 3 Panama Canal to Key West, FL November 11, 1997 to November 14, 1997 Chief Scientist – None Operator – Jonathan Shannahoff List of variables included in this dataset: COLUMN HEADER EXPLANATION 1. GROUP/SHIP: AOML_Brown for all underway data from the Ron Brown. 2. CRUISE_DESIGNATION: Cruise ID (e.g., RBYYYYnn where RB = Ron Brown, YYYY = the four digit year, and nn = the cruise number for that year). 3. JD_GMT: Decimal year day. 4. DATE_DDMMYYYY: GMT date. The date format has been changed to comply with the IOCCP recommendations. 5. TIME_HH:MM:SS: GMT time. 6. LAT_DEC_DEGREE: Latitude in decimal degrees (negative values are in the southern hemisphere). 7. LONG_DEC_DEGREE: Longitude in decimal degrees (negative values are in the western hemisphere). 8. xCO2W_PPM: Mole fraction of CO2 (dry) in the equilibrator headspace at equilibrator temperature (Teq) in parts per million. 9. xCO2A_PPM: Mole fraction of CO2 in air in parts per million. 10. EqTEMP_C: Temperature in equilibrator water in degrees centigade. Temperature in equilibrator measured with a calibrated thermistor. 11. PRES_EQUIL_hPa: Barometric pressure in the lab in hectopascals (1 hectopascal = 1 millibar). 12. SST(TSG)_C: Temperature from the ship's thermosalinograph in degrees centigrade. 13. SAL(TSG)_PERMIL: Salinity from the ship's thermosalinograph on the Practical Salinity Scale. 14. fCO2w,eq: Fugacity of CO2 in the equilibrator in microatmospheres calculated as outlined below. 15. fCO2W@SST_uatm: Fugacity of CO2 in sea water in microatmospheres calculated as outlined below. 16. fCO2A_uATM: Fugacity of CO2 in air in microatmospheres calculated as outlined below. 17. dfCO2_uatm: Sea water fCO2 - air fCO2 in microatmospheres. This uses the average air value for the current hour. The following fields have been QC'ed by the CO2 group: GROUP/SHIP CRUISE_DESIGNATION JD_GMT DATE_DDMMYYYY TIME_HH:MM:SS LAT_DEC_DEGREE LONG_DEC_DEGREE xCO2W_PPM xCO2A_PPM EqTEMP_C PRES_EQUIL_hPa fCO2w,eq fCO2W@SST_uatm fCO2A_uATM dfCO2_uatm The following fields are from the ship's onboard systems and the quality of this data cannot be verified: SST(TSG)_C Sal(TSG)_Permil Narrative description of system design: CO2 ANALYTICAL SYSTEM: The concentration of carbon dioxide (CO2) in surface ocean water is determined by measuring the concentration of CO2 in gas that is in contact with the water. Surface water is pumped ~ 100 m through 7/8" Teflon tubing from an inlet in the ship's bow to the equilibration chamber. Water comes from the bow intake ~4.2 m below the water line and the TSG is located close to the inlet. When the SST is below about 20 oC, friction in the pipes and from the pump cause heating and the Teq is higher than SST. When the SST is higher than about 25 oC, the ship’s air conditioning cools the water and the Teq is lower than SST. The equilibration chamber has an enclosed volume of gas, or headspace, and a pool of seawater that continuously overflows to a drain. As the water flows through the chamber, the dissolved gases (like CO2) partition between the water and the headspace. At equilibrium, the ratio of CO2 in the water and in the headspace is influenced most by temperature, and that relationship is known. By measuring the concentration of CO2 in the headspace and the temperature in the chamber, the partial pressure (or fugacity) of CO2 in the surface water can be calculated. INSTRUMENT DESCRIPTION The general principle of instrumental design can be found in Wanninkhof and Thoning (1993), Ho et al. (1995), and Feely et al. (1998). The concentration of CO2 in the headspace gas is measured using the adsorption of infrared (IR) radiation, which results from changes in the rotational and vibrational energy state of the CO2 molecule. The LI-COR detector passes IR radiation through two 6" cells. The reference cell is flushed with a gas of known CO2 concentration. The sample cell is flushed with the headspace gas. A vacuum-sealed, heated filament is the broadband IR source. The IR radiation alternates between the two cells via a chopping shutter disc. An optical filter selects an adsorption band specific for CO2 (4.26 micron) to reach the detector. The solid state (lead selenide) detector is kept at -12 degrees °C for excellent stability and low signal noise (less than 0.2 ppm). Several steps are taken to reduce interferences and to increase the accuracy of the measurements. After the equilibration chamber, the headspace travels through a drying trap to remove water vapor. During each analysis, the headspace gas is compared to a reference gas of known concentration. To improve the accuracy of the measurements, three different gaseous standards for CO2 are analyzed once an hour instead of the headspace gas. Analyzer: LI-COR 6251 (analog output) infrared (IR) analyzer. Method of Analysis: Differential analyses relative to the low standard. Measures dried equilibrator headspace gas. Gas flow is stopped prior to IR readings. Drying Method: The equilibrator headspace sample gas first goes through a glass condenser cooled to ~ 5 oC. The sample and standard gases pass through a short column of magnesium perchlorate before reaching the analyzer. Equilibrator (setup, size, flows): The equilibrator is based on a design by R. Weiss and was fabricated from a plexiglass housing with ~8 L water reservoir and ~16 L gaseous headspace. Water flow rate is ~11 L/min. Headspace recirculation rate is ~200 ml/min. Additional sensors: Thermistor mounted in the bottom of the equilibrator. Setra Barometer Model 370 YSI Model 600R thermosalinograph with temperature, salinity, and dissolved oxygen sensors. This TSG is mounted in the Hydro lab sink near the equilibrator and the two are teed off the uncontaminated seawater feed. The dissolved oxygen measurements are not reported in the final data file. Narrative statement identifying measurement method for each required parameter: CALCULATIONS: The mixing ratios of ambient air and equilibrated headspace air are calculated by fitting a second-order polynomial through the hourly averaged millivolt response of the detector versus mixing ratios of the standards. Mixing ratios of dried equilibrated headspace and air are converted to fugacity of CO2 in surface seawater and water saturated air in order to determine the fCO2. For ambient air and equilibrator headspace, the fCO2a (or fCO2eq) is calculated assuming 100% water vapor content: fCO2eq = xCO2eq(P-pH2O)exp(B11+2*d12)P/RT where fCO2eq is the fugacity in the equilibrator, pH2O is the water vapor pressure at the sea surface temperature, P is the atmospheric pressure (in atm), T is the SST or equilibrator temperature (in K) and R is the ideal gas constant (82.057 cm^3ˇatmˇdeg^-1ˇmol^-1). The exponential term is the fugacity correction where B11 is the second virial coefficient of pure CO2 B11 = -1636.75 + 12.0408T - 0.032795T^2 + 3.16528E-5 T^3 and d12 = 57.7 - 0.118 T is the correction for an air-CO2 mixture in units of cm^3ˇmol^-1 (Weiss, 1974). The calculation for the fugacity at SST involves a temperature correction term for the increase of fCO2 due to heating of the water from passing through the pump and through 5 cm ID PVC tubing within the ship. The empirical temperature correction from equilibrator temperature to SST is: fCO2(SST) = fCO2(eq) / Exp ((Teq-SST) * [0.03107 – 2.7851E-4 * Teq – 1.8391E-3 * ln(fco2eq * 1.0E-6)]) where SST is sea surface temperature and Teq is the equilibrator temperature in degrees °C. Sampling Cycle: The system runs on an hourly cycle during which 3 standard gases, 3 air samples from the bow tower and 8 surface water samples (from the equilibrator head space) are analyzed on the following schedule: Mins. after hour Sample 4 Low Standard 8 Mid Standard 12 High Standard 16.5 Water 21 Water 25.5 Water 30 Water 34 Air 38 Air 42 Air 46.5 Water 51 Water 55.5 Water 60 Water NOTES ON DATA: Columns have a default value of –999.99 in case of instrument malfunction, erroneous readings or missing data. Furthermore, if a suspicious xCO2 value, pressure or temperature value is encountered, the fCO2 is not calculated. Analytical Instrument Manufacturer/Model: The Ron Brown system (version 2.5) was an in-house prototype built by Jason Masters, Mike Shoemaker, and Bob Castle in 1997. The analyzer is a LI-COR 6251 (analog output) infrared analyzer. Standard Gases and Reference Gas: The three standard gases came from CMDL in Boulder and are directly traceable to the WMO scale. While individual data points above the high standard gas concentration or below the low standard gas concentration may not be accurate, the general trends should be indicative of the seawater chemistry. Description of any additional environmental control: The system is located in the Hydro Lab of the Ron Brown. The room is air-conditioned with little temperature fluctuation. Resolution of measurement: The resolution of the instrument is better than 0.1 ppm. Estimated overall uncertainty of measurement: The xCO2eq measurements are believed accurate to 0.1 ppm. The fCO2@SST measurements are believed to be precise to 0.2 ppm. List of calibration gases used: The standards used on all 1997 cruises are: STANDARD TANK # CONCENTRATION VENDOR STD1 N/A 300.45 CMDL STD2 N/A 343.11 CMDL STD3 N/A 431.31 CMDL Traceability to an internationally recognized scale (including date/place of last calibration made): All standards are obtained from NOAA/CMDL, now called the Global Monitoring Division of the Earth Research Laboratory and are directly traceable to WHO scale. Uncertainty of assigned value of each calibration gas: The uncertainty based on pre and post cruise calibrations is less than 0.05 ppm. Pressure/Temperature/Salinity: For information about the ship’s thermosalinograph, contact Chief Survey Tech Jonathan Shannahoff at jonathan.shannahoff@noaa.gov. Units: All xCO2 values are reported in parts per million (ppm) and fCO2 values are reported in microatmospheres (uatm) assuming 100% humidity at the equilibrator temperature. Bibliography: DOE (1994). Handbook of methods for the analysis of the various parameters of the carbon dioxide system in sea water; version 2. DOE. Feely, R. A., R. Wanninkhof, H. B. Milburn, C. E. Cosca, M. Stapp and P. P. Murphy (1998). A new automated underway system for making high precision pCO2 measurements onboard research ships. Analytica Chim. Acta 377: 185-191. Ho, D. T., R. Wanninkhof, J. Masters, R. A. Feely and C. E. Cosca (1997). Measurement of underway fCO2 in the Eastern Equatorial Pacific on NOAA ships BALDRIGE and DISCOVERER, NOAA data report ERL AOML-30, 52 pp., NTIS Springfield. Wanninkhof, R. and K. Thoning (1993). Measurement of fugacity of CO2 in surface water using continuous and discrete sampling methods. Mar. Chem. 44(2-4): 189-205. Weiss, R. F. (1970). The solubility of nitrogen, oxygen and argon in water and seawater. Deep-Sea Research 17: 721-735. Weiss, R. F. (1974). Carbon dioxide in water and seawater: the solubility of a non-ideal gas. Mar. Chem. 2: 203-215. Weiss, R. F., R. A. Jahnke and C. D. Keeling (1982). Seasonal effects of temperature and salinity on the partial pressure of CO2 in seawater. Nature 300: 511-513. Comments related to all 1997 data: 1. xCO2 values outside the range of the standard gases (i.e. below 300.45 ppm or above 431.31 ppm) are not as accurate as values within the range. However, the general trends should be indicative of the seawater chemistry. 2. Data from the ship’s computer system (SST and salinity) were merged into the underway system’s data file with an approximate 3 minute delay factor. This is to account for the time it takes for sea water to travel from the bow intake to the equilibrator in the Hydro Lab. 3. The Valco valve that routes the various gases to the LI-COR moved to the wrong position about 1.5% of the time causing the wrong gas to be passed through the analyzer. When this occurred during a headspace or atmospheric gas measurement, the value was marked bad and removed from the final data file. When this occurred during a standard gas phase, the voltage response of the standard gas was interpolated using the values from the preceding and following hours. 4. The equation used to convert the equilibrator thermistor voltage to temperature was incorrect, resulting in values that were approximately 0.9 degrees too high. In addition, relay closures affected the voltage readings from the thermistor. To obtain correct equilibrator temperature readings, we assumed that the YSI TSG temperature was the same as the equilibrator temperature since both sample sea water from the same source in the Hydro Lab. However, the YSI TSG temperature readings are known from calibration data to be about 0.2 degrees high. We therefore determined a corrected YSI temperature by using calibration data to fit a linear equation relating observed YSI temperature to actual temperature as given by a Guildline platinum resistance thermometer (New YSI T = 1.0026885 * Old YSI T – 0.272854). A new equation relating thermistor voltage to the corrected YSI T was then determined using all the data from leg 2 of the PACS 1997 cruise (T = 6.0955*V^3 -46.862*V^2 + 101.16V - 28.638. Comments related to the individual legs: RB199701: 1. The system was shut down 3 times – for 45 minutes on 8/5/97, for 2 hours on 8/18/97, and for 2 hours on 8/20/97. 2. The seawater intake on the Ron Brown was switched from 4.2 to 2.2 meters on 8/9/97 at 1500 and switched back to 4.2 m on 8/23/97 at 2230. 3. After spending most of the cruise on station at 7.8 N, 125 W, the ship was forced to go to San Diego for a medical evacuation operation. The system was stopped for a short time and when data collection resumed, leg 3 began. RB199702: 1. The first ~ 27 hours of data were removed due to a clogged valve. The good data begins on August 31. RB199703: 1. Misalignment of the Valco valve resulted in low gas flows in the standard 3, standard 1, and air phases. This problem was especially bad during the last 2 days of the cruise. To correct them, I computed the average LI-COR voltage in both the standard 1 and standard 3 phases when gas flow exceeded 30 ml/min. Whenever possible, I interpolated bad values in these phases using the previous and next good values in the appropriate phase. However, when more than 2 consecutive values were bad, I replaced the bad values with the computed average value. In several air phases, I deleted the first air value of the group due to incomplete flushing of the LI-COR sample cell. RB199704: 1. There was no data from the ship’s computer system for the first two hours of the leg, so I computed SST and salinity for that time period from the equilibrator temperature and YSI salinity respectively. The YSI salinity data contained some sharp drops which I believe were due to low flow through the YSI cell. I removed the first few of these "dropouts" and interpolated the missing values. Then I did a linear curve fit on the first 11 days of good salinity data and on all the temperature data to derive equations relating YSI salinity to SCS salinity and equilibrator temperature to SCS temperature. I used these computed values for the first 2 hours of missing SCS data. The equation for SCS temperature was: SCS T = 1.236951 * Eq T - 4.612866 with R^2 = 0.996192. The equation for salinity was SCS S = 0.990094 * YSI S + 0.385682 with R^2 = 0.984214. RB199705: 1. There was a high differential between sea surface temperature and equilibrator temperature that ranged from 0.5 degrees at an SST of 16.5 to 2 degrees at an SST of 12.5. I attribute this to the relatively low sea surface temperature that resulted in a greater degree of warming while the water was transported from the bow intake to the Hydro lab near the ship's stern. RB199706: 1. For the first day of this leg, gas flow in the water phase was low. This may affect some of the water xCO2 values slightly, but it should be limited to the first measurement in each group of four water readings. RB199707: 1. We received no data from the ship's computer system (SCS) for the first 10 hours of this leg. For this time period we computed sea surface temperature and salinity from equilibrator temperature and the YSI TSG salinity sensor respectively. The equations used were: SCS temperature = (1.02205 * Equilibrator temperature) - 0.44594 and SCS salinity = (1.00754 * YSI salinity) - 0.16921. 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