ĐĎॹá>ţ˙ WYţ˙˙˙V˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙˙ěĽÁ3 đż.=bjbjöĘöĘ %Z” ” .9˙˙˙˙˙˙läääääääř‚‚‚‚ Ždř]+öţţţţţţţţÜ*Ţ*Ţ*Ţ*Ţ*Ţ*Ţ*$S, s.Ě+äţţţţţ+R$ääţţ+R$R$R$ţ.äţäţÜ*R$ţÜ*R$ŠR$Ü*ääÜ*ţň  Źńe1ÉřŠ‚,&Ü*Ü*-+0]+Ü*?/R$?/Ü*R$řřääääŮ Celtic Explorer Marine Aerosol Production (MAP) 2006 Cruise Readme File Class of Data: Surface ocean carbon dioxide concentrations Dataset Identifier: MAP_2006 Statement of how to cite dataset: Celtic Explorer MAP 2006 cruise website: http://www.aoml.noaa.gov/ocd/gcc/celtic_explorer 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 the AOML ocean carbon group receives fair credit for our work. Please consult with us prior to use so we can insure that the quality and limitations of the data are accurately represented. Cruise Information: This cruise was part of the Marine Aerosol Production (MAP) program (http://macehead.nuigalway.ie/map/). The Marine Institute’s Research Vessel Celtic Explorer departed Cork, Ireland on June 11, 2006 and returned to Galway, Ireland on July 5, 2006. Underway surface pCO2, temperature, and salinity measurements were made. Scientists responsible for technical quality of dataset: Rik Wanninkhof NOAA/AOML/Ocean Chemistry Division 4301 Rickenbacker Causeway Miami, Florida 33149 Rik.Wanninkhof@noaa.gov Brian Ward National University of Ireland, Galway University Road Galway, Ireland bward@nuigalway.ie Contact person for this dataset: Betty Huss NOAA/AOML/Ocean Chemistry Division 4301 Rickenbacker Causeway Miami, Florida 33149 Betty.Huss@noaa.gov Timestamp for initial submission of dataset: 2006 Timestamp for the most recent update of dataset: 5/15/08 Timestamp period the dataset refers to: 6/15/2006 - 7/05/2006 Geographic area the dataset refers to: 52 N to 58 N 5 W to 15 W List of variables included in this dataset: COLUMN HEADER EXPLANATION 1. GROUP/SHIP: ODU_R/V_CELTIC_EXPLORER. 2. CRUISE_DESIGNATION: MAP_2006 3. JD_GMT: Decimal year day. 4. DATE_DDMMYYYY: The date format has been changed from previous files to conform with the IOCCP recommendations. 5. TIME_HH:MM:SS: GMT time. Local time = GMT + 1. 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 headspace equilibrator at equilibrator temperature (Teq) in parts per million. 9. xCO2A_PPM: Mole fraction of CO2 in air in parts per million. 10. PRES_EQUIL_hPa: Barometric pressure in the lab in hectopascals(1 hectopascal = 1 millibar). 11. PRES_SEALEVEL_hPa: Barometric pressure from ship's barometer, corrected to sea level in hectopascals (1 hectopascal = 1 millibar). 12. EQTEMP_C: Temperature in equilibrator water in degrees centigrade. Temperature in equilibrator measured with a calibrated thermistor. 13. SST(TSG)_C: Temperature from the ship's thermosalinograph in degrees centigrade. 14. SAL(TSG)_PERMIL: Salinity from the ship's thermosalinograph on the Practical Salinity Scale. 15. WATER_FLOW_L/MIN: Water flow through equilibrator in liters per minute. 16. GASFLOW_IR_ML/MIN: Gas flow through the Licor infrared analyzer before the flow is stopped in milliliters per minute. 17. TEMP_IR_C: Temperature of the Licor infrared analyzer sample cell in degrees centigrade. 18. PRES_IR_hPa: Pressure in the Licor infrared analyzer in hectopascals. NOTE: There is no pressure sensor in the Licor but since it is vented to atmosphere prior to measurement, this value is the same as the pressure in the lab (number 10 above). (1 hectopascal = 1 millibar). 19. SHIP_HEADING_TRUE_DEGREE: Ship's heading from ship's navigation system in degrees with 0 = North and 90 = East. 20. SHIP_SPEED_KNOT: Ship's speed from ship's navigation system in knots. 21. fCO2W@SST_uATM: Fugacity of CO2 in sea water in microatmospheres. 22. QC_FLAG_WATER: Quality control flag for sea water xCO2 and fCO2 values with 2 = good value, 3 = questionable value, 4 = bad value, and 9 = no measurement taken. 23. fCO2a_uATM: Fugacity of CO2 in air in microatmospheres. 24. QC_FLAG_AIR: Quality control flag for air xCO2 and fCO2 with 2 = good value, 3 = questionable value, 4 = bad value, and 9 = no measurement taken. 25. dfCO2_uATM: Sea water fCO2 - air fCO2 in microatmospheres. This uses the average air value for the current hour. 26. WIND_SPEED_TRUE_M/S: True wind speed in meters per second. 27. WIND_DIR_TRUE_DEGREE: True wind direction in degrees were 0 = North and 90 = East. The following fields have been QC'ed by the CO2 group: GROUP_SHIP CRUISE JD_GMT DATE_DDMMYYYY TIME_HH:MM:SS LAT_DEC_DEGREE LONG_DEC_DEGREE xCO2W_PPM xCO2A_PPM PRES_EQUIL_hPa EQTEMP_C WATER_FLOW_L/MIN GASFLOW_IR_ML/MIN TEMP_IR_C PRES_IR_hPa fCO2W@SST_uATM fCO2A_uATM QC_FLAG_WATER The following fields are from the ship's onboard systems and the quality of this data cannot be verified: PRES_SEALEVEL_hPa SST(TSG)_C SAL(TSG)_PERMIL SHIP_HEADING_TRUE_DEGREE SHIP_SPEED_KNOT WIND_SPEED_TRUE_M/S WIND_DIR_TRUE_DEGREE 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 from an inlet to the equilibration chamber. The chamber contains a water spray head, an enclosed gaseous headspace (~ 850 ml), and a pool of seawater (~ 750 ml) 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. CALCULATIONS: The mixing ratios of ambient air and equilibrated headspace air are calculated by fitting a second-order polynomial through the hourly averaged 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: fCO2a/eq = xCO2a/eq(P-pH2O)exp(B11+2d12)P/RT where fCO2a/eq is the fugacity in ambient air or 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 (82.0578 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 water in the equilibrator is typically 0.2 +/- 1 °C warmer than sea surface temperature. The empirical temperature correction from equilibrator temperature to SST is outlined in Takahashi et al (1993): fCO2W = fCO2eq Exp(-0.0423 (SST-Teq)) INSTRUMENT DESCRIPTION: The general principle of operation of the instrument 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 6262 analyzer passes IR radiation through two 6" cells. The reference cell is flushed with a gas that passes through beds of soda lime and magnesium perchlorate to remove CO2 and water. The sample cell is flushed with the standard or sample gas. A vacuum-sealed, heated filament is the broadband IR source. The IR radiation alternates between the two cells via a chopping shutter disc spinning at 500 Hertz. Two bandpass optical filters select adsorption bands optimized for CO2 (4.26 micron) and water (2.59 micron) to reach the detector. The solid state (lead selenide) detector is kept at -5 degrees C for excellent stability and low signal noise. To reduce the size of corrections done because of the presence of water vapor, the outside air and equilibrator headspace gas pass through Naphion gas dryers before reaching the IR analyzer. The counter flow gas used in the dryer is ambient air at reduced pressure, which also reduces the partial pressure of water vapor. When operating well, the gas dryer reduces the water content of the gas streams to less than 3 millimole/mole (volume). The infrared analyzer is calibrated regularly with four standard gases (200 - 450 ppm CO2 in air) from Scott-Marrin Inc. (Riverside, CA). Before and after use in the field, the standards are calibrated using primary reference gases from the laboratory of Dr. Charles D. Keeling, which are directly traceable to the WMO scale. After the sample cell is flushed with standard or sample gas, the flow is stopped and multiple readings of the detector response is averaged for the result. The outside air is drawn from an inlet on the 70-foot bow mast. Outside air is constantly being pulled (6 liter/min maximum flow) through ~400 feet of tubing (3/8" OD Dekoron) to the analytical system in the engine room. The seawater is drawn from the sizable flow towards the engine heat exchangers. One stream of seawater goes through a Seabird thermosalinograph that contains temperature and salinity sensors. Another stream of seawater goes to the CO2 equilibrator. The CO2 equilibrator was fabricated using a filter housing (ColeParmer, U-010509-00) with ~0.7 L water reservoir and ~0.8 L gaseous headspace. The seawater enters via a spiral spray head at a flow rate between 1.5 and 2.5 L/min. The headspace gas passes through the IR analyzer and returns to the equilibrator at a flow rate of ~80 ml/min. The headspace is maintained at ambient pressure via a vent connected to a smaller equilibration chamber. This chamber has a seawater spray head that helps ensure that any gas entering the main equilibrator's headspace will be close to its CO2 concentration. The standards used on the cruise are: STANDARD CONCENTRATION STD1 284.59 STD2 387.23 STD3 552.30 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 for fCO2w and for SST at fCO2a. Estimated overall uncertainty of measurement: The xCO2eq measurements are believed accurate to 1 ppm. The fCO2@SST measurements are believed to be precise to 2 ppm. 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 seawater: the solubility of a non-ideal gas. Mar. Chem. 2: 203-215. Takahashi, T., J. Olafsson, J. G. Goddard, D. W. Chipman, and S. C. Sutherland (1993), Seasonal variation of CO2 and nutrients in the high-latitude surface oceans: a comparative study, Global Biogeochem. Cycles, 7, 843-878. Data QC: From the start of the cruise (JD 166.38 to JD 171.82), no reliable SST were logged. 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