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Carbon Dioxide, Hydrographic, and Chemical Data Obtained During the R/V Ronald H. Brown Repeat Hydrography Cruise in the Atlantic Ocean: CLIVAR CO2 Section A16S_2005 (11 January - 24 February, 2005)
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Contributed by
R. Wanninkhof,1 S.C. Doney,2 E. Peltola,1 R.D. Castle,1 F.J. Millero,4 J.L. Bullister,3 D.A. Hansell,4 M.J. Warner,5 C. Langdon,4 G.C. Johnson,3 and C.W. Mordy3
Prepared by
Alexander Kozyr
Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, Oak Ridge, Tennessee, U.S.A.
1Atlantic Oceanographic and Meteorological Laboratory, NOAA, Miami, FL
2Woods Hole Oceanographic Institution, Woods Hole, MA
3Pacific Marine Environmental Laboratory, NOAA, Seattle, WA
4Rosenstiel School of Marine and Atmospheric Science, University of Miami, Miami, FL
5University of Washington, Seattle, WA
- Abbreviations and Acronyms
- Abstract
- 1. Background Information
- 2. Description of the Expedition
- 3. Description of Variables and Methods
- 4. How to Obtain the Data and Documentation
- 5. References
Abbreviations and Acronyms
|Atlantic Oceanographic and Meteorological Laboratory
|Brookhaven National Laboratory
|Carbon Dioxide Information Analysis Center
|Climate Variability (Program)
|carbon dioxide
|certified reference material
|conductivity, temperature, and depth sensor
|dissolved organic carbon
|U.S. Department of Energy
|expedition code
|fugacity of CO2
|Global Climate Observing System
|Global Change Research Program
|Global Ocean Observing System
|Joint Global Ocean Flux Study
|Lowered acoustic Doppler current profiler
|Lamont-Doherty Earth Observatory
|multilinear regression
|numeric data package
|nondispersive infrared analyzer
|National Oceanic and Atmospheric Administration
|National Science Foundation
|Oak Ridge National Laboratory
|partial pressure of CO2
|Pacific Marine Environmental Laboratory
|quality assurance
|quality control
|Rosenstiel School of Marine and Atmospheric Science
|research vessel
|Scripps Institution of Oceanography
|single-operator multi-parameter metabolic analyzer
|sea surface temperature
|total alkalinity
|total organic carbon
|total nitrogen
|total inorganic carbon
|University of California, Irvine
|University of Washington
|WOCE Hydrographic Program
|World Ocean Circulation Experiment
Wanninkhof, R., S.C. Doney, E. Peltola , R.D. Castle, F.J. Millero, J.L. Bullister, D.A. Hansell, M.J. Warner, C. Langdon, G.C. Johnson, and C.W. Mordy. 2006. Carbon Dioxide, Hydrographic, and Chemical Data Obtained During the R/V Ronald H. Brown Repeat Hydrography Cruise in the Atlantic Ocean: CLIVAR CO2 Section A16S_2005 (11 January - 24 February, 2005), ed. A. Kozyr. ORNL/CDIAC-151, NDP-087. Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, U.S. Department of Energy, Oak Ridge, Tennessee, 38 pp. doi: 10.3334/CDIAC/otg.ndp087.
This report presents methods, and analytical and quality control procedures for salinity, oxygen, nutrient, inorganic carbon, organic carbon, chlorofluorocarbon (CFC), and bomb 14C system parameters performed during the A16S_2005 cruise, which took place from January 11 to February 24, 2005, aboard research vessel (R/V) Ronald H. Brown under the auspices of the National Oceanic and Atmospheric Administration (NOAA). The R/V Ronald H. Brown departed Punta Arenas, Chile, on January 11, 2005, and ended its cruise in Fortaleza, Brazil, on February 24, 2005. The research conducted was one of a series of repeat hydrography sections jointly funded by NOAA and the National Science Foundation as part of the CLIVAR/CO2/repeat hydrography/tracer program. Samples were taken from 36 depths at 121 stations.
The data presented in this report include the analyses of water samples for total inorganic carbon (TCO2), fugacity of CO2 (fCO2), total alkalinity (TALK), pH, dissolved organic carbon (DOC), CFC, 14C, hydrographic, and other chemical measurements.
The R/V Ronald H. Brown A16S_2005 data set is available free of charge as a numeric data package (NDP) from the Carbon Dioxide Information Analysis Center (CDIAC). The NDP consists of the oceanographic data files and this printed documentation, which describes the procedures and methods used to obtain the data.
Keywords: carbon dioxide, total CO2, total alkalinity, pH, fugacity of CO2, carbon cycle, coulometry, potentiometry, hydrographic measurements, CLIVAR, Atlantic Ocean
1. Background Information
The cruise of research vessel (R/V) Ronald H. Brown along section A16S from Punta Arenas, Chile, to Fortaleza, Brazil, was the second in the National Oceanic and Atmospheric Administration (NOAA) -led contributions to a series of repeat hydrography cruises to measure decadal changes in circulation, heat and fresh water budgets, and carbon inventory in the ocean. The cruises repeat a subset of the World Ocean Circulation Experiment Hydrographic Program (WHP) and Joint Global Ocean Flux Study (JGOFS) lines occupied in each major ocean basin in the 1990s.
The WOCE/WHP program is driven by the need to monitor the increases in carbon dioxide (CO2) in the ocean and provide the necessary data to support continuing model development that will lead to improved forecasting skills for oceans and global climate. During the 1990s, the WOCE/JGOFS survey provided a full-depth baseline data set against which to measure future changes. By integrating the scientific needs of programs requiring measurement of the full water column, major synergies and cost savings are achieved. These measurements are of importance both for major research programs, such as Climate Variability (CLIVAR) and the U.S. Global Climate Research Project (GCRP) Ocean Carbon and Climate Change Program (OCCC), and for operational activities such as the Global Ocean Observation System (GOOS) and the Global Climate Observing System (GCOS). As outlined in the program documentation, one component of a global observing system for the physical climate/CO2 system should include periodic observations of hydrographic variables, CO2 system parameters, and other tracers. The large-scale observation component of the OCCC program has a need for systematic observations of the invasion of anthropogenic carbon in the ocean that is superimposed on a variable natural background. The five topical areas addressed by the CO2/CLIVAR repeat hydrography program are:
- carbon system studies;
- heat and freshwater storage and flux studies;
- deep and shallow water mass and ventilation studies;
- calibration of autonomous sensors; and
- data for model calibration.
A hydrographic survey consisting of a meridional lowered acoustic Doppler current profiler (LADCP)/conductivity, temperature, and depth (CTD)/rosette section in the western South Atlantic was carried out in January - February 2005 (see also Wanninkhof and Doney, 2005 for additional cruise details). The R/V Ronald H. Brown departed Punta Arenas, Chile on 11 January 2005. Starting from 60°S, a total of 121 LADCP/CTD/Rosette stations were occupied (see Fig. 1.1) and 12 Argo floats and 11 drifters were deployed from 17 January - 21 February. Up to thirty-six water samples and continuous LADCP, CTD, and bio-optical data were collected on each cast to within 20 m of the bottom. Station spacing was nominally 0.5° of latitude except near the continental slope of South Georgia Island where a shorter station spacing was used to resolve boundary currents. Fewer than 36 discrete water samples were also collected on the shallow, continental slope stations as well as for some of the early stations due to heavy weather conditions. Salinity, dissolved oxygen, and nutrient samples were analyzed from every bottle sampled on the rosette. Other parameters from the bottles were sampled at a lower density. The cruise ended in Fortaleza, Brazil, on 24 February 2005.
This data report focuses on the measurements of total inorganic carbon or dissolved inorganic carbon (TCO2 or DIC), fugacity of CO2 (fCO2), total alkalinity (TALK), pH, dissolved organic carbon (DOC), chlorofluorocarbons (CFC-11 and CFC-12), 14C, nitrate (NO3), nitrite (NO2), phosphate (PO4), silicate (SiO4), and dissolved oxygen (O2).
The methodology, instrumentation, and standardization of these parameters improved significantly during the WOCE/JGOFS era. Notable developments include release of manuals detailing the analytical methods and operating protocols (DOE 1994). Certified reference materials (CRMs) are now available for TCO2 and TALK, which are run interspersed with samples to determine calibration offsets. For this cruise, the TALK and TCO2 values were adjusted to account for the small difference between the CRMs run at sea and the certified value determined at Scripps Institution of Oceanography (SIO). The TCO2 coulometers were calibrated daily by injecting aliquots of pure CO2 (99.995%). The stability of each coulometer cell solution was confirmed with the analyses of several CRMs each day.
Fig. 1. Cruise track for the Atlantic Ocean A16S_2005 cruise in January - February 2005.
Instrumentation has improved in the last decade. Alkalinity measurements can be done with better precision through automation and close checks of the response of electrodes. Burettes are independently calibrated, and the preparation of titrant (hydrochloric acid) has undergone improved quality control and standardization (Millero et al. 1998). Measurement of pH is now done with extreme precision with spectrophotometric methods (Byrne and Breland 1989). The TCO2 measurements are done by coulometry, a precise integrative method. During the A16S_2005 cruise two single-operator multiparameter metabolic analyzers (SOMMAs) (Johnson et al. 1999) were utilized for analyses, which facilitated a sample throughput of up to 80 samples per day. The fCO2 measurements were done with an equilibration system described in Wanninkhof and Thoning (1993). Oxygen measurements were performed by Winkler titrations (Carpenter 1965) with photometric endpoint detection (Friederich, Sherman, and Codispoti 1984).
The data underwent careful quality assurance and quality control (QA/QC) both during and after the cruise. The precision of the measurements was determined from duplicate sampling and comparison of data from deep water, where little variability is expected. Outliers in the data were flagged based on several methods utilizing prior knowledge of the trends and known relationships between parameters. Depth profiles for each parameter were scrutinized for outliers. When deviations were observed, other parameters were assessed to determine whether they showed deviations as well. Inorganic carbon system parameters were linked through physical and chemical properties. In particular, if two of the four carbon system parameters are measured, the other two can be calculated, provided that the silicate concentration, the phosphate concentration, the temperature, and the salinity of the sample are known. These so-called internal consistency calculations were used to assess the difference between calculated and measured values. When the difference between the measured TALK and the TALK calculated from TCO2 and pH or fCO2 exceeded 10 µmol/kg, the three parameters were scrutinized and compared with other parameters to assess whether the datum should be labeled as questionable. Other techniques, described in detail below, include regional multi-linear regressions (MLR) between the inorganic carbon parameters and physical and chemical parameters known to correlate with them [for instance, TCO2 = f(T, S, AOU, Si, PO4)]. Again, the differences between measured and calculated parameters were inspected. Finally, the parameters were plotted against latitude for narrow depth intervals. Since changes along depth horizons are usually gradual, anomalies can be easily spotted and flagged.
This report describes procedures and methods for hydrographic measurement and the analytical procedures, calculations, and assessment of precision for nutrient, oxygen, TCO2, TALK, fCO2, pH, CFCs, 14C, and DOC measurements. A description of the QA/QC methods based on internal consistency of these parameters and the MLR technique is also provided.
2. Description of the Expedition
2.1 R/V Ronald H. Brown: Technical Details and History
The NOAA ship R/V Ronald H. Brown, a state-of-the-art oceanographic and atmospheric research platform, is the largest vessel in the NOAA fleet. With its highly advanced instruments and sensors, R/V Ronald H. Brown travels worldwide supporting scientific studies to increase our understanding of the worlds oceans and climate. Commissioned on July 19, 1997, in its home port of Charleston, South Carolina, Ronald H. Brown has sailed in the Pacific, Atlantic, and Indian Oceans. The ship was named in honor of former Secretary of Commerce Ronald H. Brown, who was killed in a plane crash on April 3, 1996, while on a trade mission to Bosnia. R/V Ronald H. Brown is operated by NOAA Marine and Aviation Operations and carries a complement of 6 NOAA Corps officers, 20 crew members, and a maximum of 33 scientists. Table 2.1. provides a detailed description of the ship.
3. Description of Variables and Methods
3.1 Hydrographic Measurements
Samples for CFCs, helium isotopes (3He), oxygen (O2), hydrochlorofluorocarbon (HCFCs), partial pressure of CO2 (pCO2), TCO2, hydrogen ion activities (pH), TALK, radiocarbon (Δ14C), tritium, DOC, chromophoric dissolved organic matter (CDOM), particulate inorganic/organic carbon (PIC/POC), salinity, and nutrients were drawn in this sequence from a CTD sampling package containing thirty-six 12-L Bullister bottles. A detailed descriptions of methods for the CTD data, LADCP data and biooptical data are given in Wanninkhof and Doney (2005). Oxygen, nutrient, and salinity samples were taken from all bottles. Oxygen draw temperature readings were commenced after station 25. For the other parameters, not all stations or all bottles were sampled. The stations at full degrees of latitude (odd numbered stations) were generally completely sampled for CFCs, TCO2, pH, and TALK, with partial sampling for DOC and CDOM. The half-degree stations were partially sampled for HCFC, PIC/POC, CFCs, TCO2, pH, and TALK. Discrete pCO2 profiles were obtained at every two degrees. 3He, Δ14C, and tritium were sampled at different intervals (primarily at full-latitude stations).
A total of 4174 bottle salinity samples were taken during the cruise, of which 127 were flagged as questionable and 3 as bad. Two samples were lost during analysis. Samples were drawn from the 12-L Bullister bottles into 250-mL Kimax borosilicate bottles. The bottles were rinsed at least three times before being filled to approximately 220 mL. A plastic insert and Nalgene cap were used to seal the sample in the bottle. At the conclusion of sampling, the time was noted and samples were placed into the salinometer lab so they could equilibrate to room temperature. Samples were analyzed after a period of at least 10 hours and typically not more than 24 hours from the time of sampling. Samples were run on a Guildline 8400B Laboratory Salinometer, serial number 60843. The salinometer had been last calibrated at Guildline in January of 2004. IAPSO Standard Seawater was used to standardize the instrument. The software used (ASALW) was developed at Scripps Institution of Oceanography. As per the instructions provided in the software, the cell was rinsed at least two times with sample at a relatively fast flow rate; the flow was adjusted to a slower rate for the final fill, and a reading was taken. The cell was drained and slowly filled for a second reading. If the two readings agreed within 0.00005, the values were accepted; otherwise, an additional reading was required. PSS-78 salinity (UNESCO, 1981) was calculated. Corrections were applied to the data for differences between beginning and ending standards.
Samples for dissolved oxygen analyses were drawn from 12-L Bullister bottles into calibrated 140-mL iodine titration flasks using Tygon tubing with silicone adapters that fit over the petcock to avoid contamination of DOC samples. Bottles were rinsed twice and filled from the bottom, then overflowed three volumes (care was taken to avoid entraining any bubbles). One-mL of MnCl2 and one-mL of NaOH/NaI were added, then the flask was stoppered and shaken. Deionized water was added to the neck of each flask to create a water seal. The flasks were stored in the lab in plastic totes at room temperature for 12 hours before analysis. A total of 4659 samples were analyzed during the cruise, of which 37 samples were flagged as questionable and 4 as bad. Three samples were not reported. The whole-bottle titration technique of Carpenter (1965) was performed with modifications by Culberson et al. (1991), but with a more dilute solution of thiosulfate (10 g/L). Dissolved oxygen analyses were performed with a Monterey Bay Aquarium Research Institute (MBARI)-designed automated oxygen titrator using photometric end-point detection based on the absorption of 365-nm wavelength ultra-violet light. The titration of the samples and the data logging were controlled by a 386 PC running the oxygen program written by Gernot Friedrich (Friederich et al. 1984). Thiosulfate was dispensed by a Dosimat 665 fitted with a 5.0-mL burette. The autotitrator and Dosimat performed well.
Dissolved nutrient (phosphate, silicic acid, nitrate, and nitrite) samples were drawn in 40-mL HDPE Boston Round sample bottles that had been stored in 10% HCl and rinsed four to five times with sample before filling. A replicate was always drawn from the deep bottle for analysis on the subsequent station. All samples were brought to room temperature prior to analysis. A separate analytical run was conducted at each station (except for the shallowest stations). An analytical run consisted of blanks and working standards, old working standards, deep water from the previous station, samples analyzed from deep to surface, replicate analysis of the four deep samples and any problem samples, and finally the working standards and blanks. The blanks were deionized water, and the standards were a zero standard in Low Nutrient Seawater (LNSW) and a high standard. Linearity of the autoanalyzer was checked every ten days, and corrections for non-linearity were applied during final data reduction.
All nutrients were measured using automated continuous flow analysis with a segmented flow and colorimetric detection. The four-channel autoanalyzer was customized using components from various systems. The major components were an Alpkem 301 sampler, two 24-channel Ismatek peristaltic pumps, four Thermo-Separation monochrometers, and custom software for digitally logging and processing the chromatographs. Glass coils and tubing from the Technicon Autoanalyzer II were used for analysis of phosphate, and micro-coils from Alpkem were used for the other three analyses. The detailed methods are described by Gordon et al. (1993). Because pump tubing destined for the cruise was lost in transit, some of the pump tube sizes suggested in the manual had to be modified. Pump tubes were changed four times during the expedition.
Silicic acid was analyzed using a modification of Armstrong et al. (1967). An acidic solution of ammonium molybdate was added to a seawater sample to produce silicomolybic acid. Oxalic acid was added to inhibit a secondary reaction with phosphate. Finally, the reduction with ascorbic acid formed the blue compound silicomolybdous acid. The color formation was detected using a 6-mm flowcell at 660 nm. The use of oxalic acid and ascorbic acid (instead of tartaric acid and stannous chloride as suggested by Gordon et al.) was to reduce the toxicity of our waste stream.
Nitrate and nitrite analyses were also modified from Armstrong et al. (1967). Nitrate was reduced to nitrite in a cadmium column, then formed into a red azo dye by complexing nitrite with sulfanilamide and N-1-naphthylethylenediamine. The color formation was detected using a 6-mm flow cell at 540 nm. The same technique was used to measure nitrite (excluding the reduction step), but the color formation was detected using a 10-mm flow cell at 540 nm.
Phosphate analysis was based on the technique of Bernhardt and Wilhelms (1967). An acidic solution of ammonium molybdate was added to the sample to produce phosphomolybdic acid, and this was reduced to the blue compound phosphomolybdous acid following the addition of hydrazine sulfate. The reaction was heated to 55°C to bring the reaction to completion, and color formation was detected using a 10-mm flow cell at 815 nm.
3.2 Total CO2 Measurements
Samples for TCO2 measurements were drawn according to procedures outlined in the Handbook of Methods for CO2 Analysis (DOE 1994) from 12-L Bullister bottles into 540-mL Pyrex bottles using Tygon tubing with a silicone adapter on the petcock to avoid contamination of DOC samples. Bottles were rinsed and filled from the bottom, leaving 5 mL of headspace; care was taken not to entrain any bubbles. After 0.2 mL of saturated HgCl2 solution was added as a preservative, the sample bottles were sealed with glass stoppers lightly covered with Apiezon-L grease and were stored at room temperature for a maximum of 12 hours prior to analysis.
TCO2 samples were collected at every degree from all depths (typically 36 for standard deep water stations) with three replicate samples. Some samples were also collected at every half-degree. The replicate seawater samples were taken from the surface, 1000 m, and bottom Bullister bottles and run at different times during the cell. The first replicate of the bottom water was used at the start of the cell with fresh coulometer solution, and the first of the 1000-m replicates was run in the middle of the cell after about 12 mg of C were titrated. The second one of the bottom replicates was run at the end of the cell after about 25 mg of C were titrated. A new coulometer cell was started with the second of the 1000-m replicates and the first of the surface replicates. In the middle of this cell, the second of the surface replicates was run and the first one of the surface duplicates of a partial station. The second of the partial station duplicates was run at the end of this cell. No systematic difference between the replicates was observed. There was no systematic dependency of results with an amount of carbon titrated for a particular cell. A total of 2482 samples for TCO2 were collected and analyzed during the cruise.
The TCO2 analytical equipment was set up in a seagoing laboratory van. The analysis was done by coulometry with two analytical systems (called AOML-1 and AOML-2) used simultaneously on the cruise. Each system consisted of a coulometer (UIC, Inc.) coupled with a single operator multi-parameter metabolic analyzer (SOMMA) inlet system developed by Kenneth Johnson (Johnson et al. 1985, 1987, 1993; Johnson 1992) now retired from Brookhaven National Laboratory (BNL). In the coulometric analysis of TCO2, all carbonate species are converted to CO2 (gas) by addition of excess hydrogen ion (acid) to the seawater sample, and the evolved CO2 gas is swept into the titration cell of the coulometer with pure air or compressed nitrogen, where it reacts quantitatively with a proprietary reagent based on ethanolamine to generate hydrogen ions. In this process, the solution changes from blue to colorless, which triggers a current through the cell and causes coulometrical generation of OH ions at the anode. The OH ions react with the H+, and the solution turns blue again. A beam of light is shone through the solution, and a photometric detector at the opposite side of the cell senses the change in transmission. Once the percent transmission reaches its original value, the coulometric titration is stopped, and the amount of CO2 that enters the cell is determined by integrating the total charge during the titration.
The coulometers were calibrated by injecting aliquots of pure CO2 (99.995%) by means of an 8-port valve outfitted with two sample loops with known gas volumes (AOML-1: 1.9951 mL at 25.05°C and 0.9807 mL at 25.10°C; AOML-2: 2.0018 mL at 25.09°C and 0.9949 mL at 25.06°C) bracketing the amount of CO2 extracted from the water samples for the two AOML systems.
The stability of each coulometer cell solution was confirmed three different ways: the Certified Reference Material (CRM), Batch 66, supplied by Dr. A. Dickson of SIO, was measured at the beginning and the middle, gas loops in the beginning and at the end, and the duplicate samples at the beginning, middle, and end of each cell solution (Fig 3.1., Table3.1.). The coulometer cell solution was replaced after 25 mg of carbon was titrated, typically after 912 hours of continuous use.
The pipette volume was determined prior to the cruise by taking aliquots at known temperature of distilled water from the volumes. The weights with the appropriate densities were used to determine the volume of the pipettes (AOML1: 28.716 mL at 20.00°C, AOML2: 22.547 mL at 20.00°C).
Calculation of the amount of CO2 injected was according to the CO2 handbook (DOE 1994). The concentration of CO2 ([CO2]) in the samples was determined according to:
where Cal. Factor is the calibration factor, Counts is the instrument reading at the end of the analysis, Blank is the counts/minute determined from blank runs performed at least once for each cell solution, Run Time is the length of coulometric titration (in minutes), and K is the conversion factor from counts to mol.
The instrument has a salinity sensor, but all TCO2 values were recalculated to a molar weight (µmol/kg) using density obtained from the CTDs salinity sensor. The TCO2 values were corrected for dilution by 0.2 mL of HgCl2 used for sample preservation. The total water volume of the sample bottles was 540 mL. The correction factor used for dilution was 1.00037. A correction was also applied for the offset from the CRM. This correction was applied for each cell using the CRM value obtained in the beginning of the cell. The results underwent initial quality control on the ship using property plots: TCO2 vs.Depth, TCO2 vs. Potential Temperature, TCO2 vs. AOU, TCO2 vs. NO3; TCO2 vs. SiO3, TCO2 vs. PO4, TCO2 vs. TALK, and TCO2 vs. pH. Also contour plots of TCO2 vs. LAT and Depthwere used to analyze the quality of the data.
Fig. 3.1. Results of the duplicate TCO2 samples collected during the R/V Ronald H. Brown cruise along the Atlantic Ocean section A16S_2005.
|Measurement method
|Std. dev.
|Duplicate samples measured back-to-back
|One duplicate measured at the beginning; one at the middle of the cell
|One duplicate measured at the middle; one at the end of the cell
|One duplicate measured at the beginning; one at the end of the cell
|Duplicates run on the same instrument but on different cells
|Duplicates run on different instruments
|Duplicates measured at the beginning of the cell, but not back-to-back
|Duplicates measured at the middle of the cell, but not back-to-back
|Duplicates measured at the end of the cell, but not back-to-back
|Total no. of measurements
The overall performance of the instruments was good during the cruise. The air purifier supplying carrier and pneumatic gas malfunctioned at station 24. Compressed tanks of ultra-high purity nitrogen gas were used thereon. At the same time, soda lime traps used to scrub any CO2 from the carrier gas were removed from the air/N2 line, since they developed cracks over time and also appeared to release CO2 in pulses into the carrier. A coulometer was replaced during the test cast runs. It did not find an endpoint and did not stop counting. A number of pinch valves failed and were replaced; some cell caps began to leak, and some electrode leads broke. Finally, the Orbo tubes (filled with silica gel to absorb possible acid vapors) tended to break and leak and were not used after station 109 on either system.
Due to concerns about the large amount of water used for a TCO2 sample and use of grease on the stoppers that could contaminate samples for dissolved organic matter (DOM), comparison tests were performed with samples drawn in 250-mL borosilicate bottles with ground glass stoppers stored under cold water with the regular sampling procedures outlined above. The results are shown in Table 3.2.
|TCO2 µmol/kg
|Bullister Bottle No
|Volume (mL)
|Average µmol/kg
1CRM = 1969.57 µmol/kg;
2Bottles with prefix S are the 250-mL bottles; the others are the 540-mL bottles used during the cruise;
3RT: run time of the sample on the coulometer in minutes.
4Average: Average of duplicate large or duplicate small bottles taken from a particular Bullister bottle.
These tests and more ad-hoc tests at the beginning of the cruise showed a small but systematic difference between the small and large sample bottles: the average for large bottles was 2121.79 µmol/kg; for small bottles, 2120.26 µmol/kg; standard deviations were 0.37 and 0.55, respectively. The cause of the artifact is not clear, but the tests led to the decision to use the 500-mL greased stopper bottles for the entire cruise.
3.3 Discrete Fugacity of CO2 Measurements
Samples for fCO2 were drawn from 12-L Bullister bottles into 500-mL Pyrex volumetric flasks using Tygon tubing with a Silicone adapter over the petcock to avoid contamination of DOC samples. Bottles were rinsed twice, filled from the bottom, and overflowed half a volume while care was taken that no bubbles were entrained. About 5 mL of water was withdrawn by removing the pinched-off sampling tube from the neck of the flask to create a small expansion volume, then 0.2 mL of saturated mercuric chloride (HgCl2) solution was added as a preservative. The sample bottles were sealed with a polyethylene-lined screw cap. The samples were stored upside down in coolers at room temperature for a maximum of 10 hours.
Thirty samples were drawn at every fourth station (at 2 intervals) for a total of 847 samples from 29 stations. In addition, samples were drawn in duplicate from the underway seawater line at 6-hour intervals between Punta Arenas and the start of the line at 60°S, 31°W.
The fCO2 was measured on the A16S_2005 cruise at a constant temperature of 20°C by equilibrating a 500-mL water aliquot in a volumetric flask with a closed headspace. The headspace was circulated through a nondispersive infrared detector that measures both CO2 and H2O levels. The analytical instrumentation is detailed in Wanninkhof and Thoning (1993) and is similar to the setup used in the S.Atl-91 cruise that occupied the same cruise line from 43°S northward in 1991 (Forde et al. 1994). Discrete fCO2 measurements were also made on the SAVE-5/HYDROS-4 cruises using a system developed by Chipman et al. (1993) that covered a similar track from 54°S to 2°N in 1989-1990 (SAVE 1992).
In short, in the system used on A16S_2005, a 500-mL water sample was equilibrated at ambient pressure with an 80-mL headspace in a volumetric flask held at a temperature of 20 °C in a thermostatted bath. The headspace was circulated through a nondispersive infrared analyzer (NDIR), LICOR, model 6262. Upon equilibration, the circulation flow was stopped and 20 consecutive 1-second readings of H2O content and CO2 content in the cell were taken and averaged. The system was a dual-channel system where one equilibration occurs while circulating through the NDIR and a second flask was equilibrated offline. Once the first sample was analyzed, the second flask was switched in line with the NDIR and the residual air in the NDIR was equilibrated with the second flask content. The second equilibration phase through the NDIR took less time as a large part of the headspace was already equilibrated offline. The two-channel configuration decreases the total analysis time to about 20 minutes for two samples. An expandable volume in the circulation loop near the flasks consisting of a small deflated balloon kept the content of flasks at room pressure.
To account for instrument drift and to maintain measurement precision, a set of six gas standards was run through the system before and after every eight seawater samples. The standards of CO2 in natural air were obtained from Scott-Marin and referenced against primary standards purchased from C.D. Keeling in 1991. The primary standards were on the WMO-78 scale. The mole fractions of the standards, which were run in the following sequence, were:
|Tank number
|Mole fraction
|378.71 ppm
|792.51 ppm
|1036.92 ppm
|1533.70 ppm
|593.64 ppm
|205.07 ppm
The standards were also used as the headspace gas for the equilibration. Since the mole fractions of the gases in the headspace prior to equilibration were known, the small perturbation of the fCO2 in the water during the equilibration process could be quantitatively accounted for. The headspace gas was selected so that it is close to the anticipated water value, thereby minimizing the correction.
The determination of fCO2 @20°C [fCO2(20)] in water from the headspace measurement involved several steps. The infra-red (IR) detector response for the standards was normalized for temperature. The IR analyzer output of dry mole fraction of CO2 (xCO2) for samples was normalized to 1 atm pressure. The sample values were converted to the true mixing ratio based on a second-order polynomial fit between the instrument xCO2 readout and the values of the three nearest concentrations of the compressed gas standards. The mixing ratio in the headspace was converted to a fugacity assuming 100% humidity and corrected to fugacity of CO2 in the water sample prior to equilibration by accounting for change in total CO2 in water during the equilibration process (for details see Wanninkhof and Thoning 1993). The change in fCO2(20) caused by the change in TCO2 was calculated using the constraint that TALK remains constant during exchange of CO2 gas between the headspace and the water. The calculation is outlined Peng et al. (1987).
Uncertainty based on duplicate sampling of the same Bullister bottle for fCO2 analysis was determined on select stations of the cruise. The comparisons are presented In Table 3.3
|Sample No.
|% difference
fCO2av = average of the duplicate samples.
∆fCO2 = absolute difference between the duplicates
% difference = ∆fCO2/fCO2av X 100
Measuring TCO2, TALK, and fCO2(20) on the cruise, offers an opportunity to assess the internal consistency of these inorganic carbon parameters. For the analyses, the apparent carbonate dissociation constants determined by Mehrbach (1973) as refitted by Dickson and Millero (1987) were used. An Excel program developed by D. Pierrot of RSMAS/University of Miami using the code developed by Lewis and Wallace (1998) facilitated the calculations. The average difference between measured alkalinity and that calculated using TCO2 and fCO2(20) was -2.03 ±4.91 µmol/kg (n=768). The agreement was the best obtained to date and suggested an excellent data quality of these parameters. A compilation of the difference plotted versus depth is shown in Fig. 3.2.
Fig. 3.2. Difference between measured TALK and that calculated from TCO2 and fCO2(20) plotted versus depth.
The distribution of differences is presented in Fig. 3.3. The figure shows a near-normal distribution with a slight negative bias suggesting predominantly random errors.
Fig. 3.3. Distribution of measured TALK – calculated TALK from TCO2 and fCO2(20).
The A16S_2005 cruise overlapped with the A16N_2003a cruise from 6˚S to 2.5˚S and measurements of fCO2(20) were performed at 4˚S and 6˚S on both cruises. The depth profiles shown in Figs. 3.4 and 3.5 show excellent agreement between the observations at the two locations. For example, for the depth interval between 1800 and 3500 dB in the core of the North Atlantic deep water where fCO2(20) is quite constant, the average of the values of the two overlap stations are well within one standard deviation (9 atm) of each other with no significant differences between the 2003 and 2005 data.
Fig. 3.4. Comparison of fCO2(20) data at 6°S for 2003 and 2005.
Fig. 3.5. Comparison of fCO2(20) data at 4°S for 2003 and 2005.
3.4 Total Alkalinity Measurements
Samples for total alkalinity measurements were drawn from 12-L Bullister bottles into 500-mL borosilicate flasks using silicone tubing fit over the petcock to avoid contamination of DOC samples. Bottles were rinsed a minimum of two times and filled from the bottom and a quarter of a volume was overflowed while taking care to avoid the entrainment of any bubbles. Approximately 15 mL of water was withdrawn from the flask by arresting the sample flow and removing the sampling tube, thus creating a small expansion volume and a reproducible headspace. The sample bottles were sealed at a ground glass joint with a glass stopper. The samples were stored at room temperature for a maximum of 7 hours. Thirty-six samples and three duplicates were drawn on odd number stations (at 1 intervals) for a total of 61 full stations. Typically, 9 depths were sampled with a duplicate at the surface at the 60 half stations. Periodically, multiple duplicate samples were drawn with a specific focus on photic zone and region of high DOC. The purpose was to determine the difference in TALK after filtration with a 0.45-m nylon membrane filter. Additional underway samples were drawn in duplicate from the underway seawater line at 6-hour intervals between Punta Arenas, Chile, and the start of the line at 60°S, 31°W
The TALK was evaluated from the proton balance at the alkalinity equivalence point, pHequiv = 4.5 at 25°C and zero ionic strength in 1 kg of sample. The method utilizes a multi-point hydrochloric acid titration of seawater according to the definition of total alkalinity (Dickson 1981).
The titration system consisted of a Metrohm 665 Dosimat titrator, an Orion 720A pH meter, and a custom-designed, plastic water-jacketed titration cell (Millero et al. 1993a). Both the seawater sample and acid titrant are temperature-equilibrated to a constant temperature of 25 ± 0.1°C with a water bath (Neslab, model RTE-17). The plastic water-jacketed cell is similar to the cells used by Bradshaw and Brewer (1988) except a larger volume (~200 mL) is employed to increase the precision. Each cell has a fill-and-drain valve, which increases the reproducibility of the volume of sample contained in the cell. The titration acidified seawater passed the carbonic acid endpoint by adding HCl stepwise through an injection tip into the cell. A typical titration recorded the (electro-magnetic field) EMF after the readings became stable (deviation less than 0.09 mV), and then enough acid was added to change the voltage a preassigned increment (13 mV). A full titration (~25 points) takes about 20 min. The electrodes used to measure the EMF of the sample during a titration consisted of a ROSS glass pH electrode (Orion, model 810100) and a double-junction Ag, AgCl reference electrode (Orion, model 900200).
A single 50-L batch of ~0.25-m HCl acid was prepared in 0.45-m NaCl by diluting concentrated HCl, AR Select Mallinckrodt, to yield a total ionic strength similar to seawater of salinity 35.0 (I ≈ 0.7 M). The acid was standardized by a coulometric technique (Marinenko and Taylor 1968, Taylor and Smith 1959) and verified with alkalinity titrations on seawater of known alkalinity. Furthermore, Andrew Dicksons laboratory performed an independent determination of the acid molality on sub-samples. The calibrated molality of the acid used was 0.2434 ± 0.0001 m HCl. The acid was stored in 500-mL glass bottles sealed with Apiezon L grease for use in the field.
The volumes of the cells used were determined to ± 0.03 mL in the laboratory by multiple titrations using seawater of known total alkalinity and CRM. Calibrations of the burette of the Dosimat with water at 25°C indicate that the systems deliver 3.000 mL (the approximate value for a titration of seawater) to a precision of ± 0.0004 mL, resulting in an error of ± 0.3 µmol/kg in TALK and TCO2. The reproducibility and precision of measurements are checked using low nutrient surface seawater and CRM, Batch Nos. 59 and 66. CRMs were utilized to account for instrument drift and to maintain measurement precision. Duplicate analyses provide additional QA and were taken from same Bullister bottle.
The assigned values of the CRM provided by A. Dickson of SIO were:
- Batch #59: Total alkalinity: 2220.98 ± 0.58 µmol/kg Salinity: 33.316
- Batch #66: Total alkalinity: 2193.27 ± 0.60 µmol/kg Salinity: 32.962
An integrated program controlled the titration, data collection, and the calculation of the carbonate parameters (TALK, pH, and TCO2) (Millero et al. 1993b). The program is patterned after those developed by Dickson (1981), Johansson and Wedborg (1982), and DOE (1994). The program uses a Levenberg-Marquardt nonlinear least-squares algorithm to calculate the TALK and TCO2 from the potentiometric titration data.
|Instrument 1
|Instrument 2
|Total Number of Sets
|Number of Sets Used
|Standard Deviation
|± 3.5 µmol/kg
|Between Systems
|Instrument 1
|Instrument 2
|Total Number of Sets
|Number of Sets Used
|Standatd Deviation
|± 2.9 µmol/kg
|± 1.6 µmol/kg
|± 1.3 µmol/kg
Note: Duplicate samples with differences three times larger than standard deviation were omitted from the analyses. The number omitted is the difference between the total number of sets and the sets used.
At the beginning of the cruise, a titration cell was swapped out for a spare cell because of a combination of instability in the electrodes and an air bubble consistently being trapped. One valve and a proximity switch were replaced without discernible downtime. Sporadically, a solenoid valve at the bottom of the titration cell would fail to engage or disengage, resulting in the loss of the sample or a failed titration due to a poor rinse or an air bubble. The titration cell on system showed some drift in CRM values on February 4, 2005; the titration cells recalibration values were used to correct this. Communication problems between the software and the components of the TALK system were remedied with the replacement of cables and/or components. A Metrohm 665 Dosimat titrator and an Orion 720A pH meter were replaced. Computer instability resulted in the loss of one sample.
3.5 pH Measurements
Samples for pH measurements were drawn from 12-L Bullister bottles into 50-mL glass syringes using polycarbonate Luer-lock valves that fit in the petcock. Syringes were rinsed a minimum of three times and filled while care was taken to avoid the entrainment of any bubbles. A rubber band ensured positive pressure on the barrel of the syringe. The samples were stored at room temperature for a maximum of 7 hours. Thirty-six samples and 3 duplicates were drawn on odd- numbered stations (at 1 intervals) for a total of 61 full stations. At even-numbered stations, surface water and a duplicate were always taken; in addition, 5 to 20 other depths were also sampled, for a total of 60 half stations. Typically, nine depths were sampled with a duplicate at the surface for the half-stations. Underway samples were drawn in duplicate from the underway seawater line at 6-hour intervals between Punta Arenas, Chile, and the start of the line at 60°S, 31°W.
Measurements of the pH of seawater on the total hydrogen ion concentration pH scale (pHt) were performed using the multi-wavelength spectrophotometric techniques of Clayton and Byrne (1993). Determination of the absorbance at several wavelengths eliminates the need to know the concentrations of indicator in the sample. Sulphonephthalein indicators such as m-cresol purple (mCP), thymol blue, and cresol red are suitable for determining pH. The system is patterned after the standard operating procedure developed by DOE (1994) and utilizes mCP. This fully automated system performs discrete analysis of pH samples approximately every 12 minutes on a sample volume of 25 mL. A microprocessor-controlled syringe and sampling valve aspirates and injects the seawater sample into the 10-cm optical cell at a precisely controlled rate. The syringe rinses and primes the optical cell with 20 mL of sample and the software permits 5 minutes for temperature stabilization. A refrigerated circulating temperature bath (Neslab, model RTE-17) regulates the temperature of the sample at 25 ± 0.01°C. An Agilent 8453 UV/VIS spectrophotometer measures background absorbance of the sample. The automated syringe and sampling valves aspirates 4.90 mL seawater and 0.008 mL of indicator and injects the mixture into the cell. After the software permits 5 min for temperature stabilization, a Guildline 9540 digital platinum resistance thermometer measures the temperature and the spectrophotometer acquires the absorbance at 434, 578, and 730 nm.
A concentrated solution of 2.0 mM of mCP (C21H18O3S) dye of known pHt = 7.91 and R = 1.625 at 25°C were used.
A precision of better than 0.001 pH is possible with care, specifically with regard to temperature equilibration and sample handling. Measurements made on duplicate samples, TRIS buffers, and CRM, Batch No. 59, validate the precision and accuracy. Duplicate analyses provide additional QA and were taken from same Bullister bottles. The pHsws for the CRM was determined by spectrophotometric methods independently in the laboratory at RMSAS, University of Miami:
- Batch #59: pHsws @ 25°C 7.9048 ± 0.0007 (n = 19)
- Salinity 33.316
The pHt of the sample is perturbed by the addition of the indicator. The magnitude of this perturbation is a function of the difference between the seawater and indicator acidity. A correction factor applied for each batch of dye adjusts for this perturbation. For a 4.90-mL sample of seawater, 0.008 mL of mCP is added and the absorbance ratio is measured. From a second addition of mCP and a second absorbance ratio measurement, a change in the absorbance ratio per mL of added indicator is calculated. The value of the absorbance ratio (Rm) measured subsequent to the initial addition of the indicator was used to calculate R from:
R = Rm + (0.00095 – 0.00133 Rm) Vind (1)
where Vind is the volume of mCP used. Clayton and Byrne (1993) calibrated the mCP indicator using TRIS buffers (Ramette et al. 1977) and the equations of Dickson (1993). These equations are used to calculate pHt, the total scale in units of moles per kilogram of solution. The conversion of the pHt (µmol/kgH2O) to the seawater scale (µmol/kgsol) can be made using equations of Dickson and Millero (1987), Dickson and Riley (1979), and Dickson (1990).
Total number of sets: 136
Number of sets used: 124
CRM Batch #59: 7.9050 ± 0.0024 (pHsws at 25°C)
TRIS buffer
Total number of sets: 296
Number of sets used: 264
TRIS Buffer (0.04 m): 8.0935 ± 0.0019 (pHt @ 25°C)
Total number of sets: 291
Number of Sets used: 214
Standard deviation: ± 0.0019 (pHsws @ 25°C)
Note: The instrumental software automatically runs a duplicate analysis when the baseline absorbance at 730 nm is beyond a set threshold, thus a large number of duplicate results were omitted. Duplicate samples with differences more than three times larger than the standard deviation were omitted from the analyses. The number omitted is the difference between the total number of sets and the sets used.
At the start of the cruise, the outflow from the optical cell leaked into the thermostat-equipped water jacket; this was repaired by replacing the tubing. Sporadically, samples drawn from the syringe entrained an air bubble because the valve was improperly opened, the tubing was pinched, or the syringe plunger was dry and became stuck in the barrel. Some syringes suffered from fatigue at the metal Luer-lock and this resulted in the sample being lost or the analysis failing. Occasionally the software lost communication with the microprocessor-controlled syringe pumps and paused analysis; the problem was resolved by following the steps outlined in the software to reestablish communication.
3.6 Dissolved Organic Carbon Measurements
Water samples were collected from the rosette. Samples collected from the surface to 250 meters were filtered using precombusted (500°C) GF/F inline filters as they were being collected from the Niskin bottle. At depths > 250 meters, the samples were collected without filtration. After collection, samples were frozen upright in 60-mL acid-cleaned high-density polypropylene bottles and remained cold until analysis. Prior to analysis, samples were returned to room temperature then acidified to pH < 2 with concentrated hydrochloric acid. Analysis was performed onshore using a Shimadzu TOC-VCSH Total Organic Carbon Analyzer with the TNM-1 Total Nitrogen detector attached. Instrument conditions were as follows:
Combustion temperature - 680°C
Carrier gas - UHP Oxygen
Carrier flow rate - 150 mL/min
Ozone generation gas - Zero Air from Whatman TOC Gas Generator
Ozone flow rate - 500 mL/min
Sample sparge time - 2.0 minutes
Minimum number of injections - 3
Maximum number of injections - 5
Number of washes - 2
CV maximum (within sample) - 2.00%
Injection volume - 100 µL
The TOC system was calibrated using potassium hydrogen phthalate in Milli-Q water; the TN system was calibrated using potassium nitrate in Milli-Q water. System performance was verified daily using Consensus Reference Water distributed by the Hansell Organic Biogeochemistry Laboratory. This reference water is from deep in the Sargasso Sea that has been acidified and sealed in 10-mL ampoules, the concentration of which (44 µmol/kg C) has been determined by the consensus of up to six expert and independent laboratories. After verifying proper operation of the TOC/TN instrument, samples were set up on an auto sampler for analysis. The run started with a QW (Q Water) blank and a reference seawater analysis. Then six samples would be analyzed followed by another pair of QW blank and reference seawater analyses. This sequence would be repeated until all samples for that run were analyzed. The run ended with a QW blank, reference water, and a non-acidified QW blank. This was done to verify that the hydrochloric acid used to acidify the samples was uncontaminated. QW blanks and reference water samples were used to evaluate system performance during the analytical run. If a problem was detected with the blanks or reference waters, the samples were reanalyzed. The repeated use of deep sea consensus reference water in the analysis of DOC samples from this cruise indicates a between sample precision of approximately 0.6 µmol/kg, or a coefficient of variation of about 1.5%.
Chlorofluorocarbon Measurements
Samples for the analysis of dissolved CFC-11, -12, -113, and carbon tetrachloride (CCl4) were drawn from 2378 of the 4192 bottles collected during the expedition. Specially designed 12-L Bullister bottles were used on the cruise to reduce CFC contamination. These bottles have the same outer diameter as standard 10-L Niskin bottles, but use a modified end-cap design to minimize the contact of the water sample with the end-cap O-rings after closing. The O-rings used in these water sample bottles were vacuum-baked prior to the first station. Stainless steel springs covered with a nylon powder coat were substituted for the internal elastic tubing provided with standard Niskin bottles. When taken, water samples for CFC and carbon tetrachloride analysis were the first samples drawn from the Bullister bottles. Care was taken to coordinate the sampling of CFCs with other samples to minimize the time between the initial opening of each bottle and the completion of sample drawing. In most cases, dissolved oxygen, 3He, and HCFC samples were collected within several minutes of the initial opening of each bottle. To minimize contact with air, the CFC samples were drawn directly through the stopcocks of the Bullister bottles into 100-mL precision glass syringes equipped with two-way metal stopcocks. The syringes were immersed in a holding tank of clean surface seawater until analyzed.
Concentrations of CFC-11 and CFC-12 were measured by shipboard electron capture gas chromatography (EC-GC) using techniques modified from those described by Bullister and Weiss (1988). For seawater analyses, water was transferred from a glass syringe to a fixed volume chamber (~30 mL). The contents of the chamber were then injected into a glass-sparging chamber. The dissolved gases in the seawater sample were extracted by passing a supply of CFC-free purge gas through the sparging chamber for a period of 4 min at 70 mL/min. Water vapor was removed from the purge gas during passage through an 18-cm long, 3/8-in. diameter glass tube packed with the desiccant magnesium perchlorate. The sample gases were concentrated on a cold-trap consisting of a 1/8-in. outside diameter (OD) stainless steel tube with a ~10-cm section packed tightly with Porapak N (60-80 mesh). A vortex cooler, using compressed air at 100 psi, was used to cool the trap to approximately −20°C. After 4 min of purging, the trap was isolated, and the trap was heated electrically to ~100°C. The sample gases held in the trap were then injected onto a precolumn (~25 cm of 1/8-in. OD stainless steel tubing packed with 80100 mesh Porasil C, held at 70°C) for the initial separation of CFC-12, -11, and -113 from carbon tetrachloride. After the CFCs had passed from the pre-column into the main analytical column (~183 cm of 1/8-in.OD stainless steel tubing packed with Carbograph 1AC, 80-100 mesh, held at 70°C) of GC1 (a HP 5890 Series II gas chromatograph with an EC detector), a valve was used to direct the precolumn flow (and more slowly eluting carbon tetrachloride peak) to a second gas chromatograph (Shimadzu Mini II GC with ECD). For the first 52 stations, the chromatographic column in the Shimadzu GC was 1 m of 1/8-in. OD stainless steel tubing packed with 80-100 mesh Porasil C.
Both of the analytical systems were calibrated frequently, with frequency listed below, using a standard gas of known CFC composition. Gas sample loops of known volume were thoroughly flushed with standard gas and injected into the system. The temperature and pressure were recorded so that the amount of gas injected could be calculated. The procedures used to transfer the standard gas to the trap, precolumn, main chromatographic column, and EC detector were similar to those used for analyzing water samples. Two sizes of gas sample loops were used. Multiple injections of these loop volumes could be made to allow the system to be calibrated over a relatively wide range of concentrations. Air samples and system blanks (injections of loops of CFC-free gas) were injected and analyzed in a similar manner. The typical analysis time for seawater, air, standard, or blank samples was ~11 min.
Concentrations of the seawater samples, and gas standards are reported relative to the SIO98 calibration scale. Dissolved CFC concentrations are given in units of picomoles per kilogram seawater (pmol/kg). CFC concentrations in seawater samples were determined by fitting their chromatographic peak areas to multi-point calibration curves, generated by injecting multiple sample loops of gas from a working standard (PMEL cylinder 45191 for CFC-11, CFC-12, CFC-113, and CCl4) into the analytical instrument. The response of the detector to the range of moles of CFC passing through the detector remained relatively constant during the cruise. Full-range calibration curves were run at intervals of 14 days during the cruise. These were supplemented with occasional injections of multiple aliquots of the standard gas at more frequent time intervals. Single injections of a fixed volume of standard gas at one atmosphere were run much more frequently (at intervals of ~90 minutes) to monitor short-term changes in detector sensitivity. The CFC-113 peak was often on a small bump on the baseline, resulting in a large dependence of the peak area on the choice of endpoints for integration. To provide better precision, the height of the peak was used instead . The precisions of measurements of the standard gas in the fixed volume (n = 690) were ± 0.67% for CFC-12 and 0.59% for CFC-11.
The efficiency of the purging process was evaluated periodically by re-stripping high- concentration surface water samples and comparing the residual concentrations to initial values. These re-strip values ranged from approximately 1% for CFC-11 and CFC-12 in cold waters to values of <1% in warm waters. A fit of the re-strip efficiency as a function of temperature was applied to the final data set. The cold-water values have been applied to all values in the preliminary data set.
There were very few measurements of CFC-11 and CFC-12 concentrations less than 0.005 pmol/kgalong A16S section.
Based on the analysis of 100 duplicate samples, the precisions (1 standard deviation) of 0.45% or 0.003 pmol/kg (whichever is greater) for dissolved CFC-11, and 0.78% or 0.004 pmol/kg for CFC-12 measurements was estimated.
A very small number of water samples had anomalously high CFC concentrations relative to adjacent samples. These samples occurred sporadically during the cruise and were not clearly associated with other features in the water column (e.g., anomalous dissolved oxygen, salinity, or temperature features). This suggests that these samples were probably contaminated with CFCs during the sampling or analysis processes. Measured concentrations for these anomalous samples are included in the data set, but are given a quality flag value of either 3 (questionable measurement) or 4 (bad measurement). A quality flag of 5 was assigned to samples drawn from the rosette but never analyzed due to various reasons (e.g., leaking stopcock, plunger jammed in syringe barrel). A total of 13 analyses of CFC-11 and 16 analyses of CFC-12 were assigned a quality flag 3. Four analyses of CFC-11 and 6 analyses of CFC-12 were assigned a quality flag 4. A total of 13 samples were given a quality flag 5 (sampled but not analyzed).
3.8 Underway pCO2 (fCO2) Measurements
The shipboard automated underway pCO2 system was situated in the hydrographic laboratory. It ran on an hourly cycle during which 3 gas standards, 8 headspace samples from the equilibrator, and 3 ambient air samples were analyzed. The system consisted of an equilibrator where surface seawater from the bow intake was equilibrated with headspace, a valve box that contained the infrared analyzer, and an electronics box with a computer and interface boards that controlled valves and log sensors.
The equilibrator, designed by R. Weiss of SIO, is made from a 58 cm H X 23 cm inside diameter (ID) cylindrical PlexiglasTM chamber. Surface seawater flows through a showerhead in the top at a rate of 10-13 L/min. The water spray through the 16-L headspace and the turbulence of the water streams impinging on the surface of 8 L of water cause the gases in water and headspace to equilibrate. Excess water flows through an outlet 20 cm from the bottom of the equilibrator into an over-the-side drain. Two vents in the top of the equilibrator ensure that the headspace remains at the measured laboratory pressure. Headspace gas circulates in a closed loop driven by a KNF pump at 200 mL/min. From the equilibrator, the gas passes through a condenser, a column of magnesium perchlorate, a mass flow meter (MFM), the 12 mL sample cell of a LicorTM Model 6251 non-dispersive infrared analyzer (IR), and back into the equilibrator headspace.
A second KNF pump draws marine air from an intake on the bow mast through ~100 m of 0.95 cm (3/8in.) OD DekoronTM tubing at a rate of 68 L/min. A filter of glass wool at the intake prevents particles from entering the gas stream. At designated times, the program diverts ~250 mL/min of air from this line into the LicorTM sample cell for analysis. Excess marine air and the two vent lines from the equilibrator empty through an endcap into an open-ended PVC tube. This means that any air drawn into the equilibrator is marine air rather than lab air with elevated and variable CO2 concentration.
Both sample streams (equilibrator headspace and marine air) are analyzed bone dry. They pass first through a cold trap (condensor) at 5°C and then through a column of magnesium perchlorate. Standard gases also run through the magnesium perchlorate.
A custom developed program run under LabView controls the system and graphically displays air and water mole-fraction of CO2 (xCO2) readings. The program logs the voltage and temperature of the infrared analyzer, water flow, gas flows, equilibrator temperature, and barometric pressure. It also logs temperature and salinity from a Seabird MicroTSG unit connected to the seawater line near the equilibrator. An RS-422 feed from the shipboard computing system (SCS) provides additional data including time, latitude, longitude, temperature, and salinity in the sea chest near the seawater intake, relative and absolute wind speed and direction, and fluorometer readings. The program writes all of this data to disk at the end of each measurement phase.
The details of instrumental design can be found in Wanninkhof and Thoning (1993), Ho et al. (1995), and Feely et al. (1998).
The system runs on an hourly cycle during which 3 standard gases, 3 marine air samples, and 8 surface water samples (from the equilibrator headspace) are analyzed on the schedule listed in Table 3.3. A Valco multi-port valve selects the gas to be analyzed. Each measurement phase starts by flowing either standard (at ~50mL/min), equilibrator headspace (at ~200 mL/min), or marine air (at ~250 mL/min) through the Licor. Fifteen seconds before the end of each phase, a solenoid valve stops the gas flow. Ten seconds later, the program logs all sensors and writes the data to disk.
|Minutes after the Hour
|Low standard
|Mid standard
|High standard
|Water (= headspace of equilibrator)
|Air (marine air from the bow line)
The headspace equilibration time, as determined by return to equilibrium after perturbation by adding nitrogen to the headspace, was approximately 2.5 min. The transit time of water from the bow to the equilibrator was determined in 1998 by injecting a slug of dye into the intake and measuring the response on a fluorometer that is located in the hydrolab, close to the equilibrator. The response time, defined as the time elapsed between peak concentration and the half peak level, t1/2, was 1.45 min. This short time suggests little dispersion of the water during transit through the tubing.
The unit is standardized every hour with three compressed air standards containing known amounts of CO2 gas in (natural) air. The standard gases were purchased from NOAA/CMDL in Boulder and are directly traceable to the World Meteorological Observatory (WMO) scale.
The standards used on the cruise were:
|Tank No.
|Mole Fraction CO2 (ppm) (xCO2)
All xCO2 values are reported in parts per million (ppm), and fCO2 values are reported in micro atmospheres (atm).
The mixing ratios of ambient air and equilibrated headspace air are calculated by fitting a second-order polynomial through the hourly-averaged voltage response of the detector versus mixing ratios of the standards preceding and following the air and water samples. Mixing ratios of dried equilibrated headspace and air are converted to fCO2 in surface seawater and water saturated air. For ambient air (a) and equilibrator headspace (eq), the fCO2a, or fCO2eq are 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 sea surface temperature (SST) or equilibrator temperature (in K), and R is the ideal gas constant (82.057 mL atm deg-1 mol-1). The exponential term is the fugacity correction where B11 is the second viral coefficient of pure CO2:
d12 = 57.7 − 0.118 T
where d12 is the correction for an air-CO2 mixture in units of mL/mol (Weiss 1974).
The calculation for the fugacity at SST as measured by the thermosalinograph involves a temperature correction term for the increase of fCO2 due to heating of the water from its passage through the pump and through 5-cm ID Teflon-sleeved stainless steel tubing within the ship. The water in the equilibrator is typically 0.2 to 0.3°C warmer than sea surface temperature. At the southern end of the transect when SST ≈ 25°C, the difference was as much as 1°C. The empirical temperature correction from equilibrator temperature to SST is outlined in Weiss et al. (1982).
dln(fCO2) = (teq − SST) X [0.03107 − 2.7851 X 10-4 teq − 1.839 X 10-3 ln(fCO2eq)]
where dln(fCO2) is the difference between the natural logarithm of the fugacity at teq and SST, and teq is the equilibrator temperature in °C.
The precision of the measurements is estimated at 0.2 ppm based on repetitive measurements of marine air. The accuracy of the air values is believed to be better than 0.5 ppm based on comparisons with flask samples on tests performed in 1995. Equilibrator headspace values are believed to be accurate to within 2 atm. The greater uncertainty is attributed to the equilibration efficiency. Outside the calibration range of the standards, an accuracy of 5 ppm (atm) is assigned based on laboratory tests where the calibrated IR output is compared with standards of known concentration outside the calibration range.
At the start of the cruise, from 1/14/05 17:04 (UTC) until 1/16/05 15:50 (UTC), problems with the electrical power caused the program to run out of sync and the equilibrator thermistor to give bad readings. Connecting the instrument to an uninterruptible power supply (UPS) eliminated the problem.
4. How to Obtain the Data and Documentation
This database (NDP-087) is available free of charge from CDIAC. The data are available from CDIAC's anonymous file transfer protocol area. The complete documentation and data can be obtained from the CDIAC oceanographic Web site.
For additional information, contact CDIAC.
5. References
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- Dickson, A.G., and F.J. Millero. 1987. A comparison of the equilibrium constants for the dissociation of carbonic acid in seawater media. Deep-Sea Research Part A, 34/10:173-343.
- Dickson, A.G., and J.P. Riley. 1979. The estimation of acid dissociation constants in seawater media from potentiometric titration with strong base, 1: The ionic product of water-KSUS-w. Marine Chemistry 7/2:89-99.
- DOE (U.S. Department of Energy). 1994. Handbook of Methods for the Analysis of the Various Parameters of the Carbon Dioxide System in Seawater. Version 2.0. ORNL/CDIAC-74. Ed. A. G. Dickson and C. Goyet. Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, Oak Ridge, Tenn.
- Forde, E. B., J.C. Hendee, and R. Wanninkhof. 1994. Hydrographic, carbon dioxide, nutrient, and productivity measurements from the South Atlantic during July and August of 1991, NOAA Data Report ERL AOML-24: NOAA/AOML
- Friederich, G. E., P. Sherman, and L. A. Codispoti. 1984. A High-Precision Automated Winkler Titration System Based on a HP-85 Computer, A Simple Colorimeter and an Inexpensive Electromechanical Buret. Bigelow Laboratory Technical Report, 42. Bigelow Laboratory for Ocean Sciences, West Boothbay Harbor, Maine.
- Gordon, L.I., J.C. Jennings Jr., A.A. Ross, and J.M. Krest. 1993. A suggested protocol for continuous automated analysis of seawater nutrients (phosphate, nitrate, nitrite, and silicic acid) in the WOCE Hydrographic program and the Joint Global Ocean Fluxes Study. WOCE Operations Manual, Vol. 3: The Observational Programme, Section 3.2: WOCE Hydrographic Programme, Part 3.1.3: WHP Operations and Methods. WHP Office Report WHPO 91-1; WOCE Report No. 68/91. November, 1994, Revision 1, Woods Hole, Mass., USA, 52 pp.
- 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.
- Johnson, K. M. 1992. Operators Manual: Single-Operator Multiparameter Metabolic Analyzer (SOMMA) for Total Carbon Dioxide (CT) with Coulometric Detection. Brookhaven National Laboratory, Brookhaven, N.Y.
- Johansson, O., and M. Wedborg. 1982. On the evaluation of potentiometric titrations of seawater with hydrochloric acid. Oceanologica Acta 5:209-18.
- Johnson, K. M., A. E. King, and J. McN. Sieburth. 1985. Coulometric TCO2 analyses for marine studies: An introduction. Marine Chemistry 16:61-82.
- Johnson, K. M., A. Kotzinger, L. Mintrop, J. C. Duinker, and D. W. R. Wallace. 1999. Coulometric total carbon dioxide analysis for marine studies: Measurement and internal consistency of underway surface TCO2 concentrations. Marine Chemistry 67:123-44.
- Johnson, K. M., P. J. Williams, L. Brandstrom, and J. McN. Sieburth. 1987. Coulometric total carbon analysis for marine studies: Automation and calibration. Marine Chemistry 21:117-33.
- Johnson, K. M., K. D. Wills, D. B. Butler, W. K. Johnson, and C. S. Wong. 1993. Coulometric total carbon dioxide analysis for marine studies: Maximizing the performance of an automated gas extraction system and coulometric detector. Marine Chemistry 44:167-87.
- Lewis, E., and D.W.R. Wallace. 1998. Program developed for CO2 system calculations. ORNL/CDIAC-105. Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, U.S. Department of Energy, Oak Ridge, Tennessee.
- Marinenko, G., and J.K. Taylor. 1968. Electrochemical equivalents of benzoic and oxalic acid. Analytical Chemistry 40:1645-51.
- Mehrbach, C., C.H. Culberson, J.E. Hawley, and R.M. Pytkowicz. 1973. Measurement of the apparent dissociation constants of carbonic acid in seawater at atmospheric pressure. Limnology and Oceanography 18:897-907
- Millero, F. J., A. G. Dickson, G. Eischeid, C. Goyet, P. R. Guenther, K. M. Johnson, K. Lee, E. Lewis, D. Purkerson, C. L. Sabine, R. Key, R. G. Schottle, D. R. W. Wallace, and C. D. Winn. 1998. Assessment of the quality of the shipboard measurements of total alkalinity on the WOCE Hydrographic Program Indian Ocean CO2 survey cruises, 19941996. Marine Chemistry 63:9-20.
- Millero F. J., J. Z. Zhang, K. Lee, and D. M. Campbell. 1993a. Titration alkalinity of seawater. Marine Chemistry 44:153-65.
- Millero, F.J., R.H. Byrne, R. Wanninkhof, R. Feely, T. Clayton, P. Murphy, and M.F. Lamb. 1993b. The internal consistency of CO2 measurements in the equatorial Pacific. Marine Chemistry 44:269-80.
- Peng, T.-H., T. Takahashi, W. S. Broecker, and J. Olafsson. 1987. Seasonal variability of carbon dioxide, nutrients and oxygen in the northern North Atlantic surface water: Observations and a model. Tellus 39B:439-58.
- Ramette, R.W., C.H. Culberson, and R.G. Bates. 1977. Acid-base properties of Tris(hydroxymethyl)aminomethane (Tris) buffers in seawater from 5 to 40°C. Analytical Chemistry 49:867-70.
- Taylor, J.K., and S.W. Smith. 1959. Precise coulometric titration of acids and bases. Journal Research of National Bureau of Standards 63:153-59.
- UNESCO, 1981. Background papers and supporting data on the practical salinity scale 1978. UNESCO Technical Papers in Marine Science, No. 37, p. 144.
- Wanninkhof, R., and K. Thoning. 1993. Measurement of fugacity of CO2 in surface water using continuous and discrete sampling methods. Marine Chemistry 44:189-205.
- Wanninkhof, R. and S.C. Doney, 2005: Cruise Report CLIVAR A16S_2005, http://whpo.ucsd.edu/data/co2clivar/atlantic/a16/a16s_2005a/index.htm
- Weiss, R.F. 1974. Carbon dioxide in water and seawater: The solubility of a non-ideal gas. Marine Chemistry 2:203-15.
- 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 300:511-13.


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Tigi Bed Head Dumb Blonde Reconstructor
The dumb blonde reconstructor from Tigi is perfect for use on highlighted, damaged or chemically treated hair.
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Music Catalog
A Far Reach
You need flash to listen to this!
This string ensemble piece represents all the phases of obtaining a large goal. The daunting and somewhat grim beginning with a goal far to reach, followed by the sadness of the grind to get to that goal, then the tension of working so hard, and then the hope of being close, and finally the excitement and joy of reaching your goal.
Visit On Newgrounds: - LD - A Far Reach


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Bic Men's Razors has named Cramer-Krasselt its creative agency of record following a review that began in January.
The incumbent, Source Marketing, will continue as agency of record on the women's portion of the Bic business, which is entering year two of its "Make Your Own Sun" campaign.
As men's business continued to grow, the company developed a new brief on positioning and strategy, according to Mary-Ellen Lacasse, director- shaver marketing at Bic. Five agencies presented on their capabilities, and four went on to pitch.
The win for Cramer-Krasselt actually came in April, and is being announced after it lost two accounts -- Bissell Vacuums in May and Panera Bread in early June. (Cramer-Krasselt told staff it had resigned the account; Panera said it had decided to put the account into review and that Cramer-Krasselt declined to participate.) In 2013, Bissel spent $25 million in measured media and Panera spent more than $58 million, according to Kantar Media.
Bic Men's has not been a very large spender, by comparison, laying out just $1 million on measured media to advertise last year, according to Kantar Media. But both the brand and the agency said a new level of investment was on the way. "This is definitely a heightened spend compared to the past," said Ms. Lacasse.
"It's a very good sized of business for us," said Cramer-Krasselt president-CEO Peter Krivkovich. It also gets the agency into the personal care category, he said.
As Bic looks to focus its efforts against the millennial man, it required "an agency with an understanding of that consumer and that could deliver great work," Ms. Lacasse said. With a new creative rollout anticipated in spring 2015, much is still to be decided, but it will include an emphasis on value, she said.


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Monday, October 27, 2014
Sunday, October 12, 2014
Remembering Back
|Source: Free Digital Photos Photographer Maggie Smith
I cannot cry
I feel nothing inside
Hollow is all that resides
Feelings once there
Now left with despair
Gloom and doom
Is all I see
What will become
Of me
Not sure if I really care
If I am here or there
Not much matters anymore
Go ahead walk out that door
Angry at what you do not see
This life is a living hell for me
Sometimes I invoke
To God to provoke
A glimmer of hope
There must be belief within me
For when I wake I pray to be
Back to the once normality
© 2011 Susan Zutautas
I have been reading so many articles on depression lately and so many of us have been there. The words above are how I remember being stuck in a funk for weeks upon weeks. It is difficult looking back and remembering how awful it felt, so someone please, say something funny to lighten my mood. Thanks so much for reading.
Thursday, October 9, 2014
Should a Would a Could a
|Myself with my mother in law Claire
The following poem is something I wrote for one of my dearest friends who just happens to be my Mother In Law.
We have had a really good relationship since we first met back in 1986, and have been great friends ever since.
Claire is notorious for saying I should have done this or I could have done that. This is what inspired me to write this poem for her.
Should a Would a Could a
Should a Would a Could a is not the place for you.
Think about tomorrow and the things you want to do.
Leave the Should a Would a Could a's where
They belong and think about the things to come,
Not where you've gone wrong.
Think about the dreams, the things you want to see.
Think about the fun that you shall have with me.
You cannot change the past, just Live for Today.
Yesterday is gone; leave it there, where it belongs.
Think about tomorrow and the things you want to do,
The Should a Would a Could a's of the past are gone.
© 2010 Susan Zutautas
© 2010 Susan Zutautas
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Most people will find that when making home repairs and overall improvements, the process never exactly meets the planning. You may think something will only take a day and a little effort, but you're likely to find that things get a bit more complicated. Work to streamline the improvement process by reading these tips.
Before beginning home improvements apply for the appropriate building permits. Any home improvement that involves plumbing navigate here, electricity, or structural changes can require a permit. Check your local laws. If you proceed without a permit then you can be fined or it could make the house harder to sell in the future.
If you put new cabinets in your home, your kitchen will glow with beauty and style. New cabinets show all of your family and friends that your kitchen is a professional place for cooking and entertainment. You can find cabinets in light wood stains and dark wood stains bathroom mirror tvs, giving you the ability to personalize your kitchen to your specific tastes.
Improve your home and lower your water bill by changing out your toilet with a more efficient model. Many companies have reduced the amount of gallons it takes to flush and they even feature options, such as flushing only liquids or solids, so you can control how much water is used, depending on what is in the toilet.
If you just purchased your home or are renovating it, you know that wallpaper borders can be a pesky item to remove. If you have the time and don't want to invest a lot of money in removing it, you can easily remove it with the following steps: 1. Get a small spray flask and fill it with water. 2. Grab a towel for the next step. Repeatedly spray the wallpaper border until it is thoroughly wet. The water activates the glue on the back and makes it slimy, which in turn makes it easier to remove. 3. Simply rub the towel over it in a circular fashion and it will start peeling off the wallpaper.
A very simple home improvement tip is to declutter. Start with this easy task: If you have kids, you may be guilty of cluttering your fridge with their work and little design magnets. Keep your appliances clear by attaching just some of your children's artwork and only a few magnets at a time. You can switch these items out every week.
Insulate exposed pipes in your home. If uninsulated, pipes can freeze during the winter. This can cause a great deal of stress and headache since you won't be able to access running water. The pipes could possibly burst. Exposed pipes may be located where you are unlikely to see them, such as, in the attic or the basement.
If you're looking for a low cost way to improve the look of your home's interior, add a fresh coat of paint. Make sure you choose a neutral color. Dark or drab colors can make a room feel oppressive and confining. Painting with neutral colors will give rooms a fresh, airy feeling of openness.
As was said earlier in the article, home improvement can turn into a great catastrophe if you do not have the knowledge necessary for some of the jobs. Now that you have the knowledge, apply it to your specific needs of home improvement. Don't let setbacks get you down, trudge through and the practice will make you better.


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NORR11 Line One Floor Lamp
Product Code: NR0133
Aluminium floor lamp with marble lamp base.
Illuminate the beauty of your interior design scheme with the NORR11 Line One Floor Lamp.
The smart contemporary floor lamp is a celebration of raw materials, clear silhouettes and gentle light, inspired by the movement and shadows of 1940s Film Noir cinema.
Great in the lounge or bedroom, the lamp features a clean line design and strong aluminium construction.
Presented in a choice of monochrome and oxidised colourways, the conical lamp head is gracefully elevated from a gently curving arm.
The lamp then creates a dynamic contrast thanks to its unique untreated marble base, providing a raw yet welcoming contrast of industrial and natural materials.
Experiment with designer lighting and furniture from the Houseology NORR11 collection to elevate your interior space in style.
Aesthetic: Due to the natural veined appearance of marble, each lamp base features a unique appearance and expression every time.
Light source: Requires 1x E14 40W Max bulb required (light bulb not included)
Cable length: 180cm
On/off switch on black cord cable.
About The Brand
Taking inspiration from Bauhaus design with accents of South Asian expression and the iconic style of the 18th century American Shaker movement, NORR11 seek to rethink and innovate design classics. In the pursuit of great design, each product is rooted in Scandinavia and steeped in Danish design heritage, offering comfortable, functional and timelessly stylish furniture pieces for contemporary living.
Why shop with Houseology
Houseology is not only the UK's premier online interior design store - it is an emporium of design ideas, advice & inspiration and a platform of tools & technology designed to make your interior design decisions and calculations easy.


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Date: Thursday 31 May 2018
Time: 7-8pm
Categories: talks free for friends
Devorah Baum shares the hilarious history of the Jewish joke in conversation with Peter Pomerantsev.
It is as old as Abraham, and like the Jews themselves it has wandered over the world, learned countless new languages, worked with a range of different materials, been performed in front of some pretty hostile crowds, but still retained its own distinctive identity.
So what is it that animates the Jewish joke? Why are Jews so often thought of as 'funny'? And how old can a joke get?
Baum will be discussing her latest book, 'The Jewish Joke', which is a brilliant - and very funny - riff on Jewish jokes about what marks them apart from other jokes, why they are important to Jewish identity, and how they work. Ranging from self-deprecation to anti-Semitism, politics to sex, it looks at the past of Jewish joking and asks whether the Jewish joke has a future. With jokes from Woody Allen, Lena Dunham and Jerry Seinfeld, as well as Freud and Marx (Groucho mostly), this is both a compendium and a commentary, light-hearted and deeply insightful.
There will be a book signing at 8pm
Doors 6pm | Cafe 6-7pm | Shop 6-7pm | Galleries open 6-7pm and 8-8.30pm
About the speakers:
Devorah Baum is the author of 'Feeling Jewish' (a book for just about anyone) (Yale, October 2017) and co-director of the documentary film 'The New Man'.
She is Lecturer in English Literature and Critical Theory at the University of Southampton and affiliate of the Parkes Institute for the Study of Jewish/non-Jewish Relations.
Peter Pomerantsev is a Visiting Senior Fellow at the LSE, an author and TV producer. He writes for publications including the FT, LRB and many others. His book on Russian propaganda, Nothing is True and Everything is Possible, won the 2016 Royal Society of Literature Ondaatje Prize, was nominated for the Samuel Johnson, Guardian First Book, Pushkin House and Gordon Burns Prizes. It is translated into over a dozen languages. He is working on his next book, which looks at developments in the 'battle for hearts and minds' across the world


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Aug. 25, 2010
MARYVILLE, Mo. - Northwest welcomes 21 new staff members and 21 new faculty to start its 2010-2011 academic year. New staff members are those who have begun working at the University since February.
|Dr. Casey Abington is an assistant professor in the accounting, economics and finance department, where she will be teaching general economics; money, credit and banking; and a graduate course in financial management. She earned her doctorate in May from Kansas State University, where she also taught.
|Jerin Adcock became library generalist/reserve at Owens Library in May. He received his bachelor's in business management and marketing from Northwest in 2008. He returned to earn his MBA, which he completed in May.
|Brooke Badger is registrar services specialist. She received her bachelor's in marketing from Northwest in May and plans to begin the MBA program at Northwest next summer. Brooke is from Des Moines, Iowa.
|Steven Banks is an instructor in the art department. He accepted a one-year appointment to teach sculpture courses, jewelry and metals, and introduction to three-dimensional design studio. He taught previously at Northwest and Saint Ambrose University. He was exhibits manager for The Putnam Museum, construction coordinator for Midcoast Fine Arts Bucktown Center for the Arts and has written numerous articles and art reviews for the River Cities' Reader.
Nate Blackford is director of strategic research in the Office of Institutional Research. Nate will lead entrepreneurial efforts, analyze needs and translate them into data requests. He previously worked in Kansas City at Service Management Group and Cerner Corporation. He earned his bachelor's and his MBA from Northwest.
|Lori Brack is an instructor with a one-year appointment in the English department. She will teach composition and introduction to literature. She was a full-time adjunct instructor at Kansas State University at Salina, and taught as an adjunct at Kansas private colleges and community colleges.
|Stacy Carrick became vice president of finance in February. A Certified Public Accountant, she received her bachelor's from Northwest in 1988 and an MBA from Webster University. Carrick served in a variety of capacities for Heartland Health in St. Joseph, most recently as the director for decision support services.
Sarah Creason is an instructor in the family and consumer sciences department. She holds an associate degree in childcare administration, a bachelor's in family and consumer sciences education and a master's in early childhood education, all from Northwest. She was preschool teacher in the Early Care and Education Center.
|Kurt Davis is a new groundskeeper on the west side of campus. He previously farmed in Ravenwood for 40 years. His son Ryan is a Northwest graduate; his other son Tyler worked on our athletic grounds this summer.
|Kyle Dennis is a lecturer in the communications, theatre and languages department. He earned his bachelor's in economics with an emphasis in finance from Southern Illinois University in 2008 and completed a master's in communication studies from Texas Tech University this month. He was a member of Southern Illinois' national champion competitive debate team and coached Texas Tech to a national championship in March.
"Kash" Vishnuprakash Dhanapal is Franken Hall director. He has a bachelor's in economics with a minor in business administration from Northern Michigan University.
|Travis Dimmitt is a project assistant for curriculum and instruction at the Northwest Missouri Regional Professional Development Center. Dimmitt taught social studies the last six years at North Nodaway High School. He earned his bachelor's from Northwest in 1998 and his master's in secondary education administration.
|Jennifer Edick is Wellness Center coordinator. Previously, she was employed in the quality assurance department at Boehringer Ingelheim Vetmedica Inc. in St. Joseph. She is completing her bachelor's in business management at Northwest.
|Clint Farnan became custodian in March. He works in the Fire Arts building, landscape services and athletic grounds areas. Prior to coming to Northwest, he was employed at Conception Abbey.
|Teresa Foster-Heerman is a custodian in Garrett-Strong. She has a degree in cosmetology and previously was employed as a custodian for Lomas Janitorial in Independence.
|Lynne Gilbert is administrative specialist to the president. Lynne arrived in July from Andrew County Soil and Water Conservation District. She has a range of experience in schools, hospitals, financial institutions, private corporations and government agencies. She earned her bachelor's in human environmental services from the University of Missouri-Columbia.
|Ashley Greeley is department secretary in the computer science and information systems department. She earned her bachelor's in office information systems and financial computing from Northwest. She previously worked six years at Nodaway Valley Bank.
|Ellen Haley is an instructor with a one-year appointment in the communication, theatre and languages department. She will teach Spanish and upper-division language education courses, in addition to Spanish courses at Stanberry High School. She's taught in Missouri public schools since earning her bachelor's from Northwest in 2006. This summer, she completed her master's at Northwest in teaching English language learners.
|Kevin Hawkins is a new officer. He is an accounting major and recent graduate of the police academy at Missouri Western State University. He was a University Police student employee for two years.
|Kevin Hiatt began as a custodian in February. He is assigned to Franken, Dietrich and East Tower Suites. Previously, he was employed seasonally with the Staffing Center in St. Joseph.
Courtney Holt became director of the Early Care and Education Laboratory Center and head teacher in the family and consumer sciences department. She has her master's in early childhood education from Northwest and her bachelor's in early childhood education from Graceland University in Lamoni, Iowa.
|David Johnson is an instructor in the accounting, economics and finance department, where he will teach fundamentals of business finance and financial institutions. Previously, he taught at Allen University in Columbia, S.C., and as finance adjunct at the Moore School of Business and the School of Hotel, Restaurant, and Tourism at the University of South Carolina.
Dr. Melvin Johnson is an instructor with a one-year appointment in the geology and geography department. He will teach a variety of lower- and upper-division geography courses. He specializes in economic geography and water resources development, conflict and conflict resolution, with areas of interest of North American and Africa.
Dr. John Katsion is an assistant professor in the communication, theatre and languages department. He will teach fundamentals of oral communication and upper-division classes in the communication area. He taught previously at Hannibal-LaGrange College in Hannibal and at Multnomah University in Portland, Ore.
|Dr. Jackie Kibler joined the Missouri Academy of Science, Mathematics and Computing as director of counseling. She returned to Northwest from the University of Montana, where she spent two years as a faculty member in the psychology department. From 2001 to 2008, Kibler was a faculty member in the psychology, sociology and counseling department at Northwest, where she continues adjunct teaching each trimester.
Monica Landess is an instructor in the curriculum and instruction department. She is director of Horace Mann Laboratory School. She was elementary principal in the Stewartsville C-2 School District since 2005. Landess earned her bachelor's in early childhood and elementary education from Northwest and a master's in educational leadership from the University of Missouri-Kansas City.
Mindee Lieske is an instructor with a one-year appointment in the English department. She will teach composition, introduction to literature, and upper-division writing courses such as technical writing and writing for the online age. Mindee also is interim coordinator of the Writing Center. She previously taught at Indiana University of Pennsylvania, California State-Northridge and the University of Southern California.
|Diana Linville is an instructor in the computer science and information systems department where she will teach computers and information technology, spreadsheet applications, advanced spreadsheets and charting, database applications, and IT hardware and software. A Northwest alumna, she previously taught at Northwest as an adjunct and at the Maryville Technical School.
|Michael Lyle became an officer in April. His background consists of police work with Springfield, Republic and Aurora Police departments. In 2004, he retired after 31 years with Southwestern Bell Corp., where he was area manager of design engineering and construction for the southwest Missouri region.
|Micheal Mandrick is a PC specialist. He graduated from Northwest this year with a bachelor's degree in interactive digital media-visual imaging. As a student he worked as a computer consultant in Owens Library, PC technician in the Electronic Campus Support Center and multimedia designer in the CITE office.
|Terry Manies is grants coordinator and works with community partners to secure external funding to support Northwest's mission. Terry has worked in grant funding at the University of Kansas Higuchi Biosciences Center, Baker University, the Kansas Department of Corrections and the Kansas Department of Social and Rehabilitation Services.
|Dr. Mohammed Meziani is an assistant professor in the chemistry and physics department. He specializes in nanoscience and organic chemistry
|Melissa Mincy started this summer as financial assistance specialist. Previously she taught second grade at Northeast Nodaway and was a Head Start preschool teacher. She has a bachelor's in education with a minor in early childhood from Northwest.
Meghan Nelson is an assistant women's basketball coach. Nelson spent the last two seasons as assistant coach at the University of Sioux Falls in South Dakota, where she earned her MBA. Nelson has a bachelor's from Southwest Minnesota State University where she completed a five-year playing and coaching career.
Dr. Douglas Overmier is an assistant professor in the music department. He serves as interim director of bands in addition to conducting instrumental ensembles and teaching conducting and arranging classes.
Dr. Jonathan Pluskota is an assistant professor in the mass communication department, where he will teach media leadership, media criticism, radio production and advise students working at KZLX. He comes to Northwest from The Art Institute of Austin where he was director of audio. He earned his bachelor's and master's from Southern Illinois where he also taught.
|Adam Rittel joined Northwest as custodian at Brown Hall. He holds a master's in risk control from the University of Wisconsin-Stout. His wife, Kristina, is employed at the Missouri Academy.
Cindy Scarbrough is preschool lead teacher in the family and consumer sciences department. She also will teach at Horace Mann Laboratory School and Early Care and Education Laboratory Center. She is a Northwest alumna.
|Tiebing Shi is an assistant professor in the marketing and management department. He will teach undergraduate and graduate level international business courses and undergraduate marketing management. Previously, he taught at Queen's School of Business in Kingston, Ontario, Canada, where he is a doctoral candidate in marketing. He received his MBA from the University of International Business and Economics in Beijing.
Dr. William Siever is an instructor in the department of computer science and information systems, where he will teach computer programming and data and file structures. He comes to Northwest from Michigan Technological University. He also was an instructor at Missouri University of Science and Technology, where he completed his doctorate.
Rená Smith is an instructor in the chemistry and physics department. She is a Northwest alumna and specializes in science education. Previously, she taught at the University of Missouri-Columbia for the teacher development program.
Janet Steins began as a custodian in June. She is assigned to the Alumni House, Martindale and the Robert P. Foster Aquatic Center. She has a son, Michael Clements, who will graduate from Northwest in December.
Dr. Deborah Taylor is an assistant professor in the educational leadership department, where she will teach foundations of educational administration, secondary school teaching practicum II, and school and society. Her previous experience includes teaching and administrative work at the U.S. State Department-sponsored school in Taiwan; in Tulsa, Okla., Public Schools; as well as at public schools in Missouri, Iowa and Bahrain in the Middle East.
Dr. Philip Wainwright is an assistant professor in the educational leadership department. His experience includes 18 years as superintendent of schools in Iowa and five years as a secondary principal. He also spent six years as dean of students for the Eastern Iowa Community College District. Most recently, he was associate professor of education at Grand View University in Des Moines, Iowa. He will teach pluralism in a multicultural society, and school and community relations, in addition to working with practicum students and supervising student teachers.
Mark Hornickel, Communication Manager
email@example.com | 660.562.1704 | Fax: 660.562.1900
Northwest Missouri State University
215 Administration Building | 800 University Drive | Maryville, MO 64468