BOREAS TGB-05 Dissolved Organic Carbon Data from NSA Beaver Ponds Summary The BOREAS TGB-05 team collected several data sets related to carbon and trace gas fluxes and concentrations in the NSA. This data set contains concentrations of dissolved organic and inorganic carbon species from water samples collected at various NSA sites. In particular, this set covers the NSA Tower Beaver Pond Site and the NSA Gillam Road Beaver Pond Site, including data from all visits to open water sampling locations during the BOREAS field campaigns from April to September 1994. The data are provided in tabular ASCII files. Table of Contents * 1 Data Set Overview * 2 Investigator(s) * 3 Theory of Measurements * 4 Equipment * 5 Data Acquisition Methods * 6 Observations * 7 Data Description * 8 Data Organization * 9 Data Manipulations * 10 Errors * 11 Notes * 12 Application of the Data Set * 13 Future Modifications and Plans * 14 Software * 15 Data Access * 16 Output Products and Availability * 17 References * 18 Glossary of Terms * 19 List of Acronyms * 20 Document Information 1. Data Set Overview 1.1 Data Set Identification BOREAS TGB-05 Dissolved Organic Carbon Data from NSA Beaver Ponds 1.2 Data Set Introduction Organic matter is a major component of the boreal forest ecosystem, and can be considered as the defining parameter for biogeochemical processes occurring in the soil, wetlands, ponds, and lakes in the boreal forest. Beaver ponds are common in the boreal forest, and dissolved organic matter (DOM) is the dominant aquatic component. 1.3 Objective/Purpose Trace Gas Biogeochemistry Team 5 (TGB-05) studied the character of DOM from an active beaver pond near Thompson, Manitoba, Canada, in conjunction with the BOReal Ecosystem-Atmosphere Study (BOREAS) project. This study spans the entire hydrologic cycle in 1994 from snowmelt and ice breakup through the spring flood, summer growing season and autumn draw down. 1.4 Summary of Parameters Dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), particulate organic carbon (POC), and DOM fractions (see Section 18). 1.5 Discussion Water samples were collected throughout the BOREAS sampling periods described above for all open water sites (including some earlier samples that were under ice) and from inflow, groundwater, and drainage sites. These samples were analyzed in a timely manner at a field lab in Thompson for various aquatic carbon species, as described in Sections 1.4 and 7. 1.6 Related Data Sets BOREAS TGB-01 Soil CH4 and CO2 Profile Data over the NSA BOREAS TGB-01 CO2 and CH4 Chamber Flux Data over the NSA BOREAS TGB-01 CH4 Tower Flux Data over the NSA BOREAS TGB-03 NEE and Air and Water Temperature Data over the NSA Fen BOREAS TGB-03 CO2 and CH4 Chamber Flux Data over the NSA BOREAS TGB-03 Soil CO2 and CH4 Profile Data over the NSA BOREAS TGB-05 Aquatic Carbon Species 1994 over the NSA BOREAS TGB-05 CO, CO2, and CH4 Chamber Flux Data over the NSA BOREAS TGB-12 CO2 Flux Data over the NSA BOREAS TGB-12 CO2 Soil Profile Data over the NSA BOREAS TGB-12 Soil Carbon Isotope Data over the NSA BOREAS TGB-12 Soil Carbon Map in Raster Format 2. Investigator(s): 2.1 Investigator(s) Name and Title Dr. Richard A. Bourbonniere, TGB-05 2.2 Title of Investigation Biogeochemistry of Dissolved Organic Matter - Disturbances 2.3 Contact Information Contact 1 --------- Dr. Rick Bourbonniere Environment Canada National Water Research Institute Burlington, ON CANADA (905) 336-4547 (905) 336-4972 (fax) RICK.BOURBON@CCIW.CA Contact 2 --------- Sara Conrad Raytheon STX Corporation NASA GSFC Greenbelt, MD (301) 286-2624 (301) 2186-0239 (fax) Sara.Golightly@gsfc.nasa.gov 3. Theory of Measurements: Chemical measurements were made on water samples. Dissolved carbon analyses were made using a Dohrmann DC-190 Carbon Analyzer. This instrument uses the High Temperature Catalytic Oxidation (HTCO) method to determine total carbon (TC) and organic carbon (DOC) species, and acidification and sparging for inorganic carbon (DIC) species. An alternate method of measuring DIC, the difference method (see below), was used for all 1994 samples. The quartz oxidation tube was filled with a catalyst made of platinum on alumina beads and placed in a furnace set at 900 degrees C; the carrier gas was Ultra High Purity Zero Air from Canox at 200 mL/min. The detector on this instrument is a Milton Roy Model 3300 nondispersive infrared (NDIR) gas analyzer (Mfg: Fuji Electric), which is a single beam detector with a wide dynamic range. The instrument was used mostly in the automatic sampling mode (ASM), but occasionally manual injection was used. TC analyses were done on whole filtered samples, DOC was determined after acidification (pH <4 using 20% phosphoric acid) and sparging (5 minutes with carrier) to remove DIC and DIC was determined by the difference: TC - DOC = DIC. POC was determined by HTCO on filters using a CHN Analyzer after acidification to remove solid carbonates (done by Environment Canadaís National Laboratory for Environmental Testing, Burlington, ON). 4. Equipment 4.1 Sensor/Instrument Description 4.1.1 Collection Environment Samples were collected under all environmental conditions. 4.1.2 Source/Platform Ground. 4.1.3 Source/Platform Mission Objectives None given. 4.1.4 Key Variables Fulvic Acid (FA), Humic Acid (HA), Hydrophobic Acid (HPOA), Hydrophobic Neutral (HPON), Hydrophilic Acid (HPIA), Hydrophilic Neutral (HPIN), and X4AC are fractions of DOM (see Section 18). 4.1.5 Principles of Operation Dissolved Carbon analyses were made using a Dohrmann DC-190 Carbon Analyzer. This instrument uses the High Temperature Catalytic Oxidation (HTCO) method to determine total (TC) and organic carbon (DOC) species, and acidification and sparging for inorganic carbon (DIC) species. An alternate measurement of DIC, the difference method (see below) was used for all 1994 samples. The quartz oxidation tube was filled with a catalyst made of Platinum on Alumina beads, placed in a furnace set at 900 degrees C, and the carrier gas was Ultra High Purity Zero Air from Canox at 200 mL/min. 4.1.6 Sensor/Instrument Measurement Geometry Not applicable. 4.1.7 Manufacturer of Sensor/Instrument Dohrmann DC-190 Carbon Analyzer Tekmar-Dohrmann P.O. Box 429576 Cincinnati, OH 45249 (800)-543-4461 (Sales) (800)-874-2004 (Service) (513)-247-7000 (Outside the USA/Canada) (513)-247-7050 (Fax) 4.2 Calibration 4.2.1 Specifications The DC-190 uses a single-point calibration method. This is possible because of the wide dynamic range of the detector and the stable, closely spaced calibration curves stored in the instrument by the factory. Calibrations for TC and DOC were done using fresh dilutions of Potassium Biphthalate (KHP), primary standard grade, diluted with E-Pure water (Barnstead). System blanks were calculated by regressing results from low ppm range standards; the intercept of a true value vs. measured value was called the system blank and was subtracted from each analysis. The calibration factor was updated for each set of 32 samples, and system blank samples were included within each set. Under the conditions described above, system blanks were typically between 1-2 mgC/L. Note that much of this is probably attributable to residual carbon in the E-Pure water, as carbon-free water was unattainable. Under these conditions, the system blank correction is probably higher than the actual system blank. Under the high TC and DOC conditions found for the waters in the Northern Study Area (NSA), the system blank accounts for 4-8% of the measured values, and the over correction could be as high as 3-6%. Without "carbon-free water," this could not be improved. 4.2.1.1 Tolerance None given. 4.2.2 Frequency of Calibration None given. 4.2.3 Other Calibration Information None given. 5. Data Acquisition Methods The DC-190 uses internal algorithms to calculate carbon concentrations that are reported directly in printed form for each analysis. Each sample was analyzed in triplicate for TC and in quadruplicate for DOC. 6. Observations 6.1 Data Notes Raw data are held by the Principal Investigator (PI). 6.2 Field Notes Extensive field notes were routinely made during sampling and recorded on microcassettes. Transcription can be made available by the PI. 7. Data Description 7.1 Spatial Characteristics 7.1.1 Spatial Coverage All of the data in this set are results of analyses of water samples taken from the NSA Tower Beaver Pond Site (TP) including its groundwater inputs, open water sites on the pond, and its inflow and outflow creeks. All site designations are TP for this data set. Sub-designations refer to the specific location within the TP watershed where the water sample was taken: P1-P10 - Ten refers to 10 open water sites on the Beaver Pond. Site P1 is the "main" site and is at the deepest part of the pond. PL, B3 - Sites along the boardwalk to the tower platform. OD, UD - Sampled from over and under the main (east) dam. NOD - Sampled from over the dam on the older pond to the north of TP. WD - Sampled from the footbridge at the west dam outlet. D, D2 - Sampled from the Highway 391 (100 m from road) end of the drainage creeks that flow from the west and east dams, respectively. I1, I2, I3 - Inflow creeks on the south end of the pond, sampled at their mouths. I3 is the main inflow of surface water to the pond. SM - Snowmelt collected during the thaw period. FP, C, H - Samples from intermittent surface inflows along the southwest, south, and southeast perimeter of TP. These flowed only occasionally after rain events during the thaw period. SZ(S), SZ(M), SZ(D) - Shallow, Middle, and Deep piezometers (wells) from a nest adjacent to TP at the west end of the main (east) dam. NZ(S), NZ(M), NZ(D) - Shallow, Middle, and Deep piezometers (wells) from a nest adjacent to the older pond to the north of TP and also near the west end of the old dam. NZDP1, NZDP2 - The first and second pools of groundwater collected from the NZ(D) piezometer over a number of days during Focused field Campaign-Thaw (FFC-T) and Intensive Field Campaign (IFC)-1. HOLE - Water sampled through a hole in the ice adjacent to the boardwalk, equivalent to B3 under ice conditions. Sample Depth - All surface samples were taken at approximately 10 cm depth. Other depths refer to the measured depths from the pond surface and piezometer depths are the deepest part of the interval sampled. The shallowest depth for any well is the deepest interval for the well above, and zero for the shallow wells. All of the data in this set are results of analyses of water samples taken from the NSA Gillam Road Beaver Pond Site including its groundwater inputs, open water sites on the pond, and its inflow and outflow creeks. All site designations are NSA Gillam Road Beaver Pond Site for this data set. Sub-designations refer to the specific location within the NSA Gillam Road Beaver Pond Site watershed where the water sample was taken: ROAD P SM - Snowmelt collected during the thaw period. SZ(S), SZ(M) ñ Shallow and Middle piezometers (wells) from a nest adjacent to the Gillam Beaver Pond S1 NZ(S), NZ(D) ñ Shallow and Deep piezometers (wells). P1-6 - Ten refers to 6 open water sites on the Beaver Pond. Site P1 is the "main" site and is at the deepest part of the pond. TD I1 - Inflow creeks on the south end of the pond, sampled at their mouths. W OD - Sampled from over and under the main (east) dam. 7.1.2 Spatial Coverage Map None given. 7.1.3 Spatial Resolution The total area of the NSA Tower Beaver pond is 5 ha, and its northern end is approximately 500 m south of Highway 391. All groundwater, inflow, and open water sites are within the 5-ha pond area, and outflow sites are either at the pond edge or adjacent to Highway 391. More details regarding the TP are found in Dove (1995). The Gillam road beaver pond is located at (55.8958N, 98.7583W) 7.1.4 Projection Not applicable. 7.1.5 Grid Description Not applicable. 7.2 Temporal Characteristics 7.2.1 Temporal Coverage All samples were collected between 22-Apr and 19-Sep-1994 (FFC-T, IFC-1, IFC-2, and IFC-3) and are of variable frequency by site (some daily for a short period, many weekly during IFCs, and some occasionally, e.g., once during an IFC, or once during the wet period.) 7.2.2 Temporal Coverage Map None given. 7.2.3 Temporal Resolution Samples are of variable frequency by site (some daily for a short period, many weekly during IFCs, and some occasionally, e.g., once during an IFC, or once during the wet period). 7.3 Data Characteristics Data characteristics are defined in the companion data definition file (TGB05DocD.def). 8. Data Organization 8.1 Data Granularity All the Dissolved Organic Carbon Data from NSA Beaver Ponds data are contained in one dataset. 8.2 Data Format(s) The data files contain numerical and character fields of varying length separated by commas. The character fields are enclosed with single apostrophe marks. There are no spaces between the fields. Sample data records are shown in the companion data definition file (TGB5DocD.def). 9. Data Manipulations 9.1 Formulae Some formulae were used in DOM fraction calculations prior to input into the data set - see Section 17, References. 9.1.1 Derivation Techniques and Algorithms None given. 9.2 Data Processing Sequence 9.2.1 Processing Steps None given. 9.2.2 Processing Changes None given. 9.3 Calculations 9.3.1 Special Corrections/Adjustments All FA data are corrected for the average ëfilter blankí for the entire season. Difference calculations for DIC, HA, HPON, and X4AC occasionally resulted in small negative values, which were edited to zero. 9.3.2 Calculated Variables None given. 9.4 Graphs and Plots None given. 10. Errors 10.1 Sources of Error The system blank for the Dohrmann DC-190 is the main source of error, but since carbon values are generally greater than 10 mgC/L, the correction is rarely more than 10% of the value and usually less than 5%. 10.2 Quality Assessment 10.2.1 Data Validation by Source All carbon determinations reported are averages of 3 (TC) or 4 (DOC) replicate analyses on the Dohrmann DC-190. 10.2.2 Confidence Level/Accuracy Judgment None given. 10.2.3 Measurement Error for Parameters The precision for TC was typically +/- 0.8 mgC/L at the 50 mgC/L level and for DOC a precision of +/- 0.5 mgC/L was typical at the 25 mgC/L level. 10.2.4 Additional Quality Assessments A few obvious outlier values were deleted from the data set. These samples had very high DOC or TC values that resulted from contamination during sampling. 10.2.5 Data Verification by Data Center Data were examined for general consistency and clarity. 11. Notes 11.1 Limitations of the Data Not all parameters were determined for all samples, and not all sites were covered for all dates. See above descriptions. 11.2 Known Problems with the Data System blanks were typically between 1-2 mgC/L. Note that much of this is probably attributable to residual carbon in the E-Pure water, as carbon-free water was unattainable. Under these conditions, the system blank correction is probably higher than the actual system blank. Under the high TC and DOC conditions found for the waters in the NSA, the system blank accounts for 4-8% of the measured values, and the overcorrection could be as high as 3-6%. Without carbon-free water, this could not be improved. 11.3 Usage Guidance Note that the definition of HA used here is more like the traditional soil science definition and differs from that used by many aquatic scientists (see references). Note that DIC by difference is subject to more error than DIC measured directly. 11.4 Other Relevant Information None given. 12. Application of the Data Set This data set was created for BOREAS investigators who need soils data in the vicinity of the NSA for further modeling and to generate maps of carbon stocks and fluxes. 13. Future Modifications and Plans None planned. 14. Software 14.1 Software Description None. 14.2 Software Access None given. 15. Data Access 15.1 Contact Information Ms. Beth Nelson BOREAS Data Manager NASA GSFC Greenbelt, MD (301) 286 4005 (301) 286 0239 (fax) Elizabeth.Nelson@gsfc.nasa.gov 15.2 Data Center Identification See Section 15.1. 15.3 Procedures for Obtaining Data Users may place requests by telephone, electronic mail, or fax. 15.4 Data Center Status/Plans The TGB-05 dissolved organic carbon data are available from the Earth Observing System Data and Information System (EOSDIS) Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC). The BOREAS contact at ORNL is: ORNL DAAC User Services Oak Ridge National Laboratory (865) 241-3952 ornldaac@ornl.gov ornl@eos.nasa.gov 16. Output Products and Availability 16.1 Tape Products Not applicable 16.2 Film Products Not applicable. 16.2 Other Products Comma-delimited ASCII text files. 17. References 17.1 Platform/Sensor/Instrument/Data Processing Documentation None. 17.2 Journal Articles and Study Reports Aiken, G.R., D.M. McKnight, K.A. Thorn, and E.M. Thurman. 1992. Isolation of hydrophilic organic acids from water using nonionic macroporous resins. Org. Geochem., 18(4):567-753. Bourbonniere, R.A. 1989. Distribution patterns of dissolved organic matter fractions in natural waters from eastern Canada. Org. Geochem, 14:97-107. Bourbonniere, R.A. and T. van Halderen. 1989. Fractional precipitation of humic acid in coloured natural waters. Water, Air & Soil Pollution, 46:187-198. Bourbonniere, R.A., L.A. Ziolkowski, S.L. Telford, M.A. Moran, K.L. Bushaw, W.L. Miller, M.A. Tarr, and R.G. Zepp. 1995. Character and biogeochemistry of dissolved organic matter in a boreal forest beaver pond near Thompson, Manitoba, Canada. In: Organic Geochemistry: Developments and Applications to Energy, Climate, Environment and Human History, J.O. Grimalt and C. Dorronsoro - eds. Published by A.I.O.G.A., Donostia-San Sebastian, SPAIN, 1144-1146. Dove, A.E. 1995. Methane dynamics of a northern boreal beaver pond. MSc Thesis, McGill University, Geography, Montreal, QC, 136 pp. Leenheer, J.A. 1981. Comprehensive approach to preparative isolation and fractionation of dissolved organic carbon from natural waters and wastewaters. Environ. Sci. Technol., 15:578-587. Malcolm, R.L. and P. MacCarthy. 1992. Quantitative evaluation of XAD-8 and XAD- 4 resins used in tandem for removing organic solutes from water. Environ. Internat., 18:597-607. Sellers, P.and F. Hall. 1994. Boreal Ecosystem-Atmosphere Study: Experiment Plan. Version 1994-3.0, NASA BOREAS Report (EXPLAN 94). Sellers, P., F. Hall, H. Margolis, B. Kelly, D. Baldocchi, G. den Hartog, J. Cihlar, M.G. Ryan, B. Goodison, P. Crill, K.J. Ranson, D. Lettenmaier, and D.E. Wickland. 1995. The boreal ecosystem-atmosphere study (BOREAS): an overview and earlyresults from the 1994 field year. Bulletin of the American Meteorological Society. 76(9):1549-1577. Sellers, P.and F. Hall. 1996. Boreal Ecosystem-Atmosphere Study: Experiment Plan. Version 1996-2.0, NASA BOREAS Report (EXPLAN 96). Sellers, P., F. Hall, and K.F. Huemmrich. 1996. Boreal Ecosystem-Atmosphere Study: 1994 Operations. NASA BOREAS Report (OPSDOC 94). Sellers, P., F. Hall, and K.F. Huemmrich. 1997. Boreal Ecosystem-Atmosphere Study: 1996 Operations. NASA BOREAS Report (OPSDOC 96). Sellers, P.J., F.G. Hall, R.D. Kelly, A. Black, D. Baldocchi, J. Berry, M. Ryan, K.J. Ranson, P.M. Crill, D.P. Lettenmaier, H. Margolis, J. Cihlar, J. Newcomer, D. Fitzjarrald, P.G. Jarvis, S.T. Gower, D. Halliwell, D. Williams, B. Goodison, D.E. Wickland, and F.E. Guertin. (1997). "BOREAS in 1997: Experiment Overview, Scientific Results and Future Directions", Journal of Geophysical Research (JGR), BOREAS Special Issue, 102(D24), Dec. 1997, pp. 28731-28770. 17.3 Archive/DBMS Usage Documentation None given. 18. Glossary of Terms The fractionation procedure for DOM results in these fraction definitions: Humic Acid (HA) - Precipitates within 24 hrs. at pH=2 from filtered whole water. Fulvic Acid (FA) - Components that are soluble at pH=2. FA Subfractions: Hydrophobic Acid (HPOA) - Adsorbs to XAD-8 at pH=2 and is eluted with 0.1 M NaOH. Hydrophobic Neutral (HPON) - Adsorbs to XAD-8 at pH=2, does not elute with 0.1 M NaOH, extracted off resin with methanol and acetonitrile. Hydrophilic Acid (HPIA) - Adsorbs to XAD-4 resin at pH=2, elutes with 0.1 M NaOH. Hydrophilic Neutral (HPIN) - Passes through both resins. "XAD-4 Acids" (X4AC) - Adsorbs to XAD-4 at pH=2, does not elute with 0.1 M NaOH, extracted off resin with methanol and acetonitrile. 19. List of Acronyms: ASCII - American Standrad Code for Inforamtion Interchange ASM - Automatic Sampling Mode (for Carbon Analyzer) BOREAS - BOReal Ecosystem-Atmosphere Study BORIS - BOREAS Information System CHN - Carbon-Hydrogen-Nitrogen DAAC - Distributed Active Archive Center DIC - Dissolved Inorganic Carbon DOC - Dissolved Organic Carbon DOY - Day of Year (Julian Day) DOM - Dissolved Organic Matter EOS - Earth Observing System EOSDIS - EOS Data and Information System FA - Fulvic Acid (DOM that is soluble at pH=2) FFC-T - Focused Field Campaign-Thaw GP - Gillam Road Beaver Pond (NSA) GSFC - Goddard Space Flight Center HA - Humic Acid (DOM that is insoluble at pH=2) HPIA - Hydrophilic Acid (fraction of FA) HPIN - Hydrophilic Neutral (fraction of FA) HPOA - Hydrophobic Acid (fraction of FA) HPON - Hydrophobic Neutral (fraction of FA) HTCO - High Temperature Catalytic Oxidation IFC - Intensive Field Campaign NASA - National Aeronautics and Space Administration NDIR - Nondispersive Infrared NSA - Northern Study Area ORNL - Oak Ridge National Laboratory PANP - Prince Albert National Park PI - Private Investigator POC - Particulate Organic Carbon SSA - Southern Study Area TGB-05 - Trace Gas biogeochemistry Team 5 TC - Total Carbon TP - Tower Beaver Pond at the NSA (and sampling sites in its watershed) URL - Uniform Resource Locator X4AC - ÏXAD-4 AcidÓ (fraction of FA) 20 Document Information 20.1 Document Revision Date Written: 13-Feb-1998 Last Updated: 11-Sep-1998 20.2 Document Review Date(s) BORIS Review: 13-Feb-1998 Science Review: 20.3 Document 20.4 Citation None given. 20.5 Document Curator 20.6 Document URL Keywords: Carbon Flux Carbon Dioxide Methane TGB05_DissOrgC.doc 09/14/98