I. Data Set Descriptors A. Title: Samantha B. Joye. 2002. Porewater nutrients, dissolved organics, redox species, and gasses in estuarine intertidal sediments at sites on Sapelo Island and near the Satilla River from Fall 2000 through Fall 2002. Georgia Coastal Ecosystems LTER Data Catalog (data set POR-GCED-0210; http://gce-lter.marsci.uga.edu/public/app/dataset_details.asp?accession=POR-GCED-0210) B. Accession Number: POR-GCED-0210 C. Description 1. Originator(s): Name: Samantha B. Joye Address: Dept. of Marine Sciences University of Georgia Athens, Georgia 30602-3636 Country: USA Email: mjoye@uga.edu 2. Abstract: Seasonal patterns of estuarine creek-bank sediment porewater nutrients, dissolved organics, redox species and gasses were investigated at several sites on Sapelo Island and the Satilla River in coastal Georgia. Porewater ammonium, nitrate+nitrite, phosphate, silica, dissolved organic carbon, nitrogen and phosphorus, reduced iron and manganese, chloride, sulfate, hydrogen sulfide, pH, dissolved inorganic carbon, methane and nitrogen gas were measured at centimeter scale resolution depth profiles with the use of porewater equilibration meters. Several relatively pristine sites on Sapelo Island (Moses Hammock, Dean Creek and Marine Institute), a site slightly impacted by development (White Oak Creek) and a presumably heavily impacted site (Dover Bluff) show different levels and patterns of several porewater constituents. 3. Study Type: Directed Study 4. Study Themes: Pore-water Chemistry, General Nutrient Chemistry, Organic Matter/Decomposition 5. LTER Core Areas: Inorganic Nutrients 6. Georeferences: geographic coordinates as data columns 7. Submission Date: Oct 16, 2002 D. Keywords: ammonium, biogeochemistry, carbon, chloride, gas flux, Inorganic Nutrients, iron, manganese, methane, nitrate, nitrogen, organic, ph, phosphate, phosphorus, porewater, silica, sulfate, sulfide II. Research Origin Descriptors A. Overall Project Description 1. Project Title: Georgia Coastal Ecosystems LTER Project 2. Principal Investigators: Name: James T. Hollibaugh Address: Dept. of Marine Sciences University of Georgia Athens, Georgia 30602-3636 Country: USA Email: aquadoc@uga.edu 3. Funding Period: May 01, 2000 to May 01, 2006 4. Objectives: To investigate the linkages between coastal and distant upland areas in central Georgia mediated by surface and ground water delivery to the coastal zone. This will be addressed by examining the relationship between variability in environmental factors driven by river flow, primarily salinity, and ecosystem processes and structure. 5. Abstract: We propose to establish a Long Term Ecological Research site on the central Georgia coast in the vicinity of Sapelo Island. This is a barrier island and marsh complex with the Altamaha River, one of the largest and least developed rivers on the east coast of the US, as the primary source of fresh water. The proposed study would investigate the linkages between local and distant upland areas mediated by water - surface water and ground water - delivery to the coastal zone. We would explicitly examine the relationship between variability in environmental factors driven by river flow, primarily salinity because we can measure it at high frequency, and ecosystem processes and structure. We will accomplish this by comparing estuary/marsh complexes separated from the Altamaha River by one or two lagoonal estuary/marsh complexes that damp and attenuate the river signal. This spatial gradient is analogous to the temporal trend in riverine influence expected as a result of development in the watershed. We will implement a monitoring system that documents physical and biological variables and use the time trends and spatial distributions of these variables and of their variance structure to address questions about the factors controlling distributions, trophic structure, diversity, and biogeochemistry. An existing GIS-based hydrologic model will be modified to incorporate changes in river water resulting from changes in land use patterns that can be expected as the watershed develops. This model will be linked to ecosystem models and will serve as an heuristic and management tool. Another consequence of coastal development is that as river flow decreases, groundwater flow increases and becomes nutrified. We will compare the effects of ground water discharge from the surficial aquifer in relatively pristine (Sapelo Island) versus more urbanized (mainland) sites to assess the relative importance of fresh water versus nutrients to productivity, structure and biomass turnover rate in marshes influenced by groundwater. We will also investigate the effect of marine processes (tides, storm surge) on mixing across the fresh/salt interface in the surficial aquifer. Additional physical studies will relate the morphology of salt marsh - tidal creek channel complexes to tidal current distributions and exchange. These findings will be incorporated into a physical model that will be coupled to an existing ecosystem model. The land/ocean margin ecosystem lies at the interface between two ecosystems in which distinctly different groups of decomposers control organic matter degradation. The terrestrial ecosystem is largely dominated by fungal decomposers, while bacterial decomposers dominate the marine ecosystem. Both groups are important in salt marsh-dominated ecosystems. Specific studies will examine, at the level of individual cells and hyphae, the relationship bacteria and fungi in the consortia that decompose standing dead Spartina and other marsh plants and examine how, or if, this changes along the salinity gradient. 6. Funding Source: NSF OCE 9982133 B. Sub-project Description 1. Site Description a. Geographic Location: GCE6 -- Dean Creek, Sapelo Island, Georgia, USA GCE10 -- Hunt Camp, Sapelo Island, Georgia, USA Coordinates: GCE6 -- NW: 081 17 58.28 W, 31 23 38.66 N NE: 081 15 51.76 W, 31 23 38.66 N SE: 081 15 51.76 W, 31 22 15.61 N SW: 081 17 58.28 W, 31 22 15.61 N GCE10 -- NW: 081 17 43.82 W, 31 29 49.29 N NE: 081 15 32.07 W, 31 29 49.29 N SE: 081 15 32.07 W, 31 27 44.35 N SW: 081 17 43.82 W, 31 27 44.35 N b. Physiographic Region: GCE6 -- Barrier island GCE10 -- Barrier island c. Landform Components: GCE6 -- Intertidal salt marsh, sand beach, maritime forest GCE10 -- Intertidal salt marsh bordering maritime forest d. Hydrographic Characteristics: GCE6 -- Site contains Dean Creek and borders Doboy Sound, and is subject to 2-3m semi-diurnal tides GCE10 -- Site borders the Mud River and contains tidal creeks and the upper reach of the Duplin River, and is subject to 2-3m semi-diurnal tides e. Topographic Attributes: GCE6 -- Flat, with elevations ranging from 0-3m above mean low tide GCE10 -- Flat, with elevations ranging from 0-3m above mean low tide f. Geology, Lithology and Soils: GCE6 -- unspecified GCE10 -- unspecified g. Vegetation Communities: GCE6 -- Vegetation is mostly short and tall Spartina alterniflora, with small amounts of Juncus and Borrichia. GCE10 -- Vegetation mostly tall and medium Spartina alterniflora, with some Juncus present. Upland heavily forested. h. History of Land Use and Disturbance: GCE6 -- Oct 01, 2000: Permanent plots were established in two nominal marsh zones based on marsh structure -- creek zone and high marsh -- and eight plots were randomly located in each zone and marked with stakes Oct 01, 2001: Plots were examined for signs of disturbance by wrack inundation, animal activity, and creek bank erosion. The following plots were lost due to catastrophic disturbance and replaced with new plots as indicated: zone 1, plot 3 (not replaced). GCE10 -- Oct 01, 2000: Permanent plots were established in two nominal marsh zones based on marsh structure -- creek zone and high marsh -- and eight plots were randomly located in each zone and marked with stakes Oct 01, 2001: Plots were examined for signs of disturbance by wrack inundation, animal activity, and creek bank erosion. No significant disturbance was observed, and no plots were replaced. i. Climate: Climate summary for Sapelo Island, Georgia, based on NWS data from 1980-2010: Daily-aggregated Values: Mean (sample standard deviation) mean air temperature: 20.09°C (7.28°C) minimum air temperature: 15.02°C (7.96°C) maximum air temperature: 24.82°C (6.98°C) total precipitation: 3.26mm (10.3mm) Yearly-aggregated Daily Values: Mean (sample standard deviation) total precipitation (1980-2010): 1124mm (266mm) 2. Experimental or Sampling Design a. Design Characteristics: Porewater equilibration meters (hereafter referred to as ‘peepers’) were constructed from ultra high molecular weight polyethylene with 30 to 40 sampling chambers at 1 or 1.5 cm intervals were filled with He purged deionized water and covered with 0.2 µm nylon membrane (Biotrans Nylon Membrane). The peepers were placed vertically in intertidal creek-bank sediments at each site and allowed to equilibrate with the surrounding porewater for 4 to 6 weeks before removal. Duplicate peepers were deployed at each site except during the August 2001 sampling period. Peepers were sampled for ammonium (NH4), nitrate+nitrite (NOx), phosphate (PO4), silica (Si), dissolved organic carbon (DOC) nitrogen (DON) and phosphorus (DOP), dissolved inorganic carbon (DIC), methane (CH4), reduced iron (Fe2+) and manganese (Mn2+), hydrogen sulfide (H2S), chloride (Cl), sulfate (SO4), nitrogen gas (N2) and pH. b. Permanent Plots: unspecified c. Data Collection Duration and Frequency: Duplicate peepers were deployed at the Dover Bluff (DB), Moses Hammock (MH) and Marine Institute (MI) sites on 13-15 August 2000, 14-16 December 2000, and 5-7 March 2001. Single peepers were deployed at DB, MH and the Dean Creek (DC) site on 24-26 June 2001. Duplicate peepers were again deployed at the DB, MH and DC sites on 26-28 Nov 2001 and at the DB, MH, DC and WOC sites on 24-26 June 2002. Dates of collection are in the data file. Beginning of Observations: Sep 22, 2000 End of Observations: Aug 02, 2002 3. Research Methods a. Field and Laboratory Methods: Method 1: Sample Preparation -- Upon collection, peepers were immediately placed in thick (0.15 mm) polypropylene He purged sleeves and transported to the laboratory. In the laboratory, porewater from the chambers was sampled anaerobically for ammonium (NH4), nitrate+nitrite (NOx), phosphate (PO4), silica (Si), dissolved organic carbon (DOC) nitrogen (DON) and phosphorus (DOP), dissolved inorganic carbon (DIC), methane (CH4), reduced iron (Fe2+) and manganese (Mn2+), hydrogen sulfide (H2S), chloride (Cl), sulfate (SO4), nitrogen gas (N2) and pH. Sampling was done within 4 hours of collection. During sampling, porewater from the equilibration meter chambers was split into several different sample containers for the various analyses. An 8 ml glass tube with ground-glass stopper was overflowed with sample for N2 analysis. 1 ml of sample was injected into a 6 ml He purged septa vial that was then acidified with 0.1 ml concentrated phosphoric acid for CH4 and DIC analysis (DIC was measured on April and August 2001 and January and August 2002 samples only). 0.1 ml sample was pipetted into 8 ml glass vial for alkalinity analysis (September 2000 and January 2001 only). 0.1 to 0.5 ml sample was pipetted into a vial containing 0.5 ml 20% zinc acetate for hydrogen sulfide analysis. 1 ml sample was used for pH determination. The remaining sample was then filtered (0.2 µm) into several separate vials. 0.1 to 0.5 ml of filtered sample was pipetted into a vial for NH4 analysis that contained the phenol reagent. 4 ml of filtered sample was acidified (0.1 ml concentrated nitric acid) for Cl, SO4, DOC, PO4, DOP, Fe2+ and Mn2+ analysis. All remaining filtered sample was saved in another vial for NOx, DON and Si determination (when Si was measured, this sample was taken in a plastic vial). All samples were stored at 4 C prior to analysis. Note that not all samples were taken or measured for each peeper chamber. Method 2: pH Measurement -- pH was measured in the glove bag immediately after removal of sample from the peeper chamber. An Orion model 250A meter and 81-02 combination pH electrode was used to measure the pH of 1 ml of unfiltered sample. The pH meter was calibrated prior to every peeper sampling using standard pH buffers. Method 3: Alkalinity Measurement -- Vials containing the alkalinity reagent (0.5 ml) were placed in the glovebag prior to sampling. Unfiltered sample (0.1 ml) was pipetted into the vials immediately after removal of sample from the peeper chamber. Alkalinity of samples and standards was measured immediately upon removal of vials from the glove-bag (reference: Sarazin, G., G. Michard, and F. Prevot. 1999. A rapid and accurate spectroscopic method for alkalinity measurements in sea water samples. Water Res. 33: 290-294). Alkalinity standards (0, 1, 5, 10, 15, 20 and 30 mM) were made in 18 megaohm deionized water from sodium bicarbonate. Samples and standards were read at 590 nm on a Shimadzu spectrophotometer in a 1 cm cell blanked with deionized water. Method 4: Sulfide Measurement -- Vials containing zinc acetate (0.5 ml) were placed in the glovebag prior to sampling. Unfiltered sample (0.1 to 0.5 ml) was pipetted into the vials, which were capped and stored at 4 C until analysis (within one month). H2S standards (0, 1, 5, 10, 20, 40, 80 µM) were prepared in He purged deionized water from sodium sulfide nanohydrate. Samples and standards were analyzed by standard colorimetric assay (reference: Cline, J. D. 1969. Spectrophotometric determination of hydrogen sulfide in natural waters. Limnol. Oceanogr. 14:454-458). Samples and standards were read at 670 nm on a Shimadzu spectrophotometer in a 1 cm cell blanked with deionized water. Method 5: Ammonium Measurement -- Vials containing the phenol reagent (0.2 ml) were placed in glovebag prior to sampling. Filtered sample (0.1 to 0.5 ml) was pipetted into the vials immediately after removal and filtration of porewater. Vials were capped and stored at 4 C until analysis, within 4 d by standard colorimetric techniques (reference: Solorzano, L. 1969. Determination of ammonia in natural waters by the phenolhypochlorite method. Limnol. Oceanogr. 14: 799-801). Ammonium standards (0, 0.5, 1.0, 2.5, 5, 10, 20, 40 and 80 uM) were made in 18 megaohm deionized water from ammonium chloride. 5 ml sample and standard volumes were reacted with the analysis reagents, allowed to incubate for 2 hours, and read at 640 nm on a Shimadzu spectrophotometer in a 1 cm cell blanked with deionized water. Method 6: Nitrate + Nitrite Measurement -- NOx was analyzed within 2 weeks by vanadium reduction and NO detection. Nitrate (potassium nitrate) and nitrite (sodium nitrite) standards (0, 0.1, 0.5, 1, 2, 5, and 10 µM) were prepared in 18 megaohm deionized water. Efficiency of reduction for both nitrate and nitrite as well as calibration were preformed during every analysis. Method 7: Phosphate Measurement -- PO4 concentration was measured on acidified samples using a standard autoanalyzer protocol (reference: Lachat Instruments FIA 8000 Autoanalyzer Method 31-115-01-1-H). Phosphate standards were prepared in 18 megaohm deionized water from potassium phosphate at 0, 0.1, 0.2, 0.5, 1.0, 2.5, 5, 10 and 20 uM concentrations. Method 8: Silica Measurement -- Si was determined on water samples by autoanalyzer (reference: Lachat Instruments FIA 8000 Method 31-114-27-1-D). Si standards were prepared in 18 megaohm deionized water from sodium silicate at 0, 1, 5, 10, 20, 40 and 80 µM concentrations. Method 9: Chloride and Sulfate Measurement -- Chloride was determined by ion chromatography on a Dionex DX 500 system on acidified samples. Chloride and sulfate standards were prepared from certified stock standards (Spex CertiPrep). Method 10: DIC and Methane Measurement -- Dissolved inorganic carbon (DIC) and methane (CH4) were analyzed on the gas phase of the acidified headspace vial after vigorous shaking to ensure equilibration between gas and liquid phase in the vial. 1 ml of headspace gas was injected into a gas chromatograph (Shimadzu GC 14A with 2 m Carbosphere column [Alltech Instruments]), to separate and CO2 and CH4 by flame ionization detection. The GC was equipped with a methanizer to reduce CO2 to CH4 for precise quantification. CO2 and CH4 gas standards (10 % CO2 and CH4 in He) was used to standardize for every run. Method 11: DOC Measurement -- Dissolved organic carbon (DOC) concentration was measured by high-temperature catalytic oxidation using a Shimadzu Instruments TOC 5000. DOC standards were prepared in 18 megaohm deionized water with potassium hydrogen phthalate at concentrations of 0, 100, 250, 500, 1000 and 2000 uM C, and were acidified (25 µl HCl into 5 ml). Acidified samples from the peepers (5 ml) and samples were purged with CO2 free air for 15 minutes prior to injection. Triplicate injections were averaged. Method 12: Total Dissolved Nitrogen Measurement -- TDN concentration was measured by high temperature catalytic oxidation using a Shimadzu Instruments TOC 5000 coupled to an Antek Instruments model 7020 NO analyzer (reference: Alvarez-Salgado, X. A., and A. E. J. Miller. 1998. Simultaneous determination of dissolved organic carbon and total dissolved nitrogen in seawater by high temperature catalytic oxidation: conditions for precise shipboard measurements. Mar. Chem. 62: 325-333). TDN standards were prepared in 18 megaohm deionized water from amino acetic acid at concentrations of 0, 25, 50, 100, 250 and 500 uM. Unacidified samples and standards were injected in triplicate. DON was calculated as the difference between the TDN and dissolved inorganic nitrogen (NH4 + NOx) on the same sample. Method recovery of several inorganic and organic nitrogen compounds (NH4+, NO3-, NO2-, Urea, Nicotonic acid) was checked periodically. Method 13: Total Dissolved Phosphorus Measurement -- TDP was measured by high temperature combustion and hydrolysis (reference: Monaghan, E. J., and K. C. Ruttenberg. 1999. Dissolved organic phosphorus in the coastal ocean: Reassessment of available methods and seasonal phosphorus profiles from the Eel River Shelf. Limnol. Oceanogr. 44: 1702-1714). Standards were prepared in 18 megaohm deionized water from potassium phosphate at 0, 0.1, 0.5, 1.0, 2.5, 5, 10 and 20 uM concentrations. Method recovery of organic phosphorus compounds was checked periodically using uracil tri-phosphate standards at the same concentrations. After evaporation, combustion and hydrolysis of samples and standards, TDP was determined as phosphate by standard colorimetric autoanalyzer assay (see phosphate analysis protocol). DOP was calculated as the difference between TDP and dissolved inorganic phosphorus (PO4) on the same sample. Method 14: Reduced Iron Measurement -- Fe2+ was determined by standard colorimetric assay on acidified porewater sample (reference: Stookey, L.L. 1970. Ferrozine – A new spectrophotometric reagent for iron. Analytical Chemistry. 42: 779-781). Standards (0, 0.5, 1, 5, 10, 20, 40, 80 µM) were prepared from a certified stock standard (Fisher Scientific). Samples and standards were read at 562 nm on a Shimadzu spectrophotometer in a 1 cm cell blanked with deionized water. Method 15: Reduced Manganese Measurement -- Mn2+ was determined by standard colorimetric assay on acidified porewater sample (reference: Armstrong, J. 1979. Application of the formaldoxime colorimetric method for the determination of manganese in the pore water of anoxic estuarine sediments. Estuaries. 3: 198-201). Standards (0, 0.5, 1, 5, 10, 20, 40, 80 µM) were prepared from a certified stock standard (Fisher Scientific). Samples and standards were read at 450 nm on a Shimadzu spectrophotometer in a 1 cm cell blanked with deionized water. Method 16: Nitrogen Gas Measurement -- N2 was measured on a membrane inlet mass spectrometer as the deviance from the N2 to Ar ratio of the sample compared to standard (atmospheric equilibrated air) following the protocol of Kana et al. (reference: Kana, T.M., Darkangelo, C., Hunt, M.D., Oldham, J.B., Bennett, G.E. and Cornwell, J.C. 1994. Membrane inlet mass spectrometer for rapid high-precision determination of N2, O2 and Ar in environmental water samples. Anal. Chem. 66:4166-4170). b. Instrumentation: Method 1: none Method 2: pH Meter Manufacturer: Orion Instruments (Model: 250A meter with 81-02 probe) Parameter: pH (Accuracy: 0.02, Range: 1 to 14) Protocol: Instrument calibrated prior to each analysis Method 3: Spectrophotometer Manufacturer: Shimadzu Instruments (Model: UV-1601) Parameter: Alkalinity (Accuracy: 0.05 mM, Range: 0.1 to 100 mM) Protocol: Instrument calibrated for every analysis (method: Sarazin, G., G. Michard, and F. Prevot. 1999. A rapid and accurate spectroscopic method for alkalinity measurements in sea water samples. Water Res. 33: 290-294.) Method 4: Spectrophotometer Manufacturer: Shimadzu Instruments (Model: UV-1601) Parameter: Hydrogen Sulfide (H2S) (Accuracy: 0.5 µM, Range: 1 to 100 µM) Protocol: Cline, J. D. 1969. Spectrophotometric determination of hydrogen sulfide in natural waters. Limnol. Oceanogr. 14:454-458. Method 5: Spectrophotometer Manufacturer: Shimadzu Instruments (Model: UV-1601) Parameter: Ammonium concentration (Accuracy: 0.1 µM, Range: 0.2 to 80 µM) Protocol: Solorzano, L. 1969. Determination of ammonia in natural waters by the phenolhypochlorite method. Limnol. Oceanogr. 14: 799-801 Method 6: NO analyzer Manufacturer: Antek Instruments (Model: 7020) Parameter: Total dissolved nitrogen concentration (Accuracy: 2 µM, Range: 10 to 1000 µM) Protocol: Alvarez-Salgado, X. A., and A. E. J. Miller. 1998. Simultaneous determination of dissolved organic carbon and total dissolved nitrogen in seawater by high temperature catalytic oxidation: conditions for precise shipboard measurements. Mar. Chem. 62: 325-333. Method 7: Flow Injection Autoanalyzer Manufacturer: Lachat Instruments (Model: FIA 8000) Parameter: Phosphate concentration (Accuracy: 0.05 µM, Readability: 0.03 µM, Range: 0.1 to 80 µM) Protocol: Lachat Instruments FIA 8000 Autoanalyzer Method 31-115-01-1-H Method 8: Flow Injection Autoanalyzer Manufacturer: Lachat Instruments (Model: FIA 8000) Parameter: Silica concentration (Accuracy: 0.1 µM, Readability: 0.05 µM, Range: 0.4 to 60µM) Protocol: Lachat Instruments FIA 8000 Autoanalyzer Method 31-114-27-1-D Method 9: Ion Chromatograph Manufacturer: Dionex Instruments (Model: DX500) Parameter: Chloride Concentration (Accuracy: 0.05 mM, Range: 0.1 to 1000 mM) Protocol: Instrument calibrated prior to each analysis Parameter: Sulfate Concentration (Accuracy: 0.01 mM, Range: 0.01 to 100 mM) Protocol: Instrument calibrated prior to each analysis Method 10: Flame Ionization Detector Gas Chromatograph Manufacturer: Shimadzu Instruments (Model: GC-14A) Parameter: Dissolved inorganic carbon concentration (Accuracy: 1 µM, Range: 5 µM to 50 mM) Protocol: Instrument calibrated prior to each analysis Parameter: Methane concentration (Accuracy: 0.5 µM, Range: 1 µM to 5000 mM) Protocol: Instrument calibrated prior to each analysis Method 11: TOC analyzer Manufacturer: Shimadzu Instruments (Model: TOC 5000) Parameter: Non-purgable organic carbon concentration (Accuracy: 2 µM, Range: 10 to 2000 µM) Protocol: Instrument calibrated prior to each analysis Method 12: NO analyzer Manufacturer: Antek Instruments (Model: 7020) Parameter: Total dissolved nitrogen concentration (Accuracy: 2 µM, Range: 10 to 1000 µM) Protocol: Alvarez-Salgado, X. A., and A. E. J. Miller. 1998. Simultaneous determination of dissolved organic carbon and total dissolved nitrogen in seawater by high temperature catalytic oxidation: conditions for precise shipboard measurements. Mar. Chem. 62: 325-333. TOC analyzer Manufacturer: Shimadzu Instruments (Model: TOC 5000) Parameter: Non-purgable organic carbon concentration (Accuracy: 2 µM, Range: 10 to 2000 µM) Protocol: Instrument calibrated prior to each analysis Method 13: Flow Injection Autoanalyzer Manufacturer: Lachat Instruments (Model: FIA 8000) Parameter: Phosphate concentration (Accuracy: 0.05 µM, Readability: 0.03 µM, Range: 0.1 to 80 µM) Protocol: Lachat Instruments FIA 8000 Autoanalyzer Method 31-115-01-1-H Method 14: Spectrophotometer Manufacturer: Shimadzu Instruments (Model: UV-1601) Parameter: Reduced Iron (Fe2+) (Readability: 0.3 mM, Range: 0.5 to 100 µM Fe/mg sediment) Protocol: Stookey, L.L. 1970. Ferrozine – A new spectrophotometric reagent for iron. Analytical Chemistry. 42: 779-781. Method 15: Spectrophotometer Manufacturer: Shimadzu Instruments (Model: UV-1601) Parameter: Reduced Manganese (Mn2+) (Accuracy: 0.1 µM, Range: 0.2 to 80 µM) Protocol: Armstrong, J. 1979. Application of the formaldoxime colorimetric method for the determination of manganese in the pore water of anoxic estuarine sediments. Estuaries. 3: 198-201. Method 16: Membrane Inlet Mass Spectrometer Manufacturer: Balzurs Instruments (Model: Quadstar 422) Parameter: Nitrogen gas concentration (Accuracy: 0.1 µM, Range: 100 to 800 µM) Protocol: Instrument calibrated prior to each analysis c. Taxonomy and Systematics: Method 1: not applicable Method 2: not applicable Method 3: not applicable Method 4: not applicable Method 5: not applicable Method 6: not applicable Method 7: not applicable Method 8: not applicable Method 9: not applicable Method 10: not applicable Method 11: not applicable Method 12: not applicable Method 13: not applicable Method 14: not applicable Method 15: not applicable Method 16: not applicable d. Permit History: Method 1: none Method 2: none Method 3: none Method 4: none Method 5: none Method 6: none Method 7: none Method 8: none Method 9: none Method 10: none Method 11: none Method 12: none Method 13: none Method 14: none Method 15: none Method 16: none 4. Project Personnel a. Personnel: 1: Samantha B. Joye 2: Nathaniel B. Weston 3: William P. Porubsky 4: Matthew Erickson b. Affiliations: 1: University of Georgia, Athens, Georgia 2: University of Georgia, Athens, Georgia 3: University of Georgia, Athens, Georgia 4: University of Georgia, Athens, Georgia III. Data Set Status and Accessibility A. Status 1. Latest Update: 19-Feb-2012 2. Latest Archive Date: 18-Nov-2011 3. Latest Metadata Update: 19-Feb-2012 4. Data Verification Status: Reviewed by GCE-LTER IM B. Accessibility 1. Storage Location and Medium: Stored at GCE-LTER Data Management Office Dept. of Marine Sciences Univ. of Georgia Athens, GA 30602-3636 USA on media: electronic data download (WWW) or compact disk 2. Contact Person: Name: Wade M. Sheldon, Jr. Address: Dept. of Marine Sciences University of Georgia Athens, Georgia 30602-3636 Country: USA Email: sheldon@uga.edu 3. Copyright Restrictions: not copyrighted 4. Restrictions: All publications based on this data set must cite the contributor and Georgia Coastal Ecosystems LTER project, and two copies of the manuscript must be submitted to the GCE-LTER Information Management Office. a. Release Date: GCE LTER Affiliates: Oct 16, 2002, Public: Oct 16, 2004 b. Citation: Data provided by the Georgia Coastal Ecosystems Long Term Ecological Research Project, supported by funds from NSF OCE 9982133 (data set POR-GCED-0210) c. Disclaimer: The user assumes all responsibility for errors in judgement based on interpretation of data and analyses presented in this data set. 5. Costs: free electronic data download via WWW, distribution on CD may be subject to nominal processing and handling fee IV. Data Structural Descriptors A. Data Set File 1. File Name: POR-GCED-0210_1_4.CSV 2. Size: 1153 records 3. File Format: ASCII text (comma-separated value format) 3a. Delimiters: single comma 4. Header Information: 5 lines of ASCII text 5. Alphanumeric Attributes: Upper case 6. Quality Control Flag Codes: I = invalid value (out of range), Q = questionable value 7. Authentication Procedures: not specified 8. Calculations: DON_Conc: Difference between total dissolved nitrogen and dissolved inorganic nitrogen DOP_Conc: Difference between total dissolved phosphorus and inorganic phosphorus 9. Processing History: Software version: GCE Data Toolbox Version 3.30 (09-Feb-2012) Data structure version: GCE Data Structure 1.1 (29-Mar-2001) Original data file processed: POR-GCED-0210.TXT (1153 records) Data processing history: 17-Oct-2002: new GCE Data Structure 1.1 created ('newstruct') 17-Oct-2002: 1153 rows imported from ASCII data file 'POR-GCED-0210.TXT' ('imp_ascii') 17-Oct-2002: 10 metadata fields in file header parsed ('parse_header') 17-Oct-2002: data structure validated ('gce_valid') 17-Oct-2002: Q/C flagging criteria applied, 'flags' field updated ('dataflag') 17-Oct-2002: imported Data, Dataset, Project, Site, Study, Status, Supplement metadata descriptors from the GCE Metabase ('imp_gcemetadata') 17-Oct-2002: Q/C flagging criteria applied, 'flags' field updated ('dataflag') 30-Oct-2003: imported Data, Dataset, Project, Site, Study, Status, Supplement metadata descriptors from the GCE Metabase ('imp_gcemetadata') 30-Oct-2003: Q/C flagging criteria applied, 'flags' field updated ('dataflag') 08-Nov-2005: imported Dataset, Project, Site, Study, Status, Supplement metadata descriptors from the GCE Metabase ('imp_gcemetadata') 08-Nov-2005: updated 66 metadata fields in the Data, Dataset, Project, Site, Status, Study, Supplement sections ('imp_gcemetadata') 17-Apr-2006: standardized case of date component column units to prevent unit conversion issues ('batch_update_datetime'): updated units for column Year from 'yyyy' to 'YYYY'; updated units for column Month from 'mm' to 'MM'; updated units for column Day from 'dd' to 'DD' 15-Nov-2011: imported Dataset, Project, Site, Study, Status, Supplement metadata descriptors from the GCE Metabase ('imp_gcemetadata') 15-Nov-2011: updated 57 metadata fields in the Dataset, Project, Site, Status, Study, Supplement sections ('imp_gcemetadata') 18-Nov-2011: imported Dataset, Project, Site, Study, Status, Supplement metadata descriptors from the GCE Metabase ('imp_gcemetadata') 18-Nov-2011: updated 57 metadata fields in the Dataset, Project, Site, Status, Study, Supplement sections ('imp_gcemetadata') 19-Feb-2012: flags for columns Depth, pH, NH4_Conc, Nox_Conc, DON_Conc, PO4_Conc, DOP_Conc, Si_Conc, DOC_Conc, H2S_Conc, Fe_Conc, Mn_Conc, Cl_Conc, SO4_Conc, Alkalinity, DIC_Calc, DIC_Meas, CH4_Conc, Salinity_Interpolated, N2_Equilibrium, N2_Conc and N2_Sat converted to data columns, flag codes updated in metadata ('flags2cols') 19-Feb-2012: updated 7 metadata fields in the Data, Status sections ('exp_ascii') 19-Feb-2012: updated 15 metadata fields in the Status, Data sections to reflect attribute metadata ('updatecols') 19-Feb-2012: parsed and formatted metadata ('listmeta') B. Variable Information 1. Variable Name: column 1. Year column 2. Month column 3. Day column 4. Station column 5. Longitude column 6. Latitude column 7. Replicate column 8. Chamber column 9. Depth column 10. Flag_Depth column 11. pH column 12. Flag_pH column 13. NH4_Conc column 14. Flag_NH4_Conc column 15. Nox_Conc column 16. Flag_Nox_Conc column 17. DON_Conc column 18. Flag_DON_Conc column 19. PO4_Conc column 20. Flag_PO4_Conc column 21. DOP_Conc column 22. Flag_DOP_Conc column 23. Si_Conc column 24. Flag_Si_Conc column 25. DOC_Conc column 26. Flag_DOC_Conc column 27. H2S_Conc column 28. Flag_H2S_Conc column 29. Fe_Conc column 30. Flag_Fe_Conc column 31. Mn_Conc column 32. Flag_Mn_Conc column 33. Cl_Conc column 34. Flag_Cl_Conc column 35. SO4_Conc column 36. Flag_SO4_Conc column 37. Alkalinity column 38. Flag_Alkalinity column 39. DIC_Calc column 40. Flag_DIC_Calc column 41. DIC_Meas column 42. Flag_DIC_Meas column 43. CH4_Conc column 44. Flag_CH4_Conc column 45. Salinity_Interpolated column 46. Flag_Salinity_Interpolated column 47. N2_Equilibrium column 48. Flag_N2_Equilibrium column 49. N2_Conc column 50. Flag_N2_Conc column 51. N2_Sat column 52. Flag_N2_Sat 2. Variable Definition: column 1. Year of sample collection column 2. Month of sample collection column 3. Day of sample collection column 4. Site location code column 5. Geographic longitude of sampling location column 6. Geographic latitude of sampling location column 7. Porewater equilibration meter replicate code column 8. Porewater equilibration chamber number, from top of meter down column 9. Depth of porewater equilibration meter chamber, relative to sediment-water interface column 10. QA/QC flags for Depth of porewater equilibration meter chamber, relative to sediment-water interface (flagging criteria, where "x" is Depth: x<-20="Q", x>70="Q") column 11. pH column 12. QA/QC flags for pH (flagging criteria, where "x" is pH: x<1="Q", x>14="Q") column 13. Ammonium concentration column 14. QA/QC flags for Ammonium concentration (flagging criteria, where "x" is NH4_Conc: x<0="I", x<0.2="Q") column 15. Nitrate+nitrite concentration column 16. QA/QC flags for Nitrate+nitrite concentration (flagging criteria, where "x" is Nox_Conc: x<0="I", x<0.1="Q") column 17. Dissolved organic nitrogen concentration column 18. QA/QC flags for Dissolved organic nitrogen concentration (flagging criteria, where "x" is DON_Conc: x<0="I", x<10="Q") column 19. Phosphate concentration column 20. QA/QC flags for Phosphate concentration (flagging criteria, where "x" is PO4_Conc: x<0="I", x<0.1="Q") column 21. Dissolved organic phosphorus concentration column 22. QA/QC flags for Dissolved organic phosphorus concentration (flagging criteria, where "x" is DOP_Conc: x<0="I", x<0.2="Q") column 23. Silica concentration column 24. QA/QC flags for Silica concentration (flagging criteria, where "x" is Si_Conc: x<0="I", x<0.2="Q") column 25. Dissolved organic carbon concentration column 26. QA/QC flags for Dissolved organic carbon concentration (flagging criteria, where "x" is DOC_Conc: x<0="I", x<10="Q") column 27. Hydrogen sulfide concentration column 28. QA/QC flags for Hydrogen sulfide concentration (flagging criteria, where "x" is H2S_Conc: x<0="I", x<1="Q") column 29. Reduced iron concentration column 30. QA/QC flags for Reduced iron concentration (flagging criteria, where "x" is Fe_Conc: x<0="I", x<0.2="Q") column 31. Reduced manganese concentration column 32. QA/QC flags for Reduced manganese concentration (flagging criteria, where "x" is Mn_Conc: x<0="I", x<0.2="Q") column 33. Chloride concentration column 34. QA/QC flags for Chloride concentration (flagging criteria, where "x" is Cl_Conc: x<0="I", x<0.1="Q") column 35. Sulfate concentration column 36. QA/QC flags for Sulfate concentration (flagging criteria, where "x" is SO4_Conc: x<0="I", x<0.01="Q") column 37. Alkalinity column 38. QA/QC flags for Alkalinity (flagging criteria, where "x" is Alkalinity: x<0="I", x<0.1="Q") column 39. Dissolved inorganic carbon concentration, calculated from pH and Alkalinity column 40. QA/QC flags for Dissolved inorganic carbon concentration, calculated from pH and Alkalinity (flagging criteria, where "x" is DIC_Calc: x<0="I") column 41. Dissolved inorganic carbon concentration, measured column 42. QA/QC flags for Dissolved inorganic carbon concentration, measured (flagging criteria, where "x" is DIC_Meas: x<0="I", x<5="Q") column 43. Methane concentration column 44. QA/QC flags for Methane concentration (flagging criteria, where "x" is CH4_Conc: x<0="I", x<0.5="Q") column 45. Salinity, interpolated by depth from chloride column 46. QA/QC flags for Salinity, interpolated by depth from chloride (flagging criteria, where "x" is Salinity_Interpolated: x<0="I") column 47. Equilibrium nitrogen gas concentration calculated from interpolated salinity and temperature column 48. QA/QC flags for Equilibrium nitrogen gas concentration calculated from interpolated salinity and temperature (flagging criteria, where "x" is N2_Equilibrium: x<0="I", x>1000="I") column 49. Measured nitrogen gas concentration column 50. QA/QC flags for Measured nitrogen gas concentration (flagging criteria, where "x" is N2_Conc: x<0="I", x>1000="I") column 51. Percent nitrogen gas saturation column 52. QA/QC flags for Percent nitrogen gas saturation (flagging criteria, where "x" is N2_Sat: x<0="I", x>500="I") 3. Units of Measurement: column 1. YYYY column 2. MM column 3. DD column 4. none column 5. degrees column 6. degrees column 7. none column 8. none column 9. cm column 10. none column 11. pH units column 12. none column 13. µM column 14. none column 15. µM column 16. none column 17. µM column 18. none column 19. µM column 20. none column 21. µM column 22. none column 23. µM column 24. none column 25. µM column 26. none column 27. µM column 28. none column 29. µM column 30. none column 31. µM column 32. none column 33. mM column 34. none column 35. mM column 36. none column 37. mM column 38. none column 39. µM column 40. none column 41. µM column 42. none column 43. µM column 44. none column 45. parts per thousand column 46. none column 47. µM column 48. none column 49. µM column 50. none column 51. % column 52. none 4. Data Type a. Storage Type: column 1. integer column 2. integer column 3. integer column 4. alphanumeric column 5. floating-point column 6. floating-point column 7. integer column 8. integer column 9. floating-point column 10. alphanumeric column 11. floating-point column 12. alphanumeric column 13. floating-point column 14. alphanumeric column 15. floating-point column 16. alphanumeric column 17. floating-point column 18. alphanumeric column 19. floating-point column 20. alphanumeric column 21. floating-point column 22. alphanumeric column 23. floating-point column 24. alphanumeric column 25. floating-point column 26. alphanumeric column 27. floating-point column 28. alphanumeric column 29. floating-point column 30. alphanumeric column 31. floating-point column 32. alphanumeric column 33. floating-point column 34. alphanumeric column 35. floating-point column 36. alphanumeric column 37. floating-point column 38. alphanumeric column 39. floating-point column 40. alphanumeric column 41. floating-point column 42. alphanumeric column 43. floating-point column 44. alphanumeric column 45. floating-point column 46. alphanumeric column 47. floating-point column 48. alphanumeric column 49. floating-point column 50. alphanumeric column 51. floating-point column 52. alphanumeric b. Variable Codes: Station: DB = Dover Bluff, MH = Moses Hammock GCE site 10, MI = Marine Institute, DC = Dean Creek GCE site 6, WOC = White Oak Creek Replicate: 0 = overlying water sample, 1 = porewater equilibration meter replicate number one, 2 = porewater equilibration meter replicate number 2 Flag_Depth: Q = questionable value Flag_NH4_Conc: Q = questionable value Flag_Nox_Conc: Q = questionable value Flag_DON_Conc: Q = questionable value Flag_PO4_Conc: Q = questionable value Flag_DOP_Conc: Q = questionable value Flag_H2S_Conc: Q = questionable value Flag_Fe_Conc: Q = questionable value Flag_Mn_Conc: Q = questionable value Flag_SO4_Conc: Q = questionable value Flag_Alkalinity: I = invalid value (out of range), Q = questionable value Flag_CH4_Conc: Q = questionable value c. Numeric Range: column 1. 2000 to 2002 column 2. 1 to 9 column 3. 1 to 31 column 4. (none) column 5. -81.438 to -81.163 column 6. 31.011 to 31.287 column 7. 0 to 2 column 8. 0 to 37 column 9. -30.5 to 58.5 column 10. (none) column 11. 6.44 to 8.45 column 12. (none) column 13. 0 to 4595.14 column 14. (none) column 15. 0 to 168.33 column 16. (none) column 17. 3.31 to 1241.41 column 18. (none) column 19. 0 to 792.45 column 20. (none) column 21. 0 to 769.29 column 22. (none) column 23. 7.04 to 1290.3 column 24. (none) column 25. 78.47 to 56304.52 column 26. (none) column 27. 0 to 32631.34 column 28. (none) column 29. 0 to 1111.1 column 30. (none) column 31. 0 to 267.45 column 32. (none) column 33. 0.11 to 614.52 column 34. (none) column 35. 0 to 29.48 column 36. (none) column 37. -9.63 to 63.02 column 38. (none) column 39. 145.65 to 37216.37 column 40. (none) column 41. 266.83 to 107870.23 column 42. (none) column 43. 0 to 1046.53 column 44. (none) column 45. 0 to 35.07 column 46. (none) column 47. 357.95 to 527.77 column 48. (none) column 49. 307.96 to 602.83 column 50. (none) column 51. 74.95 to 140.8 column 52. (none) d. Missing Value Code: 5. Data Format a. Column Type: column 1. numerical column 2. numerical column 3. numerical column 4. text column 5. numerical column 6. numerical column 7. numerical column 8. numerical column 9. numerical column 10. text column 11. numerical column 12. text column 13. numerical column 14. text column 15. numerical column 16. text column 17. numerical column 18. text column 19. numerical column 20. text column 21. numerical column 22. text column 23. numerical column 24. text column 25. numerical column 26. text column 27. numerical column 28. text column 29. numerical column 30. text column 31. numerical column 32. text column 33. numerical column 34. text column 35. numerical column 36. text column 37. numerical column 38. text column 39. numerical column 40. text column 41. numerical column 42. text column 43. numerical column 44. text column 45. numerical column 46. text column 47. numerical column 48. text column 49. numerical column 50. text column 51. numerical column 52. text b. Number of Columns: 52 c. Decimal Places: column 1. 0 column 2. 0 column 3. 0 column 4. 0 column 5. 6 column 6. 6 column 7. 0 column 8. 0 column 9. 1 column 10. 0 column 11. 2 column 12. 0 column 13. 2 column 14. 0 column 15. 2 column 16. 0 column 17. 2 column 18. 0 column 19. 2 column 20. 0 column 21. 2 column 22. 0 column 23. 2 column 24. 0 column 25. 2 column 26. 0 column 27. 2 column 28. 0 column 29. 2 column 30. 0 column 31. 2 column 32. 0 column 33. 2 column 34. 0 column 35. 2 column 36. 0 column 37. 2 column 38. 0 column 39. 2 column 40. 0 column 41. 2 column 42. 0 column 43. 2 column 44. 0 column 45. 2 column 46. 0 column 47. 2 column 48. 0 column 49. 2 column 50. 0 column 51. 2 column 52. 0 6. Logical Variable Type: column 1. datetime (discrete) column 2. datetime (discrete) column 3. datetime (discrete) column 4. coded value (none) column 5. geographic coordinate (continuous) column 6. geographic coordinate (continuous) column 7. coded value (discrete) column 8. nominal (discrete) column 9. data (continuous) column 10. coded value (none) column 11. data (continuous) column 12. coded value (none) column 13. data (continuous) column 14. coded value (none) column 15. data (continuous) column 16. coded value (none) column 17. data (continuous) column 18. coded value (none) column 19. data (continuous) column 20. coded value (none) column 21. data (continuous) column 22. coded value (none) column 23. data (continuous) column 24. coded value (none) column 25. data (continuous) column 26. coded value (none) column 27. data (continuous) column 28. coded value (none) column 29. data (continuous) column 30. coded value (none) column 31. data (continuous) column 32. coded value (none) column 33. data (continuous) column 34. coded value (none) column 35. data (continuous) column 36. coded value (none) column 37. data (continuous) column 38. coded value (none) column 39. calculation (continuous) column 40. coded value (none) column 41. data (continuous) column 42. coded value (none) column 43. data (continuous) column 44. coded value (none) column 45. calculation (continuous) column 46. coded value (none) column 47. calculation (continuous) column 48. coded value (none) column 49. data (continuous) column 50. coded value (none) column 51. calculation (continuous) column 52. coded value (none) 7. Flagging Criteria: column 1. x<2000="I", x>2006="Q" column 2. x<1="I", x>12="I" column 3. x<1="I", x>31="I" column 4. none column 5. x<-83="Q", x>-81="Q" column 6. x<30="Q", x>32="Q" column 7. x<0="I", x>2="I" column 8. x<0="I", x>40="I" column 9. x<-20="Q", x>70="Q" column 10. none column 11. x<1="Q", x>14="Q" column 12. none column 13. x<0="I", x<0.2="Q" column 14. none column 15. x<0="I", x<0.1="Q" column 16. none column 17. x<0="I", x<10="Q" column 18. none column 19. x<0="I", x<0.1="Q" column 20. none column 21. x<0="I", x<0.2="Q" column 22. none column 23. x<0="I", x<0.2="Q" column 24. none column 25. x<0="I", x<10="Q" column 26. none column 27. x<0="I", x<1="Q" column 28. none column 29. x<0="I", x<0.2="Q" column 30. none column 31. x<0="I", x<0.2="Q" column 32. none column 33. x<0="I", x<0.1="Q" column 34. none column 35. x<0="I", x<0.01="Q" column 36. none column 37. x<0="I", x<0.1="Q" column 38. none column 39. x<0="I" column 40. none column 41. x<0="I", x<5="Q" column 42. none column 43. x<0="I", x<0.5="Q" column 44. none column 45. x<0="I" column 46. none column 47. x<0="I", x>1000="I" column 48. none column 49. x<0="I", x>1000="I" column 50. none column 51. x<0="I", x>500="I" column 52. none C. Data Anomalies: Some measurements were below measured detection limits or negative, and were flagged as invalid or questionable. V. Supplemental Descriptors A. Data Acquisition 1. Data Forms: Original sample logs and data forms stored in the laboratory of Samantha Joye. 2. Form Location: Samantha B. Joye laboratory, Dept. of Marine Sciences, University of Georgia, Athens, GA 30602-3636, USA 3. Data Entry Validation: not specified B. Quality Assurance/Quality Control Procedures: QA/QC flags are generated automatically according to domain criteria specified for each data column. A flag column is generated and appended to the data table if any flags are assigned to any value, listing the flags for each column on each row. C. Supplemental Materials: Residual sample materials are stored in the laboratory of Samantha B. Joye. D. Computer Programs: Microsoft(tm) Excel E. Archival Practices: Data sets and documentation are stored in structured binary (Matlab 5.x files) and delimited ASCII text formats, and archived on magnetic tape and CD at the GCE LTER Information Management Office at the University of Georgia, Athens, Georgia, USA. F. Publications: not specified G. History of Data Set Usage 1. Data Request History: not specified 2. Data Set Update History: none 3. Review History: none 4. Questions and Comments from Users: none