PIE LTER time series of methane, CO2 and N2O ebullition measurements at four headwater streams in Massachusetts and New Hampshire.


Methane ebullition was monitored at four headwater streams during 2018 and 2019. Stationary bubble traps were deployed from approximately May through October. CC and SB were monitored in 2018 and 2019, while DB and CB were only monitored in 2019. 12 traps were deployed at CC, SB, and DB, and 9 traps were deployed at CB. The concentration measured in the emitted gas was multiplied by the volume measured in a trap to calculated the total methane flux via ebullition. The traps were visited at least once weekly. The mean, median, minimum, and maximum rate of ebullition across all traps at a site over a two week period are listed here.

Relevant publications:
Robison, A.L. (2021) Carbon emissions from streams and river: Integrating methane emission pathways and storm carbon dioxide emissions into stream and river carbon balances. Doctoral Dissertation. University of New Hampshire.
Robison, A.L., W.M. Wollheim, B. Turek, C. Bova, C Snay, & R.K. Varner (in review). Spatial and temporal heterogeneity of methane ebullition in lowland headwater streams. Limnology and Oceanography.

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Bubble trap construction, deployment, and sampling
Bubble traps were installed in each stream to estimate CH4 emissions via ebullition. The traps consisted of a 25 cm diameter plastic funnel fitted with a 60 mL plastic syringe and three-way stopcock, all sealed with water-tight sealant. To install a trap in the stream channel, a 1 m long steel stake was hammered into the stream bottom and a trap was affixed to the stake by plastic zip-ties. Locations for bubble trap deployment, hereafter referred to as patches, were selected for each stream. An initial patch near a long-term monitoring location for water quality was established at each stream, and subsequent patches were distributed approximately every 10 to 15 m upstream or downstream. Four patches were located at Cart Creek, Dube Brook, and Sawmill Brook, and three patches were chosen at College Brook due to limited access to this stream.  We assume patches are independent of one another and the distribution of patches is therefore the representative of the stream reach apart from avoidance of rocky substrates. Two seasons of monitoring were performed at Cart Creek and Sawmill Brook, and one season at College Brook and Dube Brook. Bubble traps were visited 1-2 times per week throughout the observation periods. The volume of displaced water at each trap was recorded, indicating total ebullition volume, and syringe volumes larger than 5 mL were collected via an additional syringe and stored for analysis of methane concentration

Gas concentration analysis
All gas samples were analyzed in the Trace Gas Biogeochemistry Laboratory at the University of New Hampshire. Ebullitive gas samples were always analyzed for CH4, and when enough sample was available, for CO2 and nitrous oxide (N2O) as well. The concentration in parts per million (ppmv) of CH4 was determined by analysis with a Shimadzu Gas Chromatograph Flame Ionization Detector (GC-FID; Treat et al. 2007), CO2 (ppmv) using an infrared gas analyzer (LI-6252 CO2 InfraRed Gas Analyzer [IRGA]), and N2O using a Shimadzu GC-8A with an electron capture detector (GC-ECD). Methane was standardized using the average area response of 10 injections of a standard gas mixture (Northeast Airgas, 2.006 ppmv or Maine Oxy, 1000 ppmv) to determine an instrument precision of analysis (Frolking & Crill, 1994). For CO2, an instrumentation response factor for the IRGA was identified by first using a linear regression analysis to determine the slope and y-intercept of the standards (Northeast Airgas, 980.9 ppmv). Triplicate standards were run by injecting incremental volumes of CO2 standard gas (1, 3, 4, 5, 10 mL; Treat et al. 2014). Finally, for N2O (ppmv) triplicate injections of three standard gases (0.267, 0.638, and 1.98 ppmv) were used to develop a standard curve response.

Flux calculations
Not all measured ebullitive gas volumes were analyzed for gas concentration (Table S1). To estimate the gas flux of these samples, we implemented bootstrap resampling to assign concentrations to these unanalyzed samples (Treat et al. 2018). We randomly sampled from the population of analyzed ebullitive methane  concentrations at a stream with replacement to assign a concentration to any non-measured sample volume.  This sampling was repeated 1,000 times and the resulting median concentration calculated for each missing ebullitive gas sample was used in analysis.  The ebullitive flux was then calculated as the mass of methane emitted per sampling area per unit time:

  Ebullitive flux =(Gas concentration × Volume captured)/(Area of bubble trap × Time since last measurement)  (1)

A flux was calculated for each trap for each observation period. The mean, standard deviation, median, minimum, and maximum of all traps and all measurements at a stream over a 15-day period is presented here.


Version 01: June 24, 2021, data and metadata updates to comply with importation to DEIMS7 and LTER Data Portal. Used MarcrosExportEML_HTML (working)pie_excel2007_Sep2020.xlsm 9/17/20 1:11 PM for QA/QC to EML 2.1.0.
Version 02: July 26, 2021, mean CO2 and N2O ebullition added. Renamed file from "WAT-Methane-Stream" to "WAT-Stream-Ebullition". Updates comply with importation to DEIMS7 and LTER Data Portal. Used MarcrosExportEML_HTML (working)pie_excel2007_Jul2021.xlsm 7/26/2021 9:04 AM for QA/QC to EML 2.1.0.


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