Samples for greenhouse gas (methane, carbon dioxide) analysis were collected from Falling Creek Reservoir and Beaverdam Reservoir during the ice-free period (March - November) for 2016 - 2018 from the deepest site in each reservoir. Samples were collected from several depths including: 0.1, 1.6, 3.8, 5.0, 6.2, 8.0 and 9.0 m in Falling Creek Reservoir and 0.1, 3.0, 6.0, 9.0, and 11.0 m for Beaverdam Reservoir. These sampling depths were chosen to approximately match outtake valves in Falling Creek Reservoir. Samples were collected monthly in March-April and September-November and twice weekly for Falling Creek Reservoir and weekly from Beaverdam Reservoir from May-August. Samples were collected with a 4-L Van Dorn sampler (Wildlife Supply, Yulee, FL, USA) and transferred to into two replicate 20 mL glass vials without exposure to air and crimp sealed. Samples were stored on ice and analyzed within 24 hours of collection following McClure et al. (2018).
Methane and carbon dioxide concentrations were measured in each sample on a Gas Chromatograph (GC) with a Flame Ionization Detector (FID) and Thermal Conductivity Detector (TCD) following McClure et al. (2018). Briefly, immediately prior to analysis, a 2-mL headspace was created with Helium (He) by displacing 2-mL of sample water. The headspace was equilibrated by shaking each 20-mL vial at 300 rpm for 15 minutes. The 2-mL headspace was then injected into the GC (SRI, Model 8010). The oven temperature was set to 35 degrees C with a carrier gas (He) flow rate of 15 mL/min. CH4 had a retention time of 1.3 min on the FID and CO2 had a retention time of 2.8 min on the TCD. Dissolved concentrations of CH4 and CO2 in water were calculated using the observed head-space concentrations and Henry's Law (McClure et al. 2018). The median percent difference between replicates was 11.2%.
Replicates of each sample were assessed after sample analysis using calculated percent difference between replicate samples. Samples with <30% difference were considered acceptable and both replicates were retained for analysis (flagged as '1', denoting no problems with replicates). If the percent difference between samples was >30% and <50% then the replicates were flagged but were still both used for analysis (flagged as '2', replicates retained but were high). If samples were >50%, then the replicate with the largest difference between the samples collected at depths above and below was removed and only one replicate was used for analysis (flagged as '3', only one replicate retained). Thus, both replicates are reported for flags 1 and 2 but not for flag 3. If no sample was collected or there were issues with the GC analysis, samples were flagged as '4'.
McClure R.P., Hamre K.D., Niederlehner B.R., Munger Z.W., Chen S., Lofton M.E., Schreiber M.E., Carey C.C. (2018). Metalimnetic oxygen minima alter the vertical profiles of carbon dioxide and methane in a managed freshwater reservoir. Science of the Total Environment, 636. pp. 610-620. https://doi.org/10.1016/j.scitotenv.2018.04.255