Site Description
The S1 and S2 bogs are located in the Marcell Experimental Forest (near Grand Rapids, MN, USA; 93.472 degrees W, 47.504 degrees N and 93.473 degrees W, 47.514 degrees N, respectively; Sebestyen et al., 2021a). From 1961 to 2019, mean annual precipitation was 78.7 cm and mean annual temperature was 3.6 degrees C (Sebestyen et al., 2021a). The S1 bog has an area of 8.1 ha, a maximum elevation of 430 m, and an outlet elevation of 412 m. The S2 bog has an area of 3.2 ha, a maximum elevation of 430 m, and an outlet elevation of 420 m (Sebestyen et al., 2011b). Both bogs are acidic, with pH values near 4 (Griffiths and Sebestyen, 2016; Sebestyen et al., 2021b), and ombrotrophic, with precipitation as the dominant water source (Verry, 1975). Each bog is drained by an intermittent stream (Sebestyen et al., 2011b; Verry et al., 2011). Vegetation consists mostly of black spruce (Picea mariana), Sphagnum species, and ericaceous shrubs (Sebestyen et al., 2011b). Trees in the S1 bog were experimentally harvested in 1969 and 1974 with no effect on bog water table or stream water yield (Sebestyen et al., 2011a). The S2 bog has been used as a reference peatland for experiments at surrounding sites (Sebestyen et al., 2011b).The S1 bog is the site of the Spruce and Peatland Responses Under Changing Environments (SPRUCE) experiment (Hanson et al., 2017). The cores from the S1 bog are associated with our research in the SPRUCE project (Curtinrich et al, 2021), but the cores were collected outside of enclosed plots.
Sample collection
Two peat cores were sampled from each bog (S1 and S2) in September 2017 with a stainless-steel Russian corer (5 cm diameter; Eijelkamp Agriresearch Eqiupment, Giesbeek, The Netherlands). Cores were taken from the hollow surface to 2 m depth and divided in increments of 10 cm for the first 50 cm and 25 cm thereafter. Samples were sealed in polyethylene bags, kept on ice until arrival at the field lab, and maintained at -20 degrees C until analysis. Thawed samples were homogenized inside the bags, and subsamples (still at field moisture content) were immediately subjected to several chemical extractions and moisture and pH measurements. Gravimetric moisture content was determined by drying ~10 g at 100 degrees C for > 48 h, and pH was measured by placing an electrode into a ~5 g aliquot of each field-moist sample.
Measurements
Concentrations of ferrous, Fe(II), and ferric, Fe(III), were quantified in 0.5 mol/L hydrochloric acid (HCl) extractions with an approximate ratio of 1:30 dry mass equivalent to solution. Samples were vortexed for 1 min, shaken at 120 rpm for one h on a rotary shaker, and centrifuged at 10,000 g for 10 min. The supernatant was removed by pipette and stored in the dark at 4 degrees C. Total Fe and Fe(II) were colorimetrically measured using a ferrozine method (Huang and Hall, 2017b) on a microplate spectrophotometer (Biotek Synergy HT, Winooski VT). Iron(III) was calculated as the difference between total Fe and Fe(II) (Huang and Hall, 2017). Sample values were calibrated as described in Huang and Hall (2017b) using a six-point curve.
Additional field-moist peat subsamples were extracted with 0.05 mol/L sodium dithionite in a ratio of 1:180 dry mass equivalent to solution. This extraction reduces Fe(III) to Fe(II), releasing C that was directly or indirectly associated with Fe(III). In principle, dithionite solubilizes the entire Fe(III) pool, unless it is shielded from reductive dissolution by other minerals or organics (Senesi et al., 1977). Samples were vortexed for 1 min, shaken for 16 h, and centrifuged for 10 min at 20,000 g. The supernatant was removed and residues were further extracted with 0.05 mol/L HCl to dissolve any Fe that may have precipitated with sulfides (Wagai and Mayer, 2007). Separate subsamples were extracted with 0.05 mol/L sodium sulfate to account for any organic C released following ion exchange with sulfate, the oxidation product of dithionite (Wagai and Mayer, 2007). We also measured Fe in the sulfate extractions, interpreted as the soluble or weakly exchangeable Fe pool. The dithionite and sulfate extractions were done in parallel on replicate subsamples, not sequentially, due to the difficulty of completely removing the solution without removing the peat. The dithionite and sulfate extractions were acidified to pH ~2 with hydrochloric acid (HCl) to inhibit microbial activity before storage at 4 degrees C. The concentration of Fe in these extractions was measured with ferrozine as described above (Huang and Hall, 2017b). We calculated Fe in the dithionite plus HCl extraction as the sum of Fe in the dithionite and the subsequent HCl extraction after accounting for Fe remaining in the residual supernatant.
The DOC in the dithionite and sulfate extractions was determined by wet oxidation following Huang and Hall (2017a) adapted from Lang et al (2012). Solutions were combined with powdered potassium persulfate as an oxidant, acidified with phosphoric acid, and sealed in gas-tight vials. Samples were bubbled with carbon dioxide-free air to remove dissolved inorganic carbon and headspace carbon dioxide and heated to 102 degrees C on a block heater to oxidize DOC to carbon dioxide, which was measured by injection into a tunable diode laser (Campbell Scientific TGA200A, Logan UT). Carbon dioxide concentrations were calibrated with a five-point quadratic curve. Sample DOC values were then calibrated with a linear curve using standards prepared in the same matrix as the samples. A six-point curve was used for the dithionite extraction and a seven-point curve was used for the sulfate extraction. We calculated Fe-associated C as the difference between DOC in the dithionite and sulfate extractions (Wagai and Mayer, 2007). We also expressed Fe and DOC on a volume basis using bulk density data from cores sampled previously in the S1 bog (Iversen et al., 2014).
Calcium, magnesium, iron, potassium, phosphorus, and aluminum were measured in the dithionite plus HCl, dithionite, and sulfate extractions with inductively coupled plasma optical emission spectrometry (ICP-OES; Perkin Elmer Optima 5300 DV, Waltham, MA). Iron was measured by ICP-OES to further validate the colorimetric method used in the other analyses. Check standards were run every 10 samples on the ICP. To calibrate ICP values, a four-point linear curve was used with standards prepared in the same matrix as the samples.
Values below the detection limit are reported in the data.
Detection limits:
Ferrous iron 0.04 mg/L
Ferric iron 0.07 mg/L
Dissolved organic carbon in the dithionite extraction 1.3 mg/L
Dissolved organic carbon in the sulfate extraction 0.4 mg/L
Iron in the dithionite extraction measured on the ICP 0.02 mg/L
Potassium in the dithionite extraction 0.003 mg/L
Calcium in the dithionite extraction 0.02 mg/L
Magnesium in the dithionite extraction 0.005 mg/L
Phosphorus in the dithionite extraction 0.02 mg/L
Aluminum in the dithionite extraction 0.03 mg/L
Iron in the dithionite plus HCl extraction measured on the ICP 0.4 mg/L
Potassium in the dithionite plus HCl extraction 0.008 mg/L
Calcium in the dithionite plus HCl extraction 0.1 mg/L
Magnesium in the dithionite plus HCl extraction 0.007 mg/L
Phosphorus in the dithionite plus HCl extraction 0.0009 mg/L
Aluminum in the dithionite plus HCl extraction 0.1 mg/L
Iron in the sulfate extraction measured on the ICP 0.004 mg/L
Potassium in the sulfate extraction 0.0006 mg/L
Calcium in the sulfate extraction 0.02 mg/L
Magnesium in the sulfate extraction 0.005 mg/L
Phosphorus in the sulfate extraction 0.001 mg/L
Aluminum in the sulfate extraction 0.003 mg/L
References
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