Dissolved organic matter (DOM) composition in small watersheds depends on complex antecedent conditions that ultimately influence DOM generation, processing, and stability downstream. Here, we used ultrahigh resolution Fourier‐transform ion cyclotron resonance mass spectrometry and total dissolved nitrogen and dissolved organic carbon concentrations to investigate how DOM is produced in distinct sub‐catchment types (poor fen, forested wetland, and upland forest) and transported through a watershed in the northeast Pacific coastal temperate rainforest (NPCTR). We traced a suite of previously identified source‐specific marker formulae from vegetation and soil downstream and used them to test models of terrestrial DOM inputs. Marker formulae escaped microbial degradation and were exported from the watershed, demonstrating strong land‐to‐ocean connectivity through the transfer of unmodified tree DOM from specific tree species into the marine environment. Simple hydrologic and temperature variables were better able to predict inputs of soil‐sourced DOM into the stream network than tree‐sourced DOM, highlighting the role of antecedent conditions (e.g., plant growth stage) in DOM source availability and hydrologic flow connectivity, particularly for plant‐derived material. Forested wetland pore waters featured thousands of nitrogen‐containing molecular formulae that potentially provide a path of direct organic nitrogen uptake to organisms. The modified aromaticity index peaked in midsummer (up to 0.55 for fen headwaters) suggesting DOM inputs from freshly produced vegetation provide a strong summertime terrestrial signal. As the climate changes, new watershed‐scale conditions may further complicate predictions of DOM source availability, flow connectivity, and downstream fate in NPCTR watersheds.
Hydrologic controls on carbon processing and export are a critical feature of wetland ecosystems. Hydrologic response to climate variability has important implications for carbon‐climate feedbacks, aquatic metabolism, and water quality. Little is known about how hydrologic processes along the terrestrial‐aquatic interface in low‐relief, depressional wetland catchments influence carbon dynamics, particularly regarding soil‐derived dissolved organic matter (DOM) transport and transformation. To understand the role of different soil horizons as potential sources of DOM to wetland systems, we measured water‐soluble organic matter (WSOM) concentration and composition in soils collected from upland to wetland transects at four Delmarva Bay wetlands in the eastern United States. Spectral metrics indicated that WSOM in shallow organic horizons had increased aromaticity, higher molecular weight, and plant‐like signatures. In contrast, WSOM from deeper, mineral horizons had lower aromaticity, lower molecular weights, and microbial‐like signatures. Organic soil horizons had the highest concentrations of WSOM, and WSOM decreased with increasing soil depth. WSOM concentrations also decreased from the upland to the wetland, suggesting that continuous soil saturation reduces WSOM concentrations. Despite wetland soils having lower WSOM, these horizons are thicker and continuously hydrologically connected to wetland surface and groundwater, leading to wetland soils representing the largest potential source of soil‐derived DOM to the Delmarva Bay wetland system. Knowledge of which soil horizons are most biogeochemically significant for DOM transport in wetland ecosystems will become increasingly important as climate change is expected to alter hydrologic regimes of wetland soils and their resulting carbon contributions from the landscape.more » « less
- NSF-PAR ID:
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- DOI PREFIX: 10.1029
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- Journal of Geophysical Research: Biogeosciences
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Site description. This data package consists of data obtained from sampling surface soil (the 0-7.6 cm depth profile) in black mangrove (Avicennia germinans) dominated forest and black needlerush (Juncus roemerianus) saltmarsh along the Gulf of Mexico coastline in peninsular west-central Florida, USA. This location has a subtropical climate with mean daily temperatures ranging from 15.4 °C in January to 27.8 °C in August, and annual precipitation of 1336 mm. Precipitation falls as rain primarily between June and September. Tides are semi-diurnal, with 0.57 m median amplitudes during the year preceding sampling (U.S. NOAA National Ocean Service, Clearwater Beach, Florida, station 8726724). Sea-level rise is 4.0 ± 0.6 mm per year (1973-2020 trend, mean ± 95 % confidence interval, NOAA NOS Clearwater Beach station). The A. germinans mangrove zone is either adjacent to water or fringed on the seaward side by a narrow band of red mangrove (Rhizophora mangle). 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The sites consisted of the Salt Springs (28.3298°, -82.7274°), Energy Marine Center (28.2903°, -82.7278°), and Green Key (28.2530°, -82.7496°) sites on the Gulf of Mexico coastline in Pasco County, Florida, USA. At each site, we established three plot pairs, each consisting of one saltmarsh plot and one mangrove plot. Plots were 50 m^2 in size. Plots pairs within a site were separated by 230-1070 m, and the mangrove and saltmarsh plots composing a pair were 70-170 m apart. All plot pairs consisted of directly adjacent patches of mangrove forest and J. roemerianus saltmarsh, with the mangrove forests exhibiting a closed canopy and a tree architecture (height 4-6 m, crown width 1.5-3 m). Mangrove plots were located at approximately the midpoint between the seaward edge (water-mangrove interface) and landward edge (mangrove-marsh interface) of the mangrove zone. Saltmarsh plots were located 20-25 m away from any mangrove trees and into the J. roemerianus zone (i.e., landward from the mangrove-marsh interface). Plot pairs were coarsely similar in geomorphic setting, as all were located on the Gulf of Mexico coastline, rather than within major sheltering formations like Tampa Bay, and all plot pairs fit the tide-dominated domain of the Woodroffe classification (Woodroffe, 2002, "Coasts: Form, Process and Evolution", Cambridge University Press), given their conspicuous semi-diurnal tides. There was nevertheless some geomorphic variation, as some plot pairs were directly open to the Gulf of Mexico while others sat behind keys and spits or along small tidal creeks. Our use of a plot-pair approach is intended to control for this geomorphic variation. Plot center elevations (cm above mean sea level, NAVD 88) were estimated by overlaying the plot locations determined with a global positioning system (Garmin GPS 60, Olathe, KS, USA) on a LiDAR-derived bare-earth digital elevation model (Dewberry, Inc., 2019). The digital elevation model had a vertical accuracy of ± 10 cm (95 % CI) and a horizontal accuracy of ± 116 cm (95 % CI). Soil samples were collected via coring at low tide in June 2011. From each plot, we collected a composite soil sample consisting of three discrete 5.1 cm diameter soil cores taken at equidistant points to 7.6 cm depth. Cores were taken by tapping a sleeve into the soil until its top was flush with the soil surface, sliding a hand under the core, and lifting it up. Cores were then capped and transferred on ice to our laboratory at the University of South Florida (Tampa, Florida, USA), where they were combined in plastic zipper bags, and homogenized by hand into plot-level composite samples on the day they were collected. A damp soil subsample was immediately taken from each composite sample to initiate 1 y incubations for determination of active C and N (see below). The remainder of each composite sample was then placed in a drying oven (60 °C) for 1 week with frequent mixing of the soil to prevent aggregation and liberate water. Organic wetland soils are sometimes dried at 70 °C, however high drying temperatures can volatilize non-water liquids and oxidize and decompose organic matter, so 50 °C is also a common drying temperature for organic soils (Gardner 1986, "Methods of Soil Analysis: Part 1", Soil Science Society of America); we accordingly chose 60 °C as a compromise between sufficient water removal and avoidance of non-water mass loss. 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Fines could have been slightly underestimated if any clay particles were burned off during the preceding ignition of soil. An additional subsample was taken from each composite sample to determine extractable N and organic C concentrations via 0.5 M potassium sulfate (K_2SO_4) extractions. We combined soil and extractant (ratio of 1 g dry soil:5 mL extractant) in plastic bottles, reciprocally shook the slurry for 1 h at 120 rpm, and then gravity filtered it through Fisher G6 (1.6 μm pore size) glass fiber filters, followed by colorimetric detection of nitrite (NO_2^-) + nitrate (NO_3^-) and ammonium (NH_4^+) in the filtrate (Hood Nowotny et al., 2010,Soil Science Society of America Journal 74, 1018-1027) using a microplate spectrophotometer (Biotek Epoch, Winooski, VT, USA). Filtrate was also analyzed for dissolved organic C (referred to hereafter as extractable organic C) and total dissolved N via combustion and oxidation followed by detection of the evolved CO_2 and N oxide gases on a Formacs HT TOC/TN analyzer (Skalar, Breda, The Netherlands). Extractable organic N was then computed as total dissolved N in filtrate minus extractable mineral N (itself the sum of extractable NH_4-N and NO_2-N + NO_3-N). We determined soil total C and N from dried, milled subsamples subjected to elemental analysis (ECS 4010, Costech, Inc., Valencia, CA, USA) at the University of South Florida Stable Isotope Laboratory. Median concentration of inorganic C in unvegetated surface soil at our sites is 0.5 % of soil mass (Anderson, 2019, Univ. of South Florida M.S. thesis via methods in Wang et al., 2011, Environmental Monitoring and Assessment 174, 241-257). Inorganic C concentrations are likely even lower in our samples from under vegetation, where organic matter would dilute the contribution of inorganic C to soil mass. Nevertheless, the presence of a small inorganic C pool in our soils may be counted in the total C values we report. Extractable organic C is necessarily of organic C origin given the method (sparging with HCl) used in detection. Active C and N represent the fractions of organic C and N that are mineralizable by soil microorganisms under aerobic conditions in long-term soil incubations. To quantify active C and N, 60 g of field-moist soil were apportioned from each composite sample, placed in a filtration apparatus, and incubated in the dark at 25 °C and field capacity moisture for 365 d (as in Lewis et al., 2014, Ecosphere 5, art59). Moisture levels were maintained by frequently weighing incubated soil and wetting them up to target mass. Daily CO_2 flux was quantified on 29 occasions at 0.5-3 week intervals during the incubation period (with shorter intervals earlier in the incubation), and these per day flux rates were integrated over the 365 d period to compute an estimate of active C. Observations of per day flux were made by sealing samples overnight in airtight chambers fitted with septa and quantifying headspace CO_2 accumulation by injecting headspace samples (obtained through the septa via needle and syringe) into an infrared gas analyzer (PP Systems EGM 4, Amesbury, MA, USA). To estimate active N, each incubated sample was leached with a C and N free, 35 psu solution containing micronutrients (Nadelhoffer, 1990, Soil Science Society of America Journal 54, 411-415) on 19 occasions at increasing 1-6 week intervals during the 365 d incubation, and then extracted in 0.5 M K_2SO_4 at the end of the incubation in order to remove any residual mineral N. Active N was then quantified as the total mass of mineral N leached and extracted. Mineral N in leached and extracted solutions was detected as NH_4-N and NO_2-N + NO_3-N via colorimetry as above. This incubation technique precludes new C and N inputs and persistently leaches mineral N, forcing microorganisms to meet demand by mineralizing existing pools, and thereby directly assays the potential activity of soil organic C and N pools present at the time of soil sampling. Because this analysis commences with disrupting soil physical structure, it is biased toward higher estimates of active fractions. Calculations. Non-mobile C and N fractions were computed as total C and N concentrations minus the extractable and active fractions of each element. This data package reports surface-soil constituents (moisture, fines, SOM, and C and N pools and fractions) in both gravimetric units (mass constituent / mass soil) and areal units (mass constituent / soil surface area integrated through 7.6 cm soil depth, the depth of sampling). Areal concentrations were computed as X × D × 7.6, where X is the gravimetric concentration of a soil constituent, D is soil bulk density (g dry soil / cm^3), and 7.6 is the sampling depth in cm.more » « less
The standard model for aquatic ecosystems is to link hydrologic connectivity to dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) composition and, ultimately, reactivity. Studies across effective precipitation gradients have been suggested as models for predicting how carbon cycling will change in Arctic aquatic ecosystems with projected drying (i.e., reduced hydrologic connectivity). To evaluate links between DOM dynamics and hydrologic connectivity, 41 stream samples from Greenland were analyzed across an effective precipitation gradient for DOM optical properties and elemental composition using ultrahigh‐resolution mass spectrometry. Sites with negative effective precipitation and decreased hydrologic connectivity exhibited elevated specific conductivity (SpC) and DOC concentrations as well as DOM composition indicative of decreased hydrologic connectivity, for example, lower aromaticity, assessed using carbon‐specific UV absorbance at 254 nm, decreased relative abundances of polyphenolic and condensed aromatic compounds, and increased relative abundances of highly unsaturated and phenolic compounds. Allochthonous inputs decreased as the summer progressed as exhibited by decreases in aromatic compounds. A decrease in molecular richness and N‐containing compounds coincided with the decrease in allochthonous inputs. DOC concentrations increased over the summer but more slowly than SpC, suggesting degradation processes outweighed combined evapoconcentration and production. The patterns in DOM composition suggest evapoconcentration and photodegradation are dominant controls. However, when hydrologic connectivity was high, regardless of effective precipitation, DOM reflected allochthonous sources such as snowmelt‐fed wetlands. These results highlight the challenges of modeling carbon cycling in aquatic ecosystems across effective precipitation gradients, particularly those with strong seasonality and regional variability in hydrologic inputs.
Agricultural impacts on aquatic ecosystems are well studied; however, most research has focused on temperate regions, whereas the forefront of agricultural expansion is currently in the tropics. At the vanguard of this growth is the boundary between the Amazon and Cerrado biomes in Brazil, driven primarily by expansion of soybean and corn croplands. Here we examine the impacts of cropland expansion on receiving lowland Amazon Basin headwater streams in terms of dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) composition via ultrahigh‐resolution mass spectrometry. Streams draining croplands had lower DOC concentrations and DOM molecular signatures enriched in N‐ and S‐containing formula in comparison to forested streams. Cropland streams were also enriched in aliphatic, peptide‐like, and highly unsaturated and phenolic (low O/C) compound categories in comparison to forest streams (enriched in polyphenolics, condensed aromatics, and highly unsaturated and phenolic [high O/C] compound categories) indicative of the shifting of sources from organic‐rich surface soils and litter layers to autochthonous and more microbial biomass. Distinct molecular assemblages were strongly correlated with cropland and forest catchments, highlighting headwater streams as sentinels for detecting change. On investigation of unique molecular formulae present in only cropland sites, four cropland markers provided the ability to track agricultural impacts in the region. Overall, these patterns indicate reduced organic matter inputs in croplands and greater microbial degradation at these sites leading to declining DOC concentrations, and DOM of more microbial character in receiving streams that is more biolabile, with clear ramifications for downstream ecology and biogeochemical cycles.
Dissolved organic matter (DOM) drives biogeochemical processes in aquatic ecosystems. Yet, how hydrologic restoration in nutrient‐enriched ecosystems changes DOM and the consequences of those changes for the carbon cycle remain unclear. To predict the consequences of hydrologic restoration on carbon cycling in restored wetlands, we need to understand how local environmental factors influence production, processing, and transport of DOM. We collected surface water samples along transects in restored peat (organic‐rich, macrophyte‐dominated) and marl (carbonate, periphyton‐dominated) freshwater marshes in the Everglades (Florida, U.S.A.) that varied in environmental factors (water depth, phosphorus [P] concentrations [water, macrophytes, periphyton, and soil], and primary producer biomass) to understand drivers of dissolved organic carbon (DOC) concentrations and DOM composition. Higher water depths led to a “greening” of DOM, due to increasing algal contributions, with decreasing concentrations of DOC in peat wetlands, and a “browning” of DOM, due to increasing humic contributions, with increasing DOC concentrations in marl wetlands. Soil total P was positively correlated with DOC concentrations and microbial contributions to DOM in peat wetlands, and periphyton total P was positively correlated with algal contributions to DOM in marl wetlands. Despite large variations in both vegetation biomass and periphyton biovolume across transects and sites, neither were predictors of DOC concentrations or DOM composition. Hydrologic restoration differentially alters DOM in peat and marl marshes and interacts with nutrient enrichment to shift proportions of green and brown contributions to surface water chemistry, which has the potential to modify wetland food webs, as well as the processing of carbon by micro‐organisms.