Although cryoconite holes, sediment-filled melt holes on glacier surfaces, appear small and homogenous, their microbial inhabitants may be spatially partitioned. This partitioning could be ...particularly important for maintaining biodiversity in holes that remain isolated for many years, such as in Antarctica. We hypothesized that cryoconite holes with greater species richness and biomass should exhibit greater partitioning between the sediments and water, promoting greater biodiversity through spatial niche partitioning. We tested this hypothesis by sampling frozen cryoconite holes along a gradient of biomass and biodiversity in the Taylor Valley, Antarctica, where ice-lidded cryoconite holes are a ubiquitous feature of glaciers. We extracted DNA and chlorophyll
from the sediments and water of these samples to describe biodiversity and quantify proxies for biomass. Contrary to our expectation, we found that cryoconite holes with greater richness and biomass showed less partitioning of phylotypes by the sediments versus the water, perhaps indicating that the probability of sediment microbes being mixed into the water is higher from richer sediments. Another explanation may be that organisms from the water were compressed by freezing down to the sediment layer, leaving primarily relic DNA of dead cells to be detected higher in the frozen water. Further evidence of this explanation is that the dominant sequences unique to water closely matched organisms that do not live in cryoconite holes or the Dry Valleys (e.g., vertebrates); so this cryptic biodiversity could represent unknown microbial animals or DNA from atmospheric deposition of dead biomass in the otherwise low-biomass water. Although we cannot rule out spatial niche partitioning occurring at finer scales or in melted cryoconite holes, we found no evidence of partitioning between the sediments and water in frozen holes. Future work should include more sampling of cryoconite holes at a finer spatial scale, and characterizing the communities of the sediments and water when cryoconite holes are melted and active.
Optical properties are easy-to-measure proxies for dissolved organic matter (DOM) composition, source, and reactivity. However, the molecular signature of DOM associated with such optical parameters ...remains poorly defined. The Florida coastal Everglades is a subtropical wetland with diverse vegetation (e.g., sawgrass prairies, mangrove forests, seagrass meadows) and DOM sources (e.g., terrestrial, microbial, and marine). As such, the Everglades is an excellent model system from which to draw samples of diverse origin and composition to allow classically-defined optical properties to be linked to molecular properties of the DOM pool. We characterized a suite of seasonally- and spatially-collected DOM samples using optical measurements (EEM-PARAFAC, SUVA254, S275-295, S350-400, SR, FI, freshness index, and HIX) and ultrahigh resolution mass spectrometry (FTICR-MS). Spearman's rank correlations between FTICR-MS signal intensities of individual molecular formulae and optical properties determined which molecular formulae were associated with each PARAFAC component and optical index. The molecular families that tracked with the optical indices were generally in agreement with conventional biogeochemical interpretations. Therefore, although they represent only a small portion of the bulk DOM pool, absorbance, and fluorescence measurements appear to be appropriate proxies for the aquatic cycling of both optically-active and associated optically-inactive DOM in coastal wetlands.
► We detected a pulp mill effluent-derived signal in the Gulf of Maine watershed. ► We present a novel way to characterize DOM using residuals of PARAFAC models. ► We compared site-specific and ...existing PARAFAC models using quantitative statistics. ► Results suggest value for system-specific models for detecting aquatic contaminants.
Using fluorescence spectroscopy and parallel factor analysis (PARAFAC) we characterized and modeled the fluorescence properties of dissolved organic matter (DOM) in samples from the Penobscot River, Androscoggin River, Penobscot Bay, and the Gulf of Maine (GoM). We analyzed excitation-emission matrices (EEMs) using an existing PARAFAC model (Cory and McKnight, 2005) and created a system-specific model with seven components (GoM PARAFAC). The GoM PARAFAC model contained six components similar to those in other PARAFAC models and one unique component with a spectrum similar to a residual found using the Cory and McKnight (2005) model. The unique component was abundant in samples from the Androscoggin River immediately downstream of a pulp mill effluent release site. The detection of a PARAFAC component associated with an anthropogenic source of DOM, such as pulp mill effluent, demonstrates the importance for rigorously analyzing PARAFAC residuals and developing system-specific models.
Dissolved organic matter (DOM) source and composition are critical drivers of its reactivity, impact microbial food webs and influence ecosystem functions. It is believed that DOM composition and ...abundance represent an integrated signal derived from the surrounding watershed. Recent studies have shown that land-use may have a long-term effect on DOM composition. Methods for characterizing DOM, such as those that measure the optical properties and size of the molecules, are increasingly recognized as valuable tools for assessing DOM sources, cycling, and reactivity. In this study we measured DOM optical properties and molecular weight determinations to evaluate whether the legacy of forest disturbance alters the amount and composition of stream DOM. Differences in DOM quantity and composition due to vegetation type and to a greater extent, wetland influence, were more pronounced than effects due to disturbance. Our results suggest that excitation-emission matrix fluorescence with parallel factor analysis is a more sensitive metric of disturbance than the other methods evaluated. Analyses showed that streams draining watersheds that have been clearcut had lower dissolved organic carbon (DOC) concentrations and higher microbially-derived and protein-like fluorescence features compared to reference streams. DOM optical properties in a watershed amended with calcium, were not significantly different than reference watersheds, but had higher concentrations of DOC. Collectively these results improve our understanding of how the legacy of forest disturbances and natural landscape characteristics affect the quantity and chemical composition of DOM in headwater streams, having implications for stream water quality and carbon cycling.
Leveraging big, open data is the next frontier in ecology. The National Ecological Observatory Network (NEON) is a network of monitoring sites collecting ecological data from across the United ...States. Using a case study approach, we provide examples of how NEON data can be applied to address a few big questions in aquatic ecology. First, we examined spatial patterns in stream water chemistry, to determine whether sites tend to cluster into regions based on geographic proximity. We found that this was not the case, likely because the hydrologic, geologic, and anthropogenic factors that drive heterogeneity in stream water chemistry vary across smaller spatial scales. Second, we examined temporal variability in stream water chemistry. We determined that the majority of catchments are relatively chemostatic (i.e., discharge varies by orders of magnitude more than concentrations) and that differences between catchments are likely to shift across decades due to changes in network conductivity. Third, we tested predictions of the River Continuum Concept (RCC) along a gradient from a second‐order stream to a seventh‐order river. We found that longitudinal patterns in metabolism, carbon chemistry, and macroinvertebrate community composition generally follow the patterns predicted by the RCC. NEON is only in its third year of full operations, with a planned 30‐year life. The studies presented here show the utility of NEON data, while only using a subset of the many data products that NEON produces. The massive amounts and types of data NEON generates, in conjunction with other national‐scale datasets, will allow the research community to better understand how aquatic ecosystems function and respond to drivers of long‐term change.
Dissolved humic material (HDOM) is ubiquitous to all natural waters and its source material influences its chemical structure, reactivity, and bioavailability. While terrestrially derived HDOM ...reference materials distributed by the International Humic Substances Society (IHSS) have been readily available to engineering and scientific communities, a microbially derived reference HDOM was not, despite the well-characterized differences in the chemistry and reactivity of HDOM derived from terrestrial versus microbial sources. To address this gap, we collected a microbial reference fulvic acid from Pony Lake (PLFA) for distribution through the IHSS. Pony Lake is a saline coastal pond on Ross Island, Antarctica, where the landscape is devoid of terrestrial plants. Sample collection occurred over a 17-day period in the summer season at Pony Lake. During this time, the dissolved organic carbon (DOC) concentrations increased nearly two-fold, and the fulvic acid fraction (collected using the XAD-8 method) accounted for 14.6% of the DOC. During the re-concentration and desalting procedures we isolated two other chemically distinct fulvic acid fractions: (1) PLFA-2, which was high in carbohydrates and (2) PLFA-CER, which was high in nitrogen. The chemical characteristics (elemental analysis, optical characterization with UV-vis and fluorescence spectroscopy, and 13C NMR spectroscopy) of the three fulvic acid fractions helped to explain their behavior during isolation.
Fire is an integral component of ecosystems globally and a tool that humans have harnessed for millennia. Altered fire regimes are a fundamental cause and consequence of global change, impacting ...people and the biophysical systems on which they depend. As part of the newly emerging Anthropocene, marked by human-caused climate change and radical changes to ecosystems, fire danger is increasing, and fires are having increasingly devastating impacts on human health, infrastructure, and ecosystem services. Increasing fire danger is a vexing problem that requires deep transdisciplinary, trans-sector, and inclusive partnerships to address. Here, we outline barriers and opportunities in the next generation of fire science and provide guidance for investment in future research. We synthesize insights needed to better address the long-standing challenges of innovation across disciplines to (i) promote coordinated research efforts; (ii) embrace different ways of knowing and knowledge generation; (iii) promote exploration of fundamental science; (iv) capitalize on the "firehose" of data for societal benefit; and (v) integrate human and natural systems into models across multiple scales. Fire science is thus at a critical transitional moment. We need to shift from observation and modeled representations of varying components of climate, people, vegetation, and fire to more integrative and predictive approaches that support pathways toward mitigating and adapting to our increasingly flammable world, including the utilization of fire for human safety and benefit. Only through overcoming institutional silos and accessing knowledge across diverse communities can we effectively undertake research that improves outcomes in our more fiery future.
In this study, we contrast the fluorescent properties of dissolved organic matter (DOM) in fens and bogs in a Northern Minnesota peatland using excitation emission matrix fluorescence spectroscopy ...with parallel factor analysis (EEM‐PARAFAC). EEM‐PARAFAC identified four humic‐like components and one protein‐like component and the dynamics of each were evaluated based on their distribution with depth as well as across sites differing in hydrology and major biological species. The PARAFAC‐EEM experiments were supported by dissolved organic carbon measurements (DOC), optical spectroscopy (UV‐Vis), and compositional characterization by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectroscopy (FT‐ICR MS). The FT‐ICR MS data indicate that metabolism in peatlands reduces the molecular weights of individual components of DOM, and oxygen‐rich less aromatic molecules are selectively biodegraded. Our data suggest that different hydrologic and biological conditions within the larger peat ecosystem drive molecular changes in DOM, resulting in distinctly different chemical compositions and unique fluorescent fingerprints. PARAFAC modeling of EEM data coupled with ultrahigh resolution FT‐ICR MS has the potential to provide significant molecular‐based information on DOM composition that will support efforts to better understand the composition, sources, and diagenetic status of DOM from different terrestrial and aquatic systems.
Spectral characteristics of five components of Dissolved Organic Matter (DOM) in Glacial Lake Agassiz peatland porewaters identified by PARAFAC modeling of EEM fluorescence spectra. Color contours reflect intensities expressed in Quinine Sulfate Equivalent (QSE) units; blue low, red high. The relative loadings of these components to total fluorescence vary as a function of peat type and depth, and appear to be a function of the quality of the DOM and the active microbial community present.
Purpose
The heavily forested Cache la Poudre (CLP) watershed in northern Colorado, USA, was impacted by the High Park wildfire in 2012. The wildfire burned land and vegetation immediately adjacent to ...the CLP River where blackened, ashy sediment samples were collected from five sites upstream of the City of Fort Collins drinking water intake to evaluate the spatial distribution and characteristics of burned sediments, along with quantifying and characterizing soluble compounds following a leaching experiment.
Materials and methods
At each site, samples were collected from three locations: (1) the edge of the bank adjacent to the water edge (downbank), (2) 1 m upslope of location 1 (midbank), and (3) 2 m upslope of location 1 (upperbank). All solid sediment samples were analyzed for elemental composition, and a subset of solid sediment samples were analyzed with
13
C solid-state nuclear magnetic resonance spectroscopy. Sediments were mixed with the background CLP River water collected from upstream of the wildfire and allowed to leach for 6 and 24 h to determine the quantity and quality of water-soluble constituents. Filtered samples were analyzed for dissolved organic carbon (DOC), iron, manganese, and inorganic nutrient concentrations, by optical properties, and for disinfection byproduct (DBP) formation.
Results and discussion
Percent carbon and nitrogen content of the solid sediments were good predictors of leachate DOC concentration. The mean fluorescence index was higher for wildfire-impacted sediment leachates (1.50) compared to the background CLP River water (1.37), which may be due to changes in DOM molecular weight and oxidation of organic matter. All sediment leachates showed consistently higher haloacetonitrile and chloropicrin yields (DBP concentration/DOC concentration) compared to background CLP River water, whereas carbonaceous DBPs did not.
Conclusions
The collected sediments showed that burned material accumulated downstream near the river and was composed of inputs from burned soil and biomass along with the mobilization of unburned terrestrial material. The leachates of these sediments have different characteristics compared to the background CLP River water, indicating that DOM leached from sediments following a wildfire may increase aquatic DOC concentrations and N-DBP formation.
Wetlands are key components in the global carbon cycle and export significant amounts of terrestrial carbon to the coastal oceans in the form of dissolved organic carbon (DOC). Conservative behavior ...along the salinity gradient of DOC and chromophoric dissolved organic matter (CDOM) has often been observed in estuaries from their freshwater end-member (salinity=0) to the ocean (salinity=35). While the oligo/meso-haline (salinity<10) tidal zone of upper estuaries has been suggested to be more complex and locally influenced by geomorphological and hydrological features, the environmental dynamics of dissolved organic matter (DOM) and the environmental drivers controlling its source, transport, and fate have scarcely been evaluated. Here, we investigated the distribution patterns of DOC and CDOM optical properties determined by UV absorbance at 254nm (A254) and excitation–emission matrix (EEM) fluorescence coupled with parallel factor analysis (PARAFAC) along the lower salinity range (salinity<10) of the oligo/meso-haline zone for three distinct wetland-influenced rivers; namely the Bekanbeushi River, a cool-temperate river with estuarine lake in Hokkaido, Japan, the Harney River, a subtropical river with tidally-submerged mangrove fringe in Florida, USA, and the Judan River, a small, acidic, tropical rainforest river in Borneo, Malaysia. For the first two rivers, a clear decoupling between DOC and A254 was observed, while these parameters showed similar conservative behavior for the third. Three distinct EEM-PARAFAC models established for each of the rivers provided similar spectroscopic characteristics except for some unique fluorescence features observed for the Judan River. The distribution patterns of PARAFAC components suggested that the inputs from plankton and/or submerged aquatic vegetation can be important in the Bekanbeushi River. Further, DOM photo-products formed in the estuarine lake were also found to be transported upstream. In the Harney River, whereas upriver-derived terrestrial humic-like components were mostly distributed conservatively, some of these components were also derived from mangrove inputs in the oligo/meso-haline zone. Interestingly, fluorescence intensities of some terrestrial humic-like components increased with salinity for the Judan River possibly due to changes in the dissociation state of acidic functional groups and/or increase in the fluorescence quantum yield along the salinity gradient. The protein-like and microbial humic-like components were distributed differently between three wetland rivers, implying that interplay between loss to microbial degradation and inputs from diverse sources are different for the three wetland-influenced rivers. The results presented here indicate that upper estuarine oligo/meso-haline regions of coastal wetland rivers are highly dynamic with regard to the biogeochemical behavior of DOM.
•DOM dynamics were investigated in the low salinity zones of three wetland rivers.•Biogeochemical behavior of DOM was highly dynamic in the low salinity zone.•Some fluorescent components behaved non-conservatively.•Dissociation state of acidic functional group of DOM may change in a tropical river.