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  1. Abstract

    Increasing stream metal concentrations apparently caused by climate warming have been reported for a small number of mountain watersheds containing hydrothermally altered bedrock with abundant sulfide minerals (mineralized watersheds). Such increases are concerning and could negatively impact downstream ecosystem health, water resources, and mine‐site remediation efforts. However, the pervasiveness and typical magnitude of these trends remain uncertain. We aggregated available streamwater chemistry data collected from late summer and fall over the past 40 years for 22 mineralized watersheds throughout the Colorado Rocky Mountains. Temporal trend analysis performed using the Regional Kendall Test indicates significant regional upward trends of ∼2% of the site median per year for sulfate, zinc, and copper concentrations in the 17 streams affected by acid rock drainage (ARD; median pH ≤ 5.5), equivalent to concentrations roughly doubling over the past 30 years. An examination of potential load trends utilizing streamflow data from eight “index gages” located near the sample sites provides strong support for regionally increasing sulfate and metal loads in ARD‐affected streams, particularly at higher elevations. Declining streamflows are likely contributing to regionally increasing concentrations, but increasing loads appear to be on average an equal or greater contributor. Comparison of selected site characteristics with site concentration trend magnitudes shows the highest correlation for mean annual air temperature and mean elevation (R2of 0.42 and 0.35, respectively, with all others being ≤0.14). Future research on climate‐driven controlling mechanisms should therefore focus on processes such as melting of frozen ground directly linked to site mean temperature and elevation.

     
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  2. Abstract

    Many streams originate in forested watersheds at risk of wildfires. Wildfires can introduce thermally altered organic compounds to terrestrial and aquatic systems. Understanding the degradation of leachates from these burned organic materials, referred to as dissolved pyrogenic organic material (PyDOM), is critical in determining water quality impacts in forested watersheds. This study used fluorescence spectroscopy to examine photochemical alterations of PyDOM generated by leaching organic matter burned at various temperatures. The PyDOM was exposed to natural sunlight for 25 days and the photochemical formation of hydrogen peroxide was monitored. PyDOM was characterized using ultraviolet–visible absorption, excitation–emission matrix (EEM) fluorescence spectroscopy, and fluorescence indices. Throughout the experiment, the emission intensity of the humic peak for all light-exposed leachates decreased while dark leachates exhibited no significant change in their fluorescence spectra. Additionally, hydrogen peroxide concentrations and UV absorbance decreased progressively over time, providing direct evidence that PyDOM concentrations can be significantly reduced by photodegradation. A characteristically low emission peak was observed in the EEMs of the fresh PyDOM, which could help in detecting fresh PyDOM. These results demonstrate that PyDOM derived from burned leachates is susceptible to photodegradation and that fluorescence measurements could be used as proxies for detecting PyDOM immediately post-wildfire.

     
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  3. Including a multifunctional, bioregenerative algal photobioreactor for simultaneous air revitalization and thermal control may aid in carbon loop closure for long-duration surface habitats. However, using water-based algal media as a cabin heat sink may expose the contained culture to a dynamic, low temperature environment. Including psychrotolerant microalgae, native to these temperature regimes, in the photobioreactor may contribute to system stability. This paper assesses the impact of a cycled temperature environment, reflective of spacecraft thermal loops, to the oxygen provision capability of temperate Chlorella vulgaris and eurythermic Antarctic Chlorophyta. The tested 28-min temperature cycles reflected the internal thermal control loops of the International Space Station ( C . vulgaris , 9–27°C; Chlorophyta-Ant, 4–14°C) and included a constant temperature control (10°C). Both sample types of the cycled temperature condition concluded with increased oxygen production rates ( C . vulgaris ; initial: 0.013 mgO 2 L –1 , final: 3.15 mgO 2 L –1 and Chlorophyta-Ant; initial: 0.653 mgO 2 L –1 , final: 1.03 mgO 2 L –1 ) and culture growth, suggesting environmental acclimation. Antarctic sample conditions exhibited increases or sustainment of oxygen production rates normalized by biomass dry weight, while both C . vulgaris sample conditions decreased oxygen production per biomass. However, even with the temperature-induced reduction, cycled temperature C . vulgaris had a significantly higher normalized oxygen production rate than Antarctic Chlorophyta. Chlorophyll fluorometry measurements showed that the cycled temperature conditions did not overly stress both sample types (F V /F M : 0.6–0.75), but the Antarctic Chlorophyta sample had significantly higher fluorometry readings than its C . vulgaris counterpart ( F = 6.26, P < 0.05). The steady state C . vulgaris condition had significantly lower fluorometry readings than all other conditions (F V /F M : 0.34), suggesting a stressed culture. This study compares the results to similar experiments conducted in steady state or diurnally cycled temperature conditions. Recommendations for surface system implementation are based off the presented results. The preliminary findings imply that both C . vulgaris and Antarctic Chlorophyta can withstand the dynamic temperature environment reflective of a thermal control loop and these data can be used for future design models. 
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  4. Abstract Many challenges remain before we can fully understand the multifaceted role that natural organic matter (NOM) plays in soil and aquatic systems. These challenges remain despite the considerable progress that has been made in understanding NOM’s properties and reactivity using the latest analytical techniques. For nearly 4 decades, the International Humic Substances Society (IHSS, which is a non-profit scientific society) has distributed standard substances that adhere to strict isolation protocols and reference materials that are collected in bulk and originate from clearly defined sites. These NOM standard and reference samples offer relatively uniform materials for designing experiments and developing new analytical methods. The protocols for isolating NOM, and humic and fulvic acid fractions of NOM utilize well-established preparative scale column chromatography and reverse osmosis methods. These standard and reference NOM samples are used by the international scientific community to study NOM across a range of disciplines from engineered to natural systems, thereby seeding the transfer of knowledge across research fields. Recently, powerful new analytical techniques used to characterize NOM have revealed complexities in its composition that transcend the “microbial” vs. “terrestrial” precursor paradigm. To continue to advance NOM research in the Anthropocene epoch, a workshop was convened to identify potential new sites for NOM samples that would encompass a range of sources and precursor materials and would be relevant for studying NOM’s role in mediating environmental and biogeochemical processes. We anticipate that expanding the portfolio of IHSS reference and standard NOM samples available to the research community will enable this diverse group of scientists and engineers to better understand the role that NOM plays globally under the influence of anthropogenic mediated changes. 
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  5. null (Ed.)
    Previous studies have shown that algal-derived dissolved organic matter (DOM) has a strong influence on the formation of disinfection byproducts (DBPs) during the treatment of drinking water. In the summer of 2010, we evaluated the role of nitrogen and phosphorus loading and phytoplankton abundance as drivers of the concentrations and quality of DOM and the associated DBP formation in 30 reservoirs in the mountains and plains of the State of Colorado. Optical properties such as Specific Ultraviolet Absorbance at 254 nm (SUVA 254 ) and fluorescence spectroscopy were used to characterize DOM quality. Nutrient concentrations such as total nitrogen were also assessed and were associated with high concentrations of chlorophyll a (Chl-a). In turn, high total organic carbon (TOC) concentrations were associated with high concentrations of Chl-a, and the DOM in these reservoirs had a fluorescence signature indicative of contributions from phytoplankton growth. The reservoirs with TOC concentrations above 4 mgC/L were predominantly located in the plains and many are impacted by agricultural runoff and wastewater discharges, rather than in the mountains and are characterized by warm water conditions and shallow depths. For a subset of fourteen reservoirs, we characterized the composition of the phytoplankton using a rapid imaging microscopy technique and observed a dominance by filamentous Cyanobacteria in reservoirs with TOC concentrations above 4 mgC/L. The combination of high TOC concentrations with microbial characteristics resulted in high potential for production of two major classes of regulated DBPs, trihalomethanes and haloacetic acids. While fluorescence spectroscopy was useful in confirming the contribution of phytoplankton growth to high TOC concentrations, evaluation of predictive models for DBP yields found that all equally predictive models included SUVA 254 and some of these models also included fluorescence indices or logTOC. These findings provide a limnological context in support of the recent guidelines that have been implemented for protection of high-quality drinking water supplies in the State of Colorado. 
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  6. Abstract

    Dissolved organic carbon (DOC) is a key variable impacting stream biogeochemical processes. The relationship between DOC concentration (C) and stream discharge (q) can elucidate spatial and temporal DOC source dynamics in watersheds. In the ephemeral glacial meltwater streams of the McMurdo Dry Valleys (MDV), Antarctica, the C‐qrelationship has been applied to dissolved inorganic nitrogen and weathering solutes including silica, which all exhibit chemostatic C‐qbehavior; but DOC‐qdynamics have not been studied. DOC concentrations here are low compared to temperate streams, in the range of 0.1–2 mg C l−1, and their chemical signal clearly indicates derivation from microbial biomass (benthic mats and hyporheic biofilm). To investigate whether the DOC generation rate from these autochthonous organic matter pools was sufficient to maintain chemostasis for DOC, despite these streams' large diel and interannual fluctuations in discharge, we fit the long‐term DOC‐qdata to a power law and an advection‐reaction model. Model outputs and coefficients of variation characterize the DOC‐qrelationship as chemostatic for several MDV streams. We propose a conceptual model in which hyporheic carbon storage, hyporheic exchange rates, and net DOC generation rates are key interacting components that enable chemostatic DOC‐qbehavior in MDV streams. This model clarifies the role of autochthonous carbon stores in maintaining DOC chemostasis and may be useful for examining these relationships in temperate systems, which typically have larger sources of bioavailable autochthonous organic carbon than MDV streams but where this autochthonous signal could be masked by a stronger allochthonous contribution.

     
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