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Diane M. McKnight

Publications and source records attributed to Diane M. McKnight.

At least 55 records · Page 3Linked to original sources

Determining long time-scale hyporheic zone flow paths in Antarctic streams

In the McMurdo Dry Valleys of Antarctica, glaciers are the source of meltwater during the austral summer, and the streams and adjacent hyporheic zones constitute the entire physical watershed; there are no hillslope processes in these systems. Hyporheic zones can extend several metres from each side of the stream, and are up to 70 cm deep, corresponding to a lateral cross‐section as large as 12 m 2 , and water resides in the subsurface year around. In this study, we differentiate between the near‐stream hyporheic zone, which can be characterized with stream tracer experiments, and the extended hyporheic zone, which has a longer time‐scale of exchange. We sampled stream water from Green Creek and from the adjacent saturated alluvium for stable isotopes of D and 18 O to assess the significance and extent of stream‐water exchange between the streams and extended hyporheic zones over long time‐scales (days to weeks). Our results show that water residing in the extended hyporheic zone is much more isotopically enriched (up to 11‰ D and 2·2‰ 18 O) than stream water. This result suggests a long residence time within the extended hyporheic zone, during which fractionation has occurred owing to summer evaporation and winter sublimation of hyporheic water. We found less enriched water in the extended hyporheic zone later in the flow season, suggesting that stream water may be exchanged into and out of this zone, on the time‐scale of weeks to months. The transient storage model OTIS was used to characterize the exchange of stream water with the extended hyporheic zone. Model results yield exchange rates (α) generally an order magnitude lower (10 −5 s −1 ) than those determined using stream‐tracer techniques on the same stream. In light of previous studies in these streams, these results suggest that the hyporheic zones in Antarctic streams have near‐stream zones of rapid stream‐water exchange, where ‘fast’ biogeochemical reactions may influence water chemistry, and extended hyporheic zones, in which slower biogeochemical reaction rates may affect stream‐water chemistry at longer time‐scales.

Hydrological Processes

Modeling hyporheic zone processes

Stream biogeochemistry is influenced by the physical and chemical processes that occur in the surrounding watershed. These processes include the mass loading of solutes from terrestrial and atmospheric sources, the physical transport of solutes within the watershed, and the transformation of solutes due to biogeochemical reactions. Research over the last two decades has identified the hyporheic zone as an important part of the stream system in which these processes occur. The hyporheic zone may be loosely defined as the porous areas of the stream bed and stream bank in which stream water mixes with shallow groundwater. Exchange of water and solutes between the stream proper and the hyporheic zone has many biogeochemical implications, due to differences in the chemical composition of surface and groundwater. For example, surface waters are typically oxidized environments with relatively high dissolved oxygen concentrations. In contrast, reducing conditions are often present in groundwater systems leading to low dissolved oxygen concentrations. Further, microbial oxidation of organic materials in groundwater leads to supersaturated concentrations of dissolved carbon dioxide relative to the atmosphere. Differences in surface and groundwater pH and temperature are also common. The hyporheic zone is therefore a mixing zone in which there are gradients in the concentrations of dissolved gasses, the concentrations of oxidized and reduced species, pH, and temperature. These gradients lead to biogeochemical reactions that ultimately affect stream water quality. Due to the complexity of these natural systems, modeling techniques are frequently employed to quantify process dynamics.

Advances in Water Resources

Weathering reactions and hyporheic exchange controls on stream water chemistry in a glacial meltwater stream in the McMurdo Dry Valleys

In the McMurdo Dry Valleys, Antarctica, dilute glacial meltwater flows down well‐established streambeds to closed basin lakes during the austral summer. During the 6–12 week flow season, a hyporheic zone develops in the saturated sediment adjacent to the streams. Longer Dry Valley streams have higher concentrations of major ions than shorter streams. The longitudinal increases in Si and K suggest that primary weathering contributes to the downstream solute increase. The hypothesis that weathering reactions in the hyporheic zone control stream chemistry was tested by modeling the downstream increase in solute concentration in von Guerard Stream in Taylor Valley. The average rates of solute supplied from these sources over the 5.2 km length of the stream were 6.1 × 10 −9 mol Si L −1 m −1 and 3.7 × 10 −9 mol K L −1 m −1 , yielding annual dissolved Si loads of 0.02–1.30 mol Si m −2 of watershed land surface. Silicate minerals in streambed sediment were analyzed to determine the representative surface area of minerals in the hyporheic zone subject to primary weathering. Two strategies were evaluated to compute sediment surface area normalized weathering rates. The first applies a best linear fit to synoptic data in order to calculate a constant downstream solute concentration gradient, dC / dx (constant weathering rate contribution, CRC method); the second uses a transient storage model to simulate dC / dx , representing both hyporheic exchange and chemical weathering (hydrologic exchange, HE method). Geometric surface area normalized dissolution rates of the silicate minerals in the stream ranged from 0.6 × 10 −12 mol Si m −2 s −1 to 4.5 × 10 −12 mol Si m −2 s −1 and 0.4 × 10 −12 mol K m −2 s −1 to 1.9 × 10 −12 mol K m −2 s −1 . These values are an order of magnitude lower than geometric surface area normalized weathering rates determined in laboratory studies and are an order of magnitude greater than geometric surface area normalized weathering rates determined in a warmer, wetter setting in temperate basins, despite the cold temperatures, lack of precipitation and lack of organic material. These results suggest that the continuous saturation and rapid flushing of the sediment due to hyporheic exchange facilitates weathering in Dry Valley streams.

Water Resources Research

Coupling of hydrologic transport and chemical reactions in a stream affected by acid mine drainage

Experiments in St. Kevin Gulch, an acid mine drainage stream, examined the coupling of hydrologic transport to chemical reactions affecting metal concentrations. Injection of LiCl as a conservative tracer was used to determine discharge and residence time along a 1497-m reach. Transport of metals downstream from inflows of acidic, metal-rich water was evaluated based on synoptic samples of metal concentrations and the hydrologic characteristics of the stream. Transport of SO 4 and Mn was generally conservative, but in the subreaches most affected by acidic inflows, transport was reactive. Both 0.1-um filtered and particulate Fe were reactive over most of the stream reach. Filtered Al partitioned to the particulate phase in response to high instream concentrations. Simulations that accounted for the removal of SO 4 , Mn, Fe, and Al with first-order reactions reproduced the steady-state profiles. The calculated rate constants for net removal used in the simulations embody several processes that occur on a stream-reach scale. The comparison between rates of hydrologie transport and chemical reactions indicates that reactions are only important over short distances in the stream near the acidic inflows, where reactions occur on a comparable time scale with hydrologic transport and thus affect metal concentrations.

Environmental Science & Technology

In‐stream sorption of fulvic acid in an acidic stream: A stream‐scale transport experiment

The variation of concentration and composition of dissolved organic carbon (DOC) in stream waters cannot be explained solely on the basis of soil processes in contributing subcatchments. To investigate in‐stream processes that control DOC, we injected DOC‐enriched water into a reach of the Snake River (Summit County, Colorado) that has abundant iron oxyhydroxides coating the streambed. The injected water was obtained from the Suwannee River (Georgia), which is highly enriched in fulvic acid. The fulvic acid from this water is the standard reference for aquatic fulvic acid for the International Humic Substances Society and has been well characterized. During the experimental injection, significant removal of sorbable fulvic acid occurred within the first 141 m of stream reach. We coinjected a conservative tracer (lithium chloride) and analyzed the results with the one‐dimensional transport with inflow and storage (OTIS) stream solute transport model to quantify the physical transport mechanisms. The downstream transport of fulvic acid as indicated by absorbance was then simulated using OTIS with a first‐order kinetic sorption rate constant applied to the sorbable fulvic acid. The “sorbable” fraction of injected fulvic acid was irreversibly sorbed by streambed sediments at rates (kinetic rate constants) of the order of 10 −4 –10 −3 s −1 . In the injected Suwannee River water, sorbable and nonsorbable fulvic acid had distinct chemical characteristics identified in 13 C‐NMR spectra. The 13 C‐NMR spectra indicate that during the experiment, the sorbable “signal” of greater aromaticity and carboxyl content decreased downstream; that is, these components were preferentially removed. This study illustrates that interactions between the water and the reactive surfaces will modify significantly the concentration and composition of DOC observed in streams with abundant chemically reactive surfaces on the streambed and in the hyporheic zone.

Water Resources Research

Effects of stress from mine drainage on diversity, biomass, and function of primary producers in mountain streams

This paper proposes a hypothesis that relates biodi- versity, community biomass, and ecosystem func- tion to a gradient of stress. According to this hy- pothesis, biodiversity has a low threshold of response to stress, whereas biomass and function are stable or increase under low to moderate stress and decrease only under high stress. This hypothe- sis was tested by examining communities of pri- mary producers in streams under stress from mine drainage in the Rocky Mountains of Colorado, USA. Mine drainage exerts chemical stress (low pH, dis- solved metals) as well as physical stress (deposition of metal oxides) on stream biota. Diversity of pri- mary producers was usually more sensitive to stress from mine drainage than community biomass (chlorophyll a) or primary production. Diversity was negatively related to all stresses from mine drainage, but it was especially low in streams with low pH or high concentration of dissolved zinc. Biomass and production were high in streams with only chemical stress, but they were often low in streams with physical stress caused by metal oxide deposition. Stream sites with aluminum oxide dep- osition usually had very little algal biomass. The rate of metal oxide deposition, presence of alumi- num oxides, and pH together explained 65% of the variation in biomass. The rate of net primary pro- duction was highly correlated with biomass and had a similar response to stress from mine drainage. Overall, chemical stresses (low pH, high concentra- tion of zinc) generally led to the hypothesized trends in our model of ecosystems under stress. Physical stress (deposition of metal oxides), how- ever, led to variable responses, and often decreased biomass and function even at low intensity, con- trary to the original hypothesis. Thus, the nature of ecosystem response to stress may differ for chemical and physical stresses

Colorado

pH dependence of iron photoreduction in a rocky mountain stream affected by acid mine drainage

The redox speciation of dissolved iron and the transport of iron in acidic, metal‐enriched streams is controlled by precipitation and dissolution of iron hydroxides, by photoreduction of dissolved ferric iron and hydrous iron oxides, and by oxidation of the resulting dissolved ferrous iron. We examined the pH dependence of these processes in an acidic mine‐drainage stream, St Kevin Gulch, Colorado, by experimentally increasing the pH of the stream from about 4·0 to 6·5 and following the downstream changes in iron species. We used a solute transport model with variable flow to evaluate biogeochemical processes controlling downstream transport. We found that at pH 6·4 there was a rapid and large initial loss of ferrous iron concurrent with the precipitation of aluminium hydroxide. Below this reach, ferrous iron was conservative during the morning but there was a net downstream loss of ferrous iron around noon and in the afternoon. Calculation of net oxidation rates shows that the noontime loss rate was generally much faster than rates for the ferrous iron oxidation at pH 6 predicted by Singer and Stumm (1970. Science 167 : 1121). The maintenance of ferrous iron concentrations in the morning is explained by the photoreduction of photoreactive ferric species, which are then depleted by noon.

Hydrological Processes

Effects of asynchronous snowmelt on flushing of dissolved organic carbon: A mixing model approach

In many snowmelt-dominated catchments, stream dissolved organic carbon (DOC) levels typically increase rapidly as spring melt commences, peak before maximum discharge, and decrease quickly as melting continues. We present data from Deer Creek (Summit County, CO) that shows this distinctive flushing response of DOC during snowmelt runoff, with DOC stored in landscape soils flushed to the stream in response to infiltrating melt waters. Our prior studies show that asynchronous melting of the snowpack across the landscape causes the spring DOC flush to be initiated at different times throughout the catchment. In this study we quantify characteristics of the asynchronous melt and its effect on DOC flushing. We investigated whether a simple mixing model can be used to capture the essentials of the asynchronous melting of a seasonal snowpack and its controls on DOC transport. We divided the catchment into zones of aspect and elevation, which largely determine spatial and temporal variations in the distribution of snow. TOPMODEL was used to simulate the hydrology in each zone, and the simulated flow paths were routed through a simple DOC mixing model to predict contributions of DOC to the stream. The zonal responses were aggregated to give a predicted response of hydrology and DOC fluxes for the entire catchment. Our results indicate that asynchronous melting-which determines the timing of contributions of discharge and DOC to streamflow from different areas of the landscape-can be quantified using a simple modeling approach.

Hydrological Processes

Binding of polychlorinated biphenyls to aquatic humic substances: The role of substrate and sorbate properties on partitioning

Two ortho- (2,2‘,5 and 2,2‘,5,6‘) and a non-ortho- (3,3‘,4,4‘) substituted polychlorinated biphenyl (PCB) congeners were used to study the effects of sorbate structure in binding processes to two lacustrine fulvic acids. Binding constants were determined by solubility enhancement of the solutes by the fulvic acids. The binding of the ortho-trichlorobiphenyl was significantly less than the non-ortho-substituted tetrachlorobiphenyl to both fulvic acids. Surprisingly, the measured ortho-trichlorobiphenyl binding constant to both fulvic acids was approximately the same as the ortho-substituted tetrachlorobiphenyl. The effect of the chlorines in the ortho position inhibits free rotation around the 1,1‘ carbon bond, thereby making the molecule less able to interact effectively with the fulvic acid substrate relative to its non-ortho-substituted congeners. Finally, binding of all three PCBs to the Great Dismal Swamp fulvic acid was significantly higher than for the Pony Lake sample. This observation is attributable to the former substrate's higher degree of aromaticity and polarizability, which can potentially interact more favorably with the PCBs through an increase in van der Waals type interactions.

Environmental Science & Technology

Reactive solute transport in streams: A surface complexation approach for trace metal sorption

A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron- oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The model's ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

Water Resources Research

Dry Valley streams in Antarctica: Ecosystems waiting for water

An axiom of ecology is: 'Where there is water, there is life.' In dry valley ecosystems of Antarctica, this axiom can be extended to: 'Where there has been and will be water, there is life.' Stream communities in the dry valleys can withstand desiccation on an annual basis and also for longer periods - as much as decades or even centuries. These intact ecosystems, consisting primarily of cyanobacteria and eukaryotic algae, spring back to life with the return of water. Soil organisms in the dry valleys also have remarkable survival capabilities (Virginia and Wall 1999), emerging from dormancy with the arrival of water. Streams in the dry valleys carry meltwater from a glacier or ice-field source to the lakes on the valley floors and generally flow for 4-10 weeks during the summer, depending on climatic conditions. Many of these streams contain abundant algal mats that are perennial in the sense that they are in a freeze-dried state during the winter and begin growing again within minutes of becoming wetted by the first flow of the season. The algal species present in the streams are mainly filamentous cyanobacteria (approximately 20 species of the genera Phormidium, Oscillatoria, and Nostoc), two green algal species of the genus Prasiola, and numerous diatom taxa that are characteristic of soil habitats and polar regions. Algal abundances are greatest in those streams in which periglacial processes, acting over periods of perhaps a century, have produced a stable stone pavement in the streambed. This habitat results in a less turbulent flow regime and limits sediment scour from the streambed. Because dry valley glaciers advance and retreat over periods of centuries and millennia and stream networks in the dry valleys evolve through sediment deposition and transport, some of the currently inactive stream channels may receive flow again in the future. Insights- into the process of algal persistence and reactivation will come from long-term experiments that study the effects of reintroducing water flow to channels in which flow has not occurred for decades or centuries. The present work of the McMurdo Dry Valleys LTER has led us to conclude that the legacy of past conditions constitutes a dominant influence on present-day ecosystem structure and function in the dry valleys (Moorhead et al. 1999). For example, Virginia-and Wall (1999) have found that soil nematodes are partly sustained by relict organic carbon from algae that grew during the high lake stands of 8000-10,000 years ago. Similarly, the growth of current algal populations in the lakes of the dry valleys is supported by diffusion of nutrients from relict nutrient pools in the deep bottom waters (Priscu et al. 1999). For the stream ecosystems, abundant algal mats are present in channels that have stable stone pavements, which formed through freeze-thaw cycles occurring over long periods, possibly hundreds of years. We hypothesize that these stone pavements are an important ecological legacy permitting the successful 'waiting for water' strategy. Similarly, the biodiversity of algal species that can survive the harsh conditions in the streams of the dry valleys may be stable for centuries or more, representing a second important ecological legacy.

BioScience

Sources and age of aquatic humus

As aquatic scientists have recognized the diversity of processes controlled by or dependent upon aquatic humus, it has become important to learn more about the genesis, chemical properties, and concentration of humic substances in aquatic ecosystems. There are three classes of aquatic humus (fulvic acids, humic acids, and humin), all of which share the characteristics of being heterogeneous biomolecules which are yellow to brown or black in color, high to moderate molecular weight, and biologically recalcitrant. Fulvic acids are organic acids which are soluble at any pH; humic acids are soluble above pH 2; and humin is insoluble under the full range of pH. Aquatic humus occurs in both dissolved and solid phases, with molecular weights ranging from about 500 D for dissolved fulvic acid to greater than 100,000 D for humic acids in sediments. Although the heterogeneity of these humic fractions makes rigorous chemical studies challenging, there are sufficient analytical methods at hand to make progress toward understanding the sources, formation pathways, and fate of aquatic humus.

Book chapter

Isotopes as indicators of environmental change

In addition to providing an understanding of processes within a catchment system, isotopic techniques have been instrumental in providing reconstructions of catchment climate and other environmental indicators at various time scales. Many recent changes are a direct consequence of anthropogenic activities. Isotopic analysis serves as a valuable tool for distinguishing between natural variations in long-term climatic patterns and anthropogenic effects, yielding improved understanding of natural feedback mechanisms and the development of realistic remediation strategies. This chapter discusses the examples of isotopic techniques that have been applied to understand several types of ongoing and recent environmental changes, and in paleo-environmental studies. It discusses isotope geochemistry, hydrology, and climatology to look at new ways of applying isotopic tracing techniques to provide information on environmental change. It also gives an overview on how isotopic indicators are being applied in investigations of environmental change in continental settings.

Book chapter

Analysis of transient storage subject to unsteady flow: Diel flow variation in an Antarctic stream

Transport of dissolved material in streams and small rivers may be characterized using tracer-dilution methods and solute transport models. Recent studies have quantified stream/substream interactions using models of transient storage. These studies are based on tracer-dilution data obtained during periods of steady flow. We present a modeling framework for the analysis of transient storage in stream systems with unsteady flows. The framework couples a kinematic wave routing model with a solute transport model that includes transient storage. The routing model provides time-varying flows and cross-sectional areas that are used as input to the solute transport model. The modeling framework was used to quantify stream/substream interaction in Huey Creek, an Antarctic stream fed exclusively by glacial meltwater. Analysis of tracer-dilution data indicates that there was substantial interaction between the flowing surface water and the hyporheic (substream) zone. The ratio of storage zone area to stream cross-sectional area (A<sub>s</sub>/A) was >1 in all stream reaches, indicating that the substream area contributing to hyporheic exchange was large relative to stream cross-sectional area. The rate of exchange, as governed by the transient storage exchange coefficient (α), was rapid because of a high stream gradient and porous alluvial materials. Estimates of α generally exceed those determined for other small streams. The high degree of hyporheic exchange supports the hypothesis that weathering reactions within the hyporheos account for observed increases in solute concentration with stream length, as noted in other studies of Antarctic streams.

Journal of the North American Benthological Societ

Assessment of climate change and freshwater ecosystems of the Rocky Mountains, USA and Canada

The Rocky Mountains in the USA and Canada encompass the interior cordillera of western North America, from the southern Yukon to northern New Mexico. Annual weather patterns are cold in winter and mild in summer. Precipitation has high seasonal and interannual variation and may differ by an order of magnitude between geographically close locales, depending on slope, aspect and local climatic and orographic conditions. The region's hydrology is characterized by the accumulation of winter snow, spring snowmelt and autumnal baseflows. During the 2–3-month ‘spring runoff’ period, rivers frequently discharge > 70% of their annual water budget and have instantaneous discharges 10–100 times mean low flow.

Hydrological Processes

Chemical characteristics of particulate, colloidal, and dissolved organic material in Loch Vale Watershed, Rocky Mountain National Park

The chemical relationships among particulate and colloidal organic material and dissolved fulvic acid were examined in an alpine and subalpine lake and two streams in Loch Vale Watershed, Rocky Mountain National Park. The alpine lake, Sky Pond, had the lowest dissolved organic carbon (DOC) (0.37 mgC/L), the highest particulate carbon (POC) (0.13 mgC/L), and high algal biomass. The watershed of Sky Pond is primarily talus slope, and DOC and POC may be autochthonous. Both Andrews Creek and Icy Brook gain DOC as they flow through wet sedge meadows. The subalpine lake, The Loch, receives additional organic material from the surrounding forest and had a higher DOC (0.66 mgC/L). Elemental analysis, stable carbon isotopic compositon, and 13C-NMR characterization showed that: 1) particulate material had relatively high inorganic contents and was heterogeneous in compositon, 2) colloidal material was primarily carbohydrate material with a low inorganic content at all sites; and 3) dissolved fulvic acid varied in compositon among sites. The low concentration and carbohydrate-rich character of the colloidal material suggests that this fraction is labile to microbial degradation and may be turning over more rapidly than particulate fractions or dissolved fulvic acid. Fulvic acid from Andrews Creek had the lowest N content and aromaticity, whereas Sky Pond fulvic acid had a higher N content and lower aromaticity than fulvic acid from The Loch. The UV-visible spectra of the fulvic acids demonstrate that variation in characteristics with sources of organic carbon can explain to some extent the observed nonlinear relationship between UV-B extinction coefficients and DOC concentrations in lakes.

Colorado