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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
USGS2004

Conservative and reactive solute transport in constructed wetlands

The transport of bromide, a conservative tracer, and rhodamine WT (RWT), a photodegrading tracer, was evaluated in three wastewater‐dependent wetlands near Phoenix, Arizona, using a solute transport model with transient storage. Coupled sodium bromide and RWT tracer tests were performed to establish conservative transport and reactive parameters in constructed wetlands with water losses ranging from (1) relatively impermeable (15%), (2) moderately leaky (45%), and (3) significantly leaky (76%). RWT first‐order photolysis rates and sorption coefficients were determined from independent field and laboratory experiments. Individual wetland hydraulic profiles influenced the extent of transient storage interaction in stagnant water areas and consequently RWT removal. Solute mixing and transient storage interaction occurred in the impermeable wetland, resulting in 21% RWT mass loss from main channel and storage zone photolysis (10%) and sorption (11%) reactions. Advection and dispersion governed solute transport in the leaky wetland, limiting RWT photolysis removal (1.2%) and favoring main channel sorption (3.6%). The moderately leaky wetland contained islands parallel to flow, producing channel flow and minimizing RWT losses (1.6%).

Water Resources Research↗
USGS2004

Reach-scale cation exchange controls on major ion chemistry of an Antarctic glacial meltwater stream

McMurdo dry valleys of Antarctica represent the largest of the ice-free areas on the Antarctic continent, containing glaciers, meltwater streams, and closed basin lakes. Previous geochemical studies of dry valley streams and lakes have addressed chemical weathering reactions of hyporheic substrate and geochemical evolution of dry valley surface waters. We examine cation transport and exchange reactions during a stream tracer experiment in a dry valley glacial meltwater stream. The injection solution was composed of dissolved Li + , Na + , K + , and Cl - . Chloride behaved conservatively in this stream, but Li + , Na + , and K + were reactive to varying degrees. Mass balance analysis indicates that relative to Cl - , Li + and K + were taken up in downstream transport and Na + was released. Simulations of conservative and reactive (first-order uptake or generation) solute transport were made with the OTIS (one-dimensional solute transport with inflow and storage) model. Among the four experimental reaches of Green Creek, solute transport simulations reveal that Li + was removed from stream water in all four reaches, K + was released in two reaches, taken up in one reach, and Na + was released in all four reaches. Hyporheic sediments appear to be variable with uptake of Li + in two reaches, uptake of K + in one reach, release of K + in two reaches, and uptake of Na + in one reach. Mass balances of the conservative and reactive simulations show that from 1.05 to 2.19 moles of Li + was adsorbed per reach, but less than 0.3 moles of K + and less than 0.9 moles of Na + were released per reach. This suggests that either (1) exchange of another ion which was not analyzed in this experiment or (2) that both ion exchange and sorption control inorganic solute transport. The elevated cation concentrations introduced during the experiment are typical of initial flows in each flow season, which flush accumulated dry salts from the streambed. We propose that the bed sediments (which compose the hyporheic zone) modulate the flushing of these salts during initial flows each season, due to ion exchange and sorption reactions.

Aquatic Geochemistry↗
USGS2004

Inorganic N and P dynamics of Antarctic glacial meltwater streams as controlled by hyporheic exchange and benthic autotrophic communities

The McMurdo Dry Valleys of South Victoria Land, Antarctica, contain numerous glacial meltwater streams that drain into lakes on the valley floors. Many of the streams have abundant perennial mats of filamentous cyanobacteria. The algal mats grow during streamflow in the austral summer and are in a dormant freeze-dried state during the rest of the year. NO 3 and soluble reactive P (SRP) concentrations were lower in streams with abundant algal mats than in streams with sparse algal mats. NO 3 and SRP concentrations were higher in the hyporheic zone of a stream with abundant algal mats than in the stream itself. An experimental injection of LiCl, NaNO 3 , and K 3 PO 4 was conducted in Green Creek, which has abundant algal mats. Substantial hyporheic exchange occurred. The NO 3 and PO 4 concentrations at 50 m below the injection were 55 μM and 18 μM, respectively, during the experiment. NO 3 and PO 4 concentrations were below the detection limit of 1 to 2 μM at a site 497 m below the injection during the Cl tracer arrival, indicating a high capacity for nutrient uptake by algal communities. NO 2 and NH 4 were present at sites 226 and 327 m below the injection, indicating that, in addition to denitrification and algal uptake, dissimilatory NO 3 reduction to NO 2 and NH 4 may be a NO 3 sink during transport. Transport modelling with nutrient uptake represented as a 1 st -order process yielded reach-scale parameters of 4.3 × 10 −5 to 3.9 × 10 −4 /s and 1.4 × 10 −4 to 3.8 × 10 −4 /s for uptake of NO 3 and PO 4 , respectively. The best match with the observed data was a model in which PO 4 uptake occurred only in the main channel and NO 3 uptake occurred in the main channel and in the hyporheic zone. Hyporheic NO 3 uptake was 7 to 16% of the total uptake for the different stream reaches. These results demonstrate that nutrient flux to the lakes is controlled by hyporheic exchange and nutrient uptake by algal mats in dry valley streams. Streams without algal mats contribute more nutrients to the lakes than streams with algal mats.

Journal of the North American Benthological Societ↗
USGS2003

Phosphate dynamics in an acidic mountain stream: Interactions involving algal uptake, sorption by iron oxide, and photoreduction

Acid mine drainage streams in the Rocky Mountains typically have few algal species and abundant iron oxide deposits which can sorb phosphate. An instream injection of radiolabeled phosphate (32P0,) into St. Kevin Gulch, an acid mine drainage stream, was used to test the ability of a dominant algal species, Ulothrix sp., to rapidly assimilate phosphate. Approximately 90% of the injected phosphate was removed from the water column in the 175-m stream reach. When shaded stream reaches were exposed to full sunlight after the injection ended, photoreductive dissolution of iron oxide released sorbed 32P, which was then also removed downstream. The removal from the stream was modeled as a first-order process by using a reactive solute transport transient storage model. Concentrations of 32P mass-’ of algae were typically lo-fold greater than concentrations in hydrous iron oxides. During the injection, concentrations of 32P increased in the cellular P pool containing soluble, low-molecular-weight compounds and confirmed direct algal uptake of 32P0, from water. Mass balance calculations indicated that algal uptake and sorption on iron oxides were significant in removing phosphate. We conclude that in stream ecosystems, PO, sorbed by iron oxides can act as a dynamic nutrient reservoir regulated by photoreduction.

Colorado↗
USGS2003

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↗
USGS2003

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↗
USGS2003

Transport and cycling of iron and hydrogen peroxide in a freshwater stream: Influence of organic acids

An in‐stream injection of two dissolved organic acids (phthalic and aspartic acids) was performed in an acidic mountain stream to assess the effects of organic acids on Fe photoreduction and H 2 O 2 cycling. Results indicate that the fate of Fe is dependent on a net balance of oxidative and reductive processes, which can vary over a distance of several meters due to changes in incident light and other factors. Solution phase photoreduction rates were high in sunlit reaches and were enhanced by the organic acid addition but were also limited by the amount of ferric iron present in the water column. Fe oxide photoreduction from the streambed and colloids within the water column resulted in an increase in the diurnal load of total filterable Fe within the experimental reach, which also responded to increases in light and organic acids. Our results also suggest that Fe(II) oxidation increased in response to the organic acids, with the result of offsetting the increase in Fe(II) from photoreductive processes. Fe(II) was rapidly oxidized to Fe(III) after sunset and during the day within a well‐shaded reach, presumably through microbial oxidation. H 2 O 2 , a product of dissolved organic matter photolysis, increased downstream to maximum concentrations of 0.25 μM midday. Kinetic calculations show that the buildup of H 2 O 2 is controlled by reaction with Fe(II), but this has only a small effect on Fe(II) because of the small formation rates of H 2 O 2 compared to those of Fe(II). The results demonstrate the importance of incorporating the effects of light and dissolved organic carbon into Fe reactive transport models to further our understanding of the fate of Fe in streams and lakes.

Water Resources Research↗
USGS2002

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↗
USGS2002

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↗
USGS2002

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↗
USGS2002

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↗
USGS2001

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↗
USGS2000

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↗
USGS1999

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↗
USGS1999

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↗