Modeling of Vertical Solute Dispersion in a Sediment Bed Enhanced by Wave‐Induced Interstitial Flow1

Abstract: Mass (solute) transport in a stream or lake sediment bed has a significant effect on chemical mass balances and microbial activities in the sediment. A “1D vertical dispersion model” is a useful tool to analyze or model solute transfer between river or lake water and a sediment bed. Under a motionless water column, solute transfer into and within the sediment bed is by molecular diffusion. However, surface waves or bed forms create periodic pressure waves along the sediment/water interface, which in turn induce flows in the pores of the sediment bed. The enhancement of solute transport by these interstitial periodic flows in the pores has been incorporated in a 1D depth‐dependent “enhanced dispersion coefficient (D_E).” Typically, D_E diminishes exponentially with depth in the sediment bed. Relationships have been developed to estimate D_E as a function of the characteristics of sediment (particle size, hydraulic conductivity, and porosity) and pressure waves (wave length and height). In this paper, we outline and illustrate the calculation of D_E as well as the penetration depth (d_p) of the flow effect. Sample applications to illustrate the computational procedure are provided for dissolved oxygen transfer into a stream gravel bed and release of phosphorus from a lake bed. The sensitivity of the results to input parameter values is illustrated, and compared with the errors obtained when interstitial flow is ignored. Maximum values of D_E near the sediment surface can be on the order of 1 cm²/s in a stream gravel bed with standing waves, and 0.001 cm²/s in a fine sand lake bed under progressive surface waves, much larger than molecular diffusion coefficients.     

A MODEL OF THE BEHAVIOR OF pH DETERMINING PARAMETERS IN IMPOUNDMENTS1

ABSTRACT: A computer model capable of describing the behavior of pH-determining parameters in an impoundment is presented. The steady-state model, based upon principles of water chemistry, applies the complete-mix concept to the routing of the chemical quantities, alkalinity and CO₂ acidity. An iterative procedure is used to account for surface mass transfer of carbon dioxide. A fourth-degree polynomial is solved for the hydrogen ion concentration at each point of routed alkalinity and CO₂ acidity concentrations. Field data required to verify and apply the model are described, including an example application to the Loyalhanna Creek Reservoir.     

LAKEMAP: A 2-D AND 3-D MAPPING SYSTEM FOR VISUALIZING WATER QUALITY DATA IN LAKES1

ABSTRACT: The visualization of water quality data in lakes was achieved by integrating the U.S. Environmental Protection Agency's (EPA) STORET water quality database, lake shoreline polygons from EPA's Reach File (version 3), and the UNIMAP 2-D and 3-D interactive mapping and modeling software. Based on lake name (and state abbreviation), a lake shoreline polygon can be accessed from the Reach File. The coordinates of the polygon are portrayed by the U.S. Geological Survey (USGS) 1:100,000 scale Digital Line Graph (DLG) hydrography layer. This polygon is passed, in turn, to the STORET water quality file. Monitoring stations located within the polygon boundary are extracted along with the complete sampling survey. Specific parameters, such as total phosphorus, pH, ammonia, and optional time and depth restrictions can be selected to build a file of x, y, z₁, z₁…, zn data which is imported to UNIMAP. Up to four parameters, including depth, can be selected at a time. Within UNIMAP, the data is gridded and then displayed as a 2-D color contour map, 3-D perspective contour map, or 2-D projected time or depth slices. This system operates on the EPA ES9000 mainframe computer located in Research Triangle Park (RIP), North Carolina. LAKEMAP is the culmination of an effort to bridge the gap between the vast array of environmental data collected by the EPA and the complex analytical and display software resident on the mainframe.     

Model simulations of dissolved oxygen characteristics of Minnesota lakes: Past and future

A deterministic, one-dimensional, unsteady numerical model has been developed, tested, and applied to simulate mean daily dissolved oxygen (DO) characteristics in 27 lake classes in the state of Minnesota. Reaeration and photosynthesis are the oxygen sources, while respiration, sedimentary, and biochemical water column oxygen demand are the sinks of oxygen in the model. The lake classes are differentiated by surface area (A _s), maximum depth (H _max), and trophic status expressed as Secchi depth (Z _s). Because lake stratification is most important to lake oxygen dynamics, simulated DO characteristics are plotted in terms of a stratification parameterA _s/H _max ^0.25 and Secchi depthZ _s. Simulations provide DO profiles on a daily time scale. Specific DO characteristics of ecological and environmental interest are epilimnetic DO, hypolimnetic DO, DO gradient from surface to bottom, and DO minima and maxima. Specific results are as follows: Simulated mean daily and weekly DO values in the epilimnion of all lakes for both past and future climate scenarios are near saturation over the summer season. Hypolimnetic DO values depend strongly on lake morphometry, trophic status, and time throughout the summer season. Future climate conditions are specified as the historical records from 1955 to 1979, adjusted (monthly) by the 2 × CO₂ GISS model output to account for doubling of atmospheric CO₂. With this climate change, weekly averaged epilimnetic DO is projected to drop by less than 2 mg/liter, and will remain above 7 mg/liter throughout the open water season. The hypolimnetic DO reductions after climate change are on the order of 2–8 mg/liter. Periods of anoxia are longer by as much as 80 days. Those changes would alter water quality dynamics in lakes and have a profound effect on lake ecosystems including indigenous fishes. The results presented are useful for evaluating environmental management options.     

WATERSHED AND LAKE WATER QUALITY ASSESSMENT: AN INTEGRATED MODELING APPROACH1

Watershed planning groups and action agencies seek to understand how lake water quality responds to changes in watershed management. This study developed and demonstrated the applicability of an integrated modeling approach for providing this information. An integrated model linking watershed conditions to water-quality of the receiving lake incorporated the following components: (1) an event-based AGNPS model to estimate watershed pollutant losses; (2) annualization of AGNPS results to produce annual lake pollutant loadings; (3) a base flow separation package, SAM, to estimate base flow; (4) estimates of nutrients in base flow and point sources; and (5) linkage of watershed loadings directly to EUTROMOD lake water quality algorithms. Results are presented for Melvern Lake, a 28-km² multipurpose reservoir with a 900-km² agricultural watershed in east central Kansas. Reasonable estimates of current lake quality were attained using an average phosphorus availability factor of 31 percent to calibrate model results to measured in-lake phosphorus. Comparison of a range of possible scenarios, including all cropland changed to no-till (best case) and all CRP and good-condition grasslands changed to cropland (worst case), indicated only a (4 percent change for in-lake phosphorus and a (2 percent change for chlorophyll a. These results indicated that this watershed is not sensitive to projected changes in land use and management.     

STREAM WASTE ASSIMILATIVE CAPACITY ANALYSIS USING REAERATION COEFFICIENTS MEASURED BY TRACER TECHNIQUES1

Atmospheric reaeration is a natural mechanism of oxygen transfer from the atmosphere to a water body. In practice, stream water quality models are developed with reaeration coefficients (K₂) estimated by predictive equations. This leads to uncertainties in modeling analysis because these equations are empirical in nature and may yield greatly different K₂ values for the same stream. Values of K₂ may be adjusted in model calibration, but unfortunately, values of other model parameters are no less easy to identify and require adjustment in model calibration as well. Therefore, validity of a stream model would be enhanced significantly if K₂ could be determined directly and reliably. In this research, values of K₂ in the Canandaiqua Outlet in Central New York have been measured by using a gas tracer method. A successful modeling analysis was conducted using these K₂ values. As a result, effluent limitations of several waste water discharges into the Outlet were established. It was concluded that field measurements of reaeration rate would improve modeling results significantly, and that the gas tracer method can be easily incorporated into intensive water quality surveys normally required for stream modeling.     

Comparison of several packings for CO2 chemical absorption in a packed column

CO₂ capture and storage has gained widespread attention as an option for reducing greenhouse gas emissions. Chemical absorption and stripping of CO₂ with hot potassium carbonate (K₂CO₃) solutions has been used in the past, however potassium carbonate solutions have a low CO₂ absorption efficiency. Various techniques can be used to improve the absorption efficiency of this system with one option being the addition of promoters to the solvent and another option being an improvement in the mass transfer efficiency of the equipment. This study has focused on improving the efficiency of the packed column by replacing traditional packings with newer types of packing which have been shown to have enhanced mass transfer performance. Three different packings (Super Mini Rings (SMRs), Pall Rings and Mellapak) have been studied under atmospheric conditions in a laboratory scale column for CO₂ absorption using a 30 wt% K₂CO₃ solution. It was found that SMR packing resulted in a mass transfer coefficient approximately 20% and 30% higher than that of Mellapak and Pall Rings, respectively. Therefore, the height of packed column with SMR packing would be substantially lower than with Pall Rings or Mellapak. Meanwhile, the pressure drop using SMR was comparable to other packings while the gas flooding velocity was higher when the liquid load was above 25 kg m⁻² s⁻¹. Correlations for predicting flooding gas velocities and pressure drop were fitted to the experimental data, allowing the relevant parameters to be estimated for use in later design.     

Natural analogue of the rise and dissolution of liquid CO2 in the ocean

The behavior of natural carbon dioxide (CO₂) droplets (8–10 mm in diameter) were observed in a seafloor hydrothermal system at the Okinawa Trough. The natural CO₂ droplet contain 95–98% of CO₂, 2–3% of H₂S, and other gas species. The ascending CO₂ droplets were tracked by a remotely operated vehicle (ROV), and depth, temperature, salinity, pH and partial pressure of CO₂ (pCO₂) in seawater near the CO₂ droplets were measured during droplet ascent by a conductivity-temperature-depth sensor (CTD) and in situ pH/pCO₂ sensor. The visual images of the rising CO₂ droplets were recorded with a high definition television camera on the ROV. A mapping survey (400 m × 400 m; 4 horizontal layers) revealed a dominant distribution of low pH area over the natural CO₂ venting site. The size and rise rate of CO₂ droplets decreased during their ascent in the water column from depths of 1424 to 679 m (a tracking interval of 745 m). The CO₂ droplets dissolved gradually to become small flakes of CO₂ hydrate while rising, and these ascending flakes were found to disappear at 679 m depth. Although a pH as low as 5 was detected just above the liquid CO₂ venting site on the seafloor, no detectable pH depression in the water column ambient to the rising CO₂ droplets was observed. The results of the pH mapping survey showed only localized pH depression over the CO₂ venting site.     

Predicting δCDIC dynamics in CCS: A scheme based on a review of inorganic carbon chemistry under elevated pressures and temperatures

Stable carbon isotopes are important tools to assess potential storage sites for CO₂, as they allow the quantification of ionic trapping via isotope mass balances. In deep geological formations high p/T conditions need to be considered, because CO₂ dissolution, equilibrium constants and isotope fractionation of dissolved inorganic carbon (DIC) depend on temperature, pressure and solute composition. After reviewing different approaches to account for these dependencies, an expanded scheme is presented for speciation and carbon isotope fractionation of DIC and dissolution of CaCO₃ for pCO₂ up to 100 bar, pH down to 3 and temperatures of up to 200 °C. The scheme evaluates the influence of respective parameters on isotope ratios during CO₂ sequestration. The pCO₂ and pH are the dominant controlling factors in the DIC/δ¹³C/pH system. The fugacity of CO₂ has major impact on DIC concentrations at temperatures below 100 °C at high pCO₂. Temperature dependency of activities and equilibrium dominates at temperatures above 100 °C. Isotope ratios of DIC are expected to be about 1–2‰ more depleted in ¹³C compared to the free CO₂ at pCO₂ values above 10 bar. This depletion is controlled by carbon isotope fractionation between CO₂ and H₂CO₃* which is the dominant species of DIC at the resulting pH below 5.     

Evaluation of Lake Modification Alternatives for Lake Sihwa, Korea

After the construction of an embankment at the Bay of Sihwa in Korea, a lake of 56.5 km² surface area and 330 million m³ volume was created. Because of rapid socioenvironmental changes and the lowering of water quality in Lake Sihwa, various external measures have been proposed and some of them are being implemented. In this paper, we examine two alternatives for in-lake modification: one alternative is zoning of the lake by constructing two submerged dams and the other is channeling of the lake through reclamation. Water quality modeling was conducted for both alternatives to assess their effects. Results of the modeling revealed that the reduction of the lake size through two different approaches, when accompanied with other external measures, would improve the water quality, but to different degrees. The zonation is expected to improve the freshwater quality up to the level supplying 45 million m³ of water per year for agricultural use. The quality of channeled water would be inappropriate for agricultural use, but suitable for outdoor activities such as recreation or fishing regardless of reclamation plans considered.     

Validation of a dynamic model of hydrogen permeation through Pd-based membranes

Pd-based membranes have been studied for pure hydrogen separation from syngas: in particular, a mathematical model of a Pd membrane for hydrogen separation has been developed.This model can be used in process and assessment studies of the parameters which characterize the mass transfer phenomena (such as: hydrogen permeability, surface coverage and limiting step). By coupling the permeation and water gas shift reaction kinetics, it can also be used to evaluate the performances of the membrane reactor. Further, it can be helpful to evaluate the best assembly and sizing of a H₂/CO₂ separation system.The model takes into account the kinetics of H₂ adsorption/desorption on Pd surface, the H₂ permeation into the palladium bulk and in the porous layer, and the kinetics of CO, CO₂, H₂O, O₂, H₂S competitive adsorption/desorption on Pd surface. It is also comprehensive of flux equations and bulk mass, momentum and energy balance.The results released by the model were compared to the experimental data during both the transient phase and the steady state conditions. A satisfactory agreement between model and experimental data was found.     

Hollow fiber membrane separation process in the presence of gaseous and particle impurities for post-combustion CO2 capture

The membrane separation process for CO₂ capture can be interfered by the gaseous components and the fine particles in flue gas, especially in desulfurized flue gas. In this work, the pint-sized Polyimide(PI) hollow fiber membrane contactors were self-packed to investigate the membrane CO₂ separation from flue gas containing fine particles and gaseous contaminants (SO₂,SO₃,H₂O). First, the effects of SO₂, SO₃, water vapor, and gypsum particles on the CO₂ capture were studied independently and synergistically. The results showed that the effect of SO₂ on the membrane separation properties is indistinctive; however, the membrane performance was damaged seriously with the addition of SO₃. The high humidity promoted the CO₂ separation initially before inhibiting the PI membrane performance. Moreover, the decrease of the CO₂/N₂ selectivity and the permeation rate were accelerated with the coexistence of SO₂. The membrane performance showed an obvious deterioration in the presence of gypsum particles, with a 21% decrease in the CO₂/N₂ selectivity and 51% decrease in the permeation rate. Furthermore, the gypsum particles exerted dramatic damage. Under the WFGD conditions, the combined effects of SO₂, water vapor, and the gypsum particles influenced the stability of the membrane significantly. This tendency is mainly attributed to the deposition of fine particles and aerosol on the membrane surface, which occupied the effective area and enhanced the mass transfer resistance. This study of impurities’ influence could play an important role in further industrial application of membrane CO₂ capture.     

Modeling CO2 capture with aqueous monoethanolamine

Hilliard completed several thermodynamic models in Aspen Plus^® for modeling CO₂ removal with amine solvents, including MEA–H₂O–CO₂. This solvent was selected to make a system model for CO₂ removal by absorption/stripping. Both the absorber and the stripper used RateSep? to rigorously calculate mass transfer rates. The accuracy of the new model was assessed using a recent pilot plant run with 35 wt.% (9 m) MEA. Absorber loading and removal were predicted within 6%, and the temperature profile was approached within 5 °C. An average 3.8% difference between measured and calculated values was achieved in the stripper. A three-stage flash configuration which efficiently utilizes solar energy was developed. It reduces energy use by 6% relative to a simple stripper. Intercooling was used to reach 90% removal in the absorber at these optimized conditions.     

Spatiotemporal Variability in Water Sources Controls Chemical and Physical Properties of a Semi‐arid Urban River System

We conducted synoptic surveys over three seasons in one year to evaluate the variability in water sources and geochemistry of an urban river with complex water infrastructure in the state of Utah. Using stable isotopes of river water (δ¹⁸O and δ²H) within a Bayesian mixing model framework and a separate hydrologic mass balance approach, we quantified both the proportional inputs and magnitude of discharge associated with “natural” (lake, groundwater, and tributary inputs) and “engineered” (effluent and canal inflows) sources. The relative importance of these major contributors to streamflow varied both spatially and seasonally. Spatiotemporal patterns of dissolved oxygen, temperature, pH, calcium, chloride, nitrate, and orthophosphate indicated seasonal shifts in dominant sources of river water played an important role in determining water quality. We show although urban rivers are clearly influenced by novel water sources created by water infrastructure, they continue to reflect the imprint of “natural” water sources, including diffuse groundwater. Resource managers thus may need to account for the quantity of both surface waters and also historically overlooked groundwater inputs to address water quality concerns in urban rivers.     

The modelling of a hybrid combined cycle with pressurised fluidised bed combustion and CO2 capture

This study investigates the possibility of capturing CO₂ from flue gas under pressurised conditions, which could prove to be beneficial in comparison to working under atmospheric conditions. Simulations of two hybrid combined cycles with pressurised fluidised bed combustion and CO₂ capture are presented. CO₂ is captured from pressurised flue gas by means of chemical absorption after the boiler but before expansion. The results show a CO₂ capture penalty of approximately 8 percentage points (including 90% CO₂ capture rate and compression to 110 bar), which makes the efficiency for the best performing cycle 43.9%. It is 5.2 percentage points higher than the most probable alternative, i.e. using a natural gas fired combined cycle and a pulverised coal fired condensing plant separately with the same fuel split ratio. The largest part of the penalty is associated with the lower mass flow of flue gas after CO₂ capture, which leads to a decrease in work output in the expander and potential for feed water heating. The penalty caused by the regeneration of absorbent is quite low, since the high pressure permits the use of potassium carbonate, which requires less regeneration heat than for example the more commonly proposed monoethanolamine. Although the efficiencies of the cycles look promising it will be important to perform a cost estimate to be able to make a fair comparison with other systems. Such a cost estimate has not been done in this study. A significant drawback of these hybrid cycles in that respect is the complex nature of the systems that will have a negative effect on the economy.     

PROJECTED INCREASES IN MUNICIPAL WATER USE IN THE GREAT LAKES DUE TO CO2-INDUCED CLIMATIC CHANGE1

ABSTRACT: Two scenarios of CO₂-induced climatic change are used to estimate changes in water use for a number of municipalities in the Great Lakes region of Canada and the United States. Both scenarios, based on General Circulation Models produced by the Goddard Institute for Space Studies (GISS) and Geophysical Fluid Dynamics Lab (GFDL), project warmer temperatures for the region. Using regression models based on monthly potential evapotranspiration for individual cities, it is projected that annual per capita water use will increase by a small amount, which will probably have only a marginal effect on water supplies in the Great Lakes basin. This method could also be used to assess the potential impacts of CO₂-induced climatic change on water use by the agriculture and power sectors, as well as the effectiveness of water policy initiatives, such as price changes. More work is needed to project water use during peak periods (warm dry spells), which may occur more frequently in a 2 × CO₂ climate in this region.     

THE USE OF A SIMPLE MODEL AND UNCERTAINTY ANALYSIS IN LAKE MANAGEMENT1

ABSTRACT: A simple, black-box lake model was developed for phosphorus, using nonlinear regression analysis on a data base of north temperate lakes. The uncertainty associated with the model was then combined with the parameter uncertainty and the independent variable uncertainty to provide an estimate of the confidence limits associated with a predicted value. The prediction uncertainty is often neglected, yet it is an important measure of the usefulness of a model. Prediction uncertainty reflects the modeler's confidence in the model, and it should be used by a decision maker as a weight indicating the value of the model prediction. A procedure is outlined that combined lake modeling and uncertainty analysis for use in lake quality assessment and lake management. An example is provided illustrating the use of this procedure in nutrient budget sampling design, data analysis, and the evaluation of lake management strategies for a 208 program in New Hampshire.     

Investigations on CO2 storage capacity in saline aquifers—Part 2: Estimation of storage capacity coefficients

Many studies on geological carbon dioxide (CO₂) storage capacity neglect the influence of complex coupled processes which occur during and after the injection of CO₂. Storage capacity is often overestimated since parts of the reservoirs cannot be reached by the CO₂ plume due to gravity segregation and are thus not accessible for storage. This work investigates the effect of reservoir parameters like depth, temperature, absolute and relative permeability, and capillary pressure on the processes during CO₂ injection and thus on estimates of effective storage capacity. The applied statistical characteristics of parameters are based on a large reservoir parameter database. Different measured relative permeability relations are considered. The methodology of estimating storage capacity is discussed. Using numerical 1D and 3D experiments, detailed time-dependent storage capacity estimates are derived. With respect to the concept developed in this work, it is possible to estimate effective CO₂ storage capacity in saline aquifers. It is shown that effective CO₂ mass stored in the reservoir varies by a factor of 20 for the reservoir setups considered. A high influence of the relative permeability relation on storage capacity is shown.     

FATE OF NITROGEN AND PHOSPHORUS ENTERING A GULF COAST FRESHWATER LAKE: A CASE STUDY1

ABSTRACT: Nitrogen and P fluxes, transformations and water quality functions of Lake Verret (a coastal Louisiana freshwater lake), were quantified. Ortho-P, total-P, NH₄⁺-N NO₃ -N and TKN in surface water collected from streams feeding Lake Verret averaged 104, 340, 59, 185, and 1,060 mg 1^?1, respectively. Lake Verret surface water concentrations of ortho-P, total-P, NH⁺-N, NO₃^?_-N and TKN averaged 66, 191, 36, 66, and 1,292 μg 1^?1. The higher N and P concentrations were located in areas of the lake receiving drainage. Nitrification and denitrification processes were significant in removing appreciable inorganic N from the system. In situ denitrification rates determined from acetylene inhibition techniques show the lake removes 560 mg N m^?2 yr^?1. Laboratory investigations using sediment receiving 450 μg NH⁺₄-N (N-15 labeled) showed that the lake has the potential to remove up to 12.8 g N m^?2 yr^?1. Equilibrium studies of P exchanges between the sediment and water column established the potential or adsorption capacity of bottom sediment in removing P from the overlying water. Lake Verret sediment was found to adsorb P from the water column at concentrations above 50 μg P 1^?1 and the adsorption rates were as great as 300 μg P cm^?2 day^?1 Using the ¹³⁷C s dating techniques, approximately 18 g N m^?2 yr^?1 and 1.2 g P m^?2 yr^?1 were removed from the system via sedimentation. Presently elevated nutrient levels are found only in the upper reaches of the lake receiving nutrient input from runoff from streams draining adjacent agricultural areas. Nitrification, denitrification, and adsorption processes at the sediment water interface over a relatively short distance reduces the N and P levels in the water column. However, if the lake receives additional nutrient loading, elevated levels will likely cover a larger portion of the lake, further reducing water quality in the lake.     

NITROGEN TRANSFORMATIONS IN SEDIMENTS AS AFFECTED BY CHEMICAL AMENDMENTS1

ABSTRACT: A study was conducted to elucidate some of the chemical factors affecting the rate and pathways of N transformations in lake sediments. The main emphasis was placed on modifying a noncalcareous sediment with CaCO₃ to approximate the composition of a calcareous sediment. Additionally, the effects of Ca²⁺, CO₃^2-, Mg2⁺ and OH^- were evaluated by using appropriate chemicals. Further, the effect of aluminum sulfate was evaluated with both sediment types. Sediment pH at 7 days was not affected by CaCO₃, but was decreased by aluminum sulfate. The CaCO₃ treatment increased the rate of ammonification, nitrification, reduction of acetylene to ethylene and methane formation, while with few exceptions the other treatments decreased the rate of the transformations studied. Aluminum sulfate, which has been proposed as a lake restoration treatment, increased ammonification but decreased most of the other transformations.