Modeling potential vadose-zone transport of nitrogen from onsite wastewater systems at the development scale

Water in the urban front-range corridor of Colorado has become an increasingly critical resource as the state faces both supply issues as well as anthropogenic degradation of water quality in several aquifers used for drinking water. A proposed development (up to 1100 homes over two quarter-quarter sections) at Todd Creek, Colorado, a suburb of Westminster located about 20 miles northeast of Denver, is considering use of onsite wastewater systems (OWS) to treat and remove domestic wastewater. Local health and environmental agencies have concerns for potential impacts to local water quality. Nitrogen treatment in the vadose zone and subsequent transport to ground water at a development scale is the focus of this investigation. The numerical model HYDRUS 1D was used, with input based on site-specific data and several transport parameters estimated from statistical distribution, to simulate nitrate concentrations reaching ground water. The model predictions were highly sensitive to mass-loading of nitrogen from OWS and the denitrification rate coefficient. The mass loading is relatively certain for the large number of proposed OWS. However, reasonable values for the denitrification rate coefficients vary over three orders of magnitude. Using the median value from a cumulative frequency distribution function, based on rates obtained from the literature, resulted in simulated output nitrate concentrations that were less than 1% of regulatory maximum concentrations. Reasonable rates at the lower end of the reported range, corresponding to lower 95% confidence interval estimates, result in simulated nitrate concentrations reaching groundwater above regulatory limits.     

Kinetic study and modeling on photocatalytic degradation of para-chlorobenzoate at different light intensities

In order to clarify the dependence of apparent adsorption constant Ks in the Langmuir-Hinshelwood (L-H) model on the incident light intensity, photocatalytic degradation kinetic characteristics were experimentally investigated at different light intensities using para-chlorobenzoate (4-CBA) as a model compound. In all cases 4-CBA initial degradation rates showed dependence on 4-CBA initial concentration, which can be described by the L-H model. However, the adsorption constant Ks and rate constant kr obviously varied with light intensity. To account for the experimental finding, slight modification of the classic kinetic model developed by Turchi and Ollis was tentatively proposed by assuming insufficiency of H2O/OH- available for photo-activated holes' scavenging. Such a kinetic model predicts that both k(r) and Ks(-1) are linearly proportional to the square root of the intensity in a rather large intensity range. The validity of the modified model was proved by fitting it to the experimental data.     

Assimilating concentration observations for transport and dispersion modeling in a meandering wind field

Assimilating concentration data into an atmospheric transport and dispersion model can provide information to improve downwind concentration forecasts. The forecast model is typically a one-way coupled set of equations: the meteorological equations impact the concentration, but the concentration does not generally affect the meteorological field. Thus, indirect methods of using concentration data to influence the meteorological variables are required. The problem studied here involves a simple wind field forcing Gaussian dispersion. Two methods of assimilating concentration data to infer the wind direction are demonstrated. The first method is Lagrangian in nature and treats the puff as an entity using feature extraction coupled with nudging. The second method is an Eulerian field approach akin to traditional variational approaches, but minimizes the error by using a genetic algorithm (GA) to directly optimize the match between observations and predictions. Both methods show success at inferring the wind field. The GA-variational method, however, is more accurate but requires more computational time. Dynamic assimilation of a continuous release modeled by a Gaussian plume is also demonstrated using the genetic algorithm approach.     

Pesticide transport in an aerobic aquifer with variable pH--modeling of a field scale injection experiment

Three-dimensional reactive transport simulations were undertaken to study the sorption and degradation dynamics of three herbicides in a shallow aerobic aquifer with spatially variable pH during a 216 days injection experiment. Sorption of two phenoxy acids [(+/-)-2-(4-chloro-2-methylphenoxy) propanoic acid] (MCPP) and [(+/-)-2-(2,4-dichlorophenoxy)propanoic acid] (dichlorprop) was found to be negligible. Degradation of the phenoxy acids was rapid after an initial lag phase. Degradation of the phenoxy acids could only be reproduced satisfactorily by growth-linked microbial degradation. The model fit to the field data was slightly improved if degradation was assumed to be influenced by the local pH that was observed to increase with depth ( approximately 4.5--5.7). In the observed pH-range the nitroaromatic herbicide [2-Methyl-4,6-dinitrophenol] (DNOC) was partly dissociated (pK(a)=4.31) and present in both the neutral and ionized form. The model simulations demonstrated that most of the observed spatial variation in sorption of DNOC could be explained by assuming that only the neutral form of DNOC was subject to sorption. A varying flow field was observed during the injection experiment and the model simulations documented that this most likely resulted in different migration paths for DNOC and the non-sorbing solutes. The model simulations indicated that degradation of DNOC was an important process. The degradation rate of DNOC remained constant over time and was simulated adequately by first-order kinetics. Again, the model fit to field observation was slightly improved if local pH was assumed to influence the degradation rate. Only the maximum utilization rate was estimated from the field data, while the remaining degradation parameters where successfully transferred from the laboratory study.     

Variably saturated flow and multicomponent biogeochemical reactive transport modeling of a uranium bioremediation field experiment

Three-dimensional, coupled variably saturated flow and biogeochemical reactive transport modeling of a 2008 in situ uranium bioremediation field experiment is used to better understand the interplay of transport and biogeochemical reactions controlling uranium behavior under pulsed acetate amendment, seasonal water table variation, spatially variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. While the simulation of the 2008 Big Rusty acetate biostimulation field experiment in Rifle, Colorado was generally consistent with behaviors identified in previous field experiments at the Rifle IFRC site, the additional process and property detail provided several new insights. A principal conclusion from this work is that uranium bioreduction is most effective when acetate, in excess of the sulfate-reducing bacteria demand, is available to the metal-reducing bacteria. The inclusion of an initially small population of slow growing sulfate-reducing bacteria identified in proteomic analyses led to an additional source of Fe(II) from the dissolution of Fe(III) minerals promoted by biogenic sulfide. The falling water table during the experiment significantly reduced the saturated thickness of the aquifer and resulted in reactants and products, as well as unmitigated uranium, in the newly unsaturated vadose zone. High permeability sandy gravel structures resulted in locally high flow rates in the vicinity of injection wells that increased acetate dilution. In downgradient locations, these structures created preferential flow paths for acetate delivery that enhanced local zones of TEAP reactivity and subsidiary reactions. Conversely, smaller transport rates associated with the lower permeability lithofacies (e.g., fine) and vadose zone were shown to limit acetate access and reaction. Once accessed by acetate, however, these same zones limited subsequent acetate dilution and provided longer residence times that resulted in higher concentrations of TEAP reaction products when terminal electron donors and acceptors were not limiting. Finally, facies-based porosity and reactive surface area variations were shown to affect aqueous uranium concentration distributions with localized effects of the fine lithofacies having the largest impact on U(VI) surface complexation. The ability to model the comprehensive biogeochemical reaction network, and spatially and temporally variable processes, properties, and conditions controlling uranium behavior during engineered bioremediation in the naturally complex Rifle IFRC subsurface system required a subsurface simulator that could use the large memory and computational performance of a massively parallel computer. In this case, the eSTOMP simulator, operating on 128 processor cores for 12h, was used to simulate the 110-day field experiment and 50 days of post-biostimulation behavior.     

Kinetic modeling of microbially-driven redox chemistry of radionuclides in subsurface environments: coupling transport, microbial metabolism and geochemistry

Microbial reactions play an important role in regulating pore water chemistry as well as secondary mineral distribution in many subsurface systems and, therefore, may directly impact radionuclide migration in those systems. This paper presents a general modeling approach to couple microbial metabolism, redox chemistry, and radionuclide transport in a subsurface environment. To account for the likely achievement of quasi-steady state biomass accumulations in subsurface environments, a modification to the traditional microbial growth kinetic equation is proposed. The conditions for using biogeochemical models with or without an explicit representation of biomass growth are clarified. Based on the general approach proposed in this paper, the couplings of uranium reactions with biogeochemical processes are incorporated into computer code BIORXNTRN Version 2.0. The code is then used to simulate a subsurface contaminant migration scenario, in which a water flow containing both uranium and a complexing organic ligand is recharged into an oxic carbonate aquifer. The model simulation shows that Mn and Fe oxyhydroxides may vary significantly along a flow path. The simulation also shows that uranium(VI) can be reduced and therefore immobilized in the anoxic zone created by microbial degradation.     

Kinetic modeling of fenton oxidation of phenol and monochlorophenols

A kinetic model, consisting of 28 reactions, was proposed to understand the key mechanism of the Fenton oxidation of phenol and o-, m-, and p-chlorophenols. Particular attention is paid to the interactions of the organic intermediates with the Fe species. The proposed model reasonably predicts the decomposition kinetics and by-product formation for the different phenols at widely varying levels of Fe2+, H2O2, and the phenols. For the phenols and intermediates, change in concentrations with time was predicted within 20-30% deviation from the measured data. The single model predicts the overall kinetics of Fenton oxidation of all the tested phenols by adjusting the rate constant of hydroxyl radical for each phenol. Sensitivity analysis indicates that the key reactions are those that directly govern the levels of OH radical and Fe2+. Both the model prediction and the experimental results show that the decomposition rate could be complicated particularly by the availability of Fe2+. Understanding the interactions of the organic intermediates with Fe2+ is thus of critical importance to improve the decomposition performance.     

Second-order modeling of arsenite transport in soils

Rate limited processes including kinetic adsorption-desorption can greatly impact the fate and behavior of toxic arsenic compounds in heterogeneous soils. In this study, miscible displacement column experiments were carried out to investigate the extent of reactivity during transport of arsenite in soils. Arsenite breakthrough curves (BTCs) of Olivier and Windsor soils exhibited strong retardation with diffusive effluent fronts followed by slow release or tailing during leaching. Such behavior is indicative of the dominance of kinetic retention reactions for arsenite transport in the soil columns. Sharp decrease or increase in arsenite concentration in response to flow interruptions (stop-flow) further verified that non-equilibrium conditions are dominant. After some 40-60 pore volumes of continued leaching, 30-70% of the applied arsenite was retained by the soil in the columns. Furthermore, continued arsenite slow release for months was evident by the high levels of residual arsenite concentrations observed during leaching. In contrast, arsenite transport in a reference sand material exhibited no retention where complete mass recovery in the effluent solution was attained. A second-order model (SOM) which accounts for equilibrium, reversible, and irreversible retention mechanisms was utilized to describe arsenite transport results from the soil columns. Based on inverse and predictive modeling results, the SOM model successfully depicted arsenite BTCs from several soil columns. Based on inverse and predictive modeling results, a second-order model which accounts for kinetic reversible and irreversible reactions is recommended for describing arsenite transport in soils.     

Characterisation of soil emissions of nitric oxide at field and laboratory scale using high resolution method

Agricultural soils may account for 10% of anthropogenic emissions of NO, a precursor of tropospheric ozone with potential impacts on air quality and global warming. However, the estimation of this biogenic source strength and its relationships to crop management is still challenging because of the spatial and temporal variability of the NO fluxes.Here, we present a combination of new laboratory- and field-scale methods to characterise NO emissions and single out the effects of environmental drivers.First, NO fluxes were continuously monitored over the growing season of a maize-cropped field located near Paris (France), using 6 automatic chambers. Mineral fertilizer nitrogen was applied from May to October 2005. An additional field experiment was carried out in October to test the effects of N fertilizer form on the NO emissions. The automatic chambers were designed to measure simultaneously the NO and N₂O gases. Laboratory measurements were carried out in parallel using soil cores sampled at same site to test the response of NO fluxes to varying soil N–NH₄ and water contents, and temperatures. The effects of soil core thickness were also analysed.The highest NO fluxes occurred during the first 5 weeks following fertilizer application. The cumulative loss of NO–N over the growing season was estimated at 1.5 kg N ha^?1, i.e. 1.1% of the N fertilizer dose (140 kg N ha^?1). All rainfall events induced NO peak fluxes, whose magnitude decreased over time in relation to the decline of soil inorganic N. In October, NO emissions were enhanced with ammonium forms of fertilizer N. Conversely, the application of nitrate-based fertilizers did not significantly increase NO emissions compared to an unfertilized control. The results of the subsequent laboratory experiments were in accordance with the field observations in magnitude and time variations. NO emissions were maximum with a water soil content of 15% (w w^?1), and with a NH₄–N content of 180 mg NH₄–N kg soil^?1. The response of NO fluxes to soil temperature was fitted with two exponential functions, involving a Q₁₀ of 2.0 below 20 °C and a Q₁₀ of 1.4 above. Field and laboratory experiments indicated that most of the NO fluxes originated from the top 10 cm of soil. The characterisation of this layer in terms of mean temperature, NH₄ and water contents is thus paramount to explaining the variations of NO fluxes.     

Urban scale modeling of particle number concentration in Stockholm

A three-dimensional dispersion model has been implemented over the urban area of Stockholm (35×35 km) to assess the spatial distribution of number concentrations of particles in the diameter range 3–400 nm. Typical number concentrations in the urban background of Stockholm is 10 000 cm⁻³, while they are three times higher close to a major highway outside the city and seven times higher within a densely trafficked street canyon site in the city center. The model, which includes an aerosol module for calculating the particle number losses due to coagulation and dry deposition, has been run for a 10-day period. Model results compare well with measured data, both in levels and in temporal variability. Coagulation was found to be of little importance in terms of time averaged concentrations, contributing to losses of only a few percent as compared to inert particles, while dry deposition yield particle number losses of up to 25% in certain locations. Episodic losses of up to 10% due to coagulation and 50% due to deposition, are found some kilometers downwind of major roads, rising in connection with low wind speed and suppressed turbulent mixing. Removal due to coagulation and deposition will thus be more significant for the simulation of extreme particle number concentrations during peak episodes.The study shows that dispersion models with proper aerosol dynamics included may be used to assess particle number concentrations in Stockholm, where ultrafine particles principally originate from traffic emissions. Emission factors may be determined from roadside measurements, but ambient temperature must be considered, as it has a strong influence on particle number emissions from vehicles.     

Kinetic and dynamic aspects of soil-plant-snail transfer of cadmium in the field

The proper use of bioaccumulation in the assessment of environmental quality involves accounting for chemical fluxes in organisms. Cadmium (Cd) accumulation kinetics in a soil-plant-snail food chain were therefore investigated in the field under different soil contamination (from 0 to 40 mg kg(-1)), soil pH (6 and 7) and season. Allowing for an accurate and sensitive assessment of Cd transfer to snails, toxicokinetics appears an interesting tool in the improvement of risk assessment procedures and a way to quantify metal bioavailability for a defined target. On the basis of uptake fluxes, snails proved to be sensitive enough to distinguish moderate soil contaminations. The soil pH did not appear, in the range studied, as a modulating parameter of the Cd transfer from soil to snail whereas the season, by influencing the snail mass, may modify the internal concentrations. The present data specifying a time integrated assessment of environmental factors on metal bioavailability and transfer to terrestrial snails should ensure their rational use in environmental biomonitoring.     

Ammonia emission, deposition and impact assessment at the field scale: a case study of sub-grid spatial variability

A local ammonia (NH3) inventory for a 5x5 km area in central England was developed, to investigate the variability of emissions, deposition and impacts of NH3 at a field scale, as well as to assess the validity of the UK 5-km grid inventory. Input data were available for the study area for 1993 and 1996 on a field by field basis, allowing NH3 emissions to be calculated for each individual field, separately for livestock grazing, livestock housing and manure storage, landspreading of manures and fertiliser N application to crops and grassland. An existing atmospheric transport model was modified and applied to model air concentrations and deposition of NH3 at a fine spatial resolution (50 m grid). From the mapped deposition estimates and land cover information, critical loads and exceedances were derived. to study the implications of local variability for regional NH3 impacts assessments. The results show that the most extreme local variability in NH3 emissions, deposition and impacts is linked to housing and storage losses. However, landspreading of manures and intensive cattle grazing are other important area sources, which vary substantially in the landscape. Overall, the range of predicted emissions from agricultural land within the study area is 0-2000 kg N ha(-1) year(-1) in 1993 and 0-8000 kg N ha(-1) year(-1) in 1996, respectively, with the peak at a poultry farm located in the study area. On average, the estimated field level NH3 emissions over the study area closely match the emission for the equivalent 5-km grid square in the national inventory for 1996. Deposition and expected impacts are highly spatially variable, with the edges of woodland and small "islands" of semi-natural vegetation in intensive agricultural areas being most at risk from enhanced deposition. Conversely the centres of larger nature reserves receive less deposition than average. As a consequence of this local variability it is concluded that national assessments at the 5 km grid level underestimate the occurrence of critical loads exceedances due to NH3 in agricultural landscapes.     

Modeling short-term variability of semivolatile organic chemicals in air at a local scale: an integrated modeling approach

Monitoring campaigns from different locations have recently shown how air concentrations of persistent semivolatile contaminants such as polychlorinated biphenyls (PCBs) often exhibit short-term (less than 24 h) variations. The observed patterns have been ascribed to different factors, such as temperature-mediated air-surface exchange and variability of planetary boundary layer (PBL) height and dynamics. Here, we present a new modeling approach developed in order to investigate the short-term variability in air concentrations of organic pollutants at a local scale. A new dynamic multimedia box model is supplied by a meteorological preprocessor (AERMET) with hourly values of air compartment height and wind speed. The resulting model is tested against an existing dataset of PCB air concentrations measured in Zurich, Switzerland. Results show the importance of such modeling approach in elucidating the short- and long-term behavior of semivolatile contaminants in the air/soil system.     

Modeling virus survival and transport in the subsurface

The significance of viruses as agents of waterborne disease in the United States is just beginning to be recognized. The ability to predict how far viruses can be transported and how long they can remain infective in soil and groundwater is desirable from the standpoint of planning the placement of sources of contamination so that they will not have an impact on drinking-water wells. This, in turn should have the effect of decreasing the number of waterborne disease outbreaks caused by viruses. This article reviews the factors that affect the survival and migration of viruses in soils and groundwater. It also discusses the efforts that have been made to mathematically model the movement of viruses in the subsurface, including the assumptions made by the modelers. At this time, it appears that modeling efforts are constrained by a lack of quantitative information on virus interactions with soil and fluid media, rather than on mathematical solution techniques.     

The effect of entrapped nonaqueous phase liquids on tracer transport in heterogeneous porous media: laboratory experiments at the intermediate scale

This work considers the applicability of conservative tracers for detecting high-saturation nonaqueous-phase liquid (NAPL) entrapment in heterogeneous systems. For this purpose, a series of experiments and simulations was performed using a two-dimensional heterogeneous system (10x1.2 m), which represents an intermediate scale between laboratory and field scales. Tracer tests performed prior to injecting the NAPL provide the baseline response of the heterogeneous porous medium. Two NAPL spill experiments were performed and the entrapped-NAPL saturation distribution measured in detail using a gamma-ray attenuation system. Tracer tests following each of the NAPL spills produced breakthrough curves (BTCs) reflecting the impact of entrapped NAPL on conservative transport. To evaluate significance, the impact of NAPL entrapment on the conservative-tracer breakthrough curves was compared to simulated breakthrough curve variability for different realizations of the heterogeneous distribution. Analysis of the results reveals that the NAPL entrapment has a significant impact on the temporal moments of conservative-tracer breakthrough curves.     

Multi-component reactive transport modeling of natural attenuation of an acid groundwater plume at a uranium mill tailings site

Natural attenuation of an acidic plume in the aquifer underneath a uranium mill tailings pond in Wyoming, USA was simulated using the multi-component reactive transport code PHREEQC. A one-dimensional model was constructed for the site and the model included advective-dispersive transport, aqueous speciation of 11 components, and precipitation-dissolution of six minerals. Transport simulation was performed for a reclamation scenario in which the source of acidic seepage will be terminated after 5 years and the plume will then be flushed by uncontaminated upgradient groundwater. Simulations show that successive pH buffer reactions with calcite, Al(OH)3(a), and Fe(OH)3(a) create distinct geochemical zones and most reactions occur at the boundaries of geochemical zones. The complex interplay of physical transport processes and chemical reactions produce multiple concentration waves. For SO4(2-) transport, the concentration waves are related to advection-dispersion, and gypsum precipitation and dissolution. Wave speeds from numerical simulations compare well to an analytical solution for wave propagation.     

Flow transiency on analytical modeling of subsurface solute transport

Environmental Science and Pollution Research - Groundwater flow velocity and dispersivity might be temporally or spatially variable rather than constant. In this paper, linearly-asymptotically or...     

Predicting bioremediation of hydrocarbons: Laboratory to field scale

There are strong drivers to increasingly adopt bioremediation as an effective technique for risk reduction of hydrocarbon impacted soils. Researchers often rely solely on chemical data to assess bioremediation efficiently, without making use of the numerous biological techniques for assessing microbial performance. Where used, laboratory experiments must be effectively extrapolated to the field scale. The aim of this research was to test laboratory derived data and move to the field scale. In this research, the remediation of over thirty hydrocarbon sites was studied in the laboratory using a range of analytical techniques. At elevated concentrations, the rate of degradation was best described by respiration and the total hydrocarbon concentration in soil. The number of bacterial degraders and heterotrophs as well as quantification of the bioavailable fraction allowed an estimation of how bioremediation would progress. The response of microbial biosensors proved a useful predictor of bioremediation in the absence of other microbial data. Field-scale trials on average took three times as long to reach the same endpoint as the laboratory trial. It is essential that practitioners justify the nature and frequency of sampling when managing remediation projects and estimations can be made using laboratory derived data. The value of bioremediation will be realised when those that practice the technology can offer transparent lines of evidence to explain their decisions.