Biodegradation modelling of a dissolved gasoline plume applying independent laboratory and field parameters

Biodegradation of organic contaminants in groundwater is a microscale process which is often observed on scales of 100s of metres or larger. Unfortunately, there are no known equivalent parameters for characterizing the biodegradation process at the macroscale as there are, for example, in the case of hydrodynamic dispersion. Zero- and first-order degradation rates estimated at the laboratory scale by model fitting generally overpredict the rate of biodegradation when applied to the field scale because limited electron acceptor availability and microbial growth are not considered. On the other hand, field-estimated zero- and first-order rates are often not suitable for predicting plume development because they may oversimplify or neglect several key field scale processes, phenomena and characteristics. This study uses the numerical model BIO3D to link the laboratory and field scales by applying laboratory-derived Monod kinetic degradation parameters to simulate a dissolved gasoline field experiment at the Canadian Forces Base (CFB) Borden. All input parameters were derived from independent laboratory and field measurements or taken from the literature a priori to the simulations. The simulated results match the experimental results reasonably well without model calibration. A sensitivity analysis on the most uncertain input parameters showed only a minor influence on the simulation results. Furthermore, it is shown that the flow field, the amount of electron acceptor (oxygen) available, and the Monod kinetic parameters have a significant influence on the simulated results. It is concluded that laboratory-derived Monod kinetic parameters can adequately describe field scale degradation, provided all controlling factors are incorporated in the field scale model. These factors include advective–dispersive transport of multiple contaminants and electron acceptors and large-scale spatial heterogeneities.     

Estimation of primary drainage three-phase relative permeability for organic liquid transport in the vadose zone

The modeling of transport of organic liquid contaminants through the vadose zone often requires three-phase relative permeabilities. Since these are difficult to measure, predictive models are usually used. The objective of this study is to assess the ability of eight common models to predict the drainage relative permeability to oil in a three-phase system (water-oil-air). A comparison of the models' estimates using data set from Oak [Oak, M.J., 1990. Three-phase relative permeability of water-wet Berea. In: Seventh Symposium on Enhanced Oil Recovery, Paper SPE/Doe 20183. Tulsa, OK, April 22-25] showed that they provide very different predictions for the same system. The goodness of the models does not increase with the amount of data or computation that the models require. Also, the calculations showed how different interpretations of the models and of the terminology associated with them can significantly impact the predictions. Thus, considerable error may be introduced into the simulations of organic liquid transport in the vadose zone depending on the selection and interpretation of the three-phase relative permeability model.     

A simplified approach to modelling underground migration of radionuclides from contaminated river sediments

Accidental releases of waste water from the first Czechoslovak nuclear power plant, A1, caused contamination of sediments of the Dudváh river, flowing into the Vah river, in Slovakia. Rather high concentrations of ¹³⁷Cs and ⁹⁰Sr (2150Bq dm⁻³ and 215Bq dm⁻³, respectively) were found in bottom sediments of a former channel of the re-engineered river body at a distance of about 250 m from a village, Siladice, with water-supply wells. In order to assess the possibility of contamination of the wells, underground migration of both radionuclides from the contaminated area was simulated using an original layered convection-diffusion model. K_d values determined in laboratory experiments were used. The analysis of the hydrological situation in the area reveals that the critical condition is a dominant horizontal groundwater flow near the water table in the direction from the Váh bank to Siladice, in the periods when the contaminated body lies under the water table. The simulation calculated under conservative conditions showed that the contamination of water-supply wells would not exceed permissible concentration limits.     

A modelling approach to determine the origin of urban ground water

A simple modelling approach was developed to link patterns of urban land-use with ground water flow and chemistry in three dimensions and was applied to characterize the origin of recharge in the aquifer beneath the old industrial city of Nottingham, UK. The approach involved dividing land uses into types, and times into periods, and assigning the recharge from each an individual tracer-solute with a unit concentration. The computer code MT3DMS was used to track the multiple tracer-solutes in transient, three-dimensional simulations of the important urban aquifer. A depth-specific hydrochemical dataset collected in parallel supported the model predictions. At depth under the industrial area studied, a large component of ground water originated of older agricultural origin, with relatively low nitrate concentrations. Shallower ground water originated mainly from residential and industrial areas, with higher nitrate concentrations probably arising from leaking sewers and contaminated land. The results highlighted the spectrum of ground water from different origins that amalgamate even at short well screens in a non-pumped borehole and remind us that the non-point-source pollution of ground water from anthropogenic activities will involve more years of slow degradation of quality.     

Combined application of conservative transport modelling and compound-specific carbon isotope analyses to assess in situ attenuation of benzene, toluene, and o-xylene

In recent years, compound specific isotope analyses (CSIA) have developed into one of the most powerful tools for the quantification of in situ biodegradation of organic contaminants. In this approach, the calculation of the extent of biodegradation of organic contaminants in aquifers is usually based on the Rayleigh equation, and thus neglects physical transport processes such as dispersion that contribute to contaminant dilution in aquifers. Here we combine compound specific isotope analyses with a conservative transport model to study the attenuation of aromatic hydrocarbons at a former gasworks site. The conservative transport model was first used to simulate concentration reductions caused by dilution at wells downgradient of a BTEX source. In a second step, the diluted concentrations, together with the available stable carbon isotope ratios and carbon fractionation factors for benzene, toluene and o-xylene were applied in the Rayleigh equation to quantify the degree of biodegradation at each of those wells. At the investigated site, where other attenuation processes such as sorption and volatilisation were proven to be negligible, the combined approach is recommended for benzene, which represents a compound for which the effect of biodegradation is comparable to or less than the effect of dilution. As demonstrated for toluene and o-xylene, the application of the Rayleigh equation alone is sufficient if dilution can be proved to be insignificant in comparison to biodegradation. The analysis also suggests that the source width and the position of the observation wells relative to the plume center line are significantly related to the degree of dilution.     

A prediction-based approach to modelling temporal and spatial variability of traffic-related air pollution in Montreal, Canada

Concentrations of traffic-related air pollution can be highly variable at the local scale and can have substantial seasonal variability. This study was designed to provide estimates of intra-urban concentrations of ambient nitrogen dioxide (NO₂) in Montreal, Canada, that would be used subsequently in health studies of chronic diseases and long-term exposures to traffic-related air pollution. We measured concentrations of NO₂ at 133 locations in Montreal with passive diffusion samplers in three seasons during 2005 and 2006. We then used land use regression, a proven statistical prediction method for describing spatial patterns of air pollution, to develop separate estimates of spatial variability across the city by regressing NO₂ against available land-use variables in each of these three periods. We also developed a “pooled” model across these sampling periods to provide an estimate of an annual average. Our modelling strategy was to develop a predictive model that maximized the model R². This strategy is different from other strategies whose goal is to identify causal relationships between predictors and concentrations of NO₂.Observed concentrations of NO₂ ranged from 2.6 ppb to 31.5 ppb, with mean values of 12.6 ppb in December 2005, 14.0 ppb in May 2006, and 8.9 ppb in August 2006. The greatest variability was observed during May. Concentrations of NO₂ were highest downtown and near major highways, and they were lowest in the western part of the city. Our pooled model explained approximately 80% of the variability in concentrations of NO₂. Although there were differences in concentrations of NO₂ between the three sampling periods, we found that the spatial variability did not vary significantly across the three sampling periods and that the pooled model was representative of mean annual spatial patterns.     

A field trial to assess the performance of CO2-supersaturated water injection for residual volatile LNAPL recovery

A pilot scale field trial was conducted to evaluate the recovery of volatile, light non-aqueous phase liquids (LNAPLs) using a novel remediation method termed supersaturated water injection (SWI). SWI uses a patented technology to efficiently dissolve high concentrations of CO₂ into water at elevated pressures. This water is injected into the subsurface resulting in the nucleation of CO₂ bubbles at and away from the injection point. The nucleating bubbles coalesce, rise and volatilize residual LNAPL ganglia. In this study, an LNAPL composed of 103 kg of volatile pentane and hexane, and 30 kg of non-volatile Soltrol was emplaced below the water table at residual saturation. The SWI technology removed 78% of the pentane and 50% of the less volatile hexane. Contaminant mass was still being removed when the system was shut down for practical reasons. The mass removed is comparable to that expected for air sparging but a much smaller volume of gas was injected using the SWI system.     

A steady state redox zone approach for modeling the transport and degradation of xenobiotic organic compounds from a landfill site

A redox zonation approach is used as a framework for obtaining biodegradation rate constants of xenobiotic compounds in a landfill plume (Grindsted, Denmark). The aquifer is physically heterogeneous in terms of a complex zonation of different geological units close to the landfill and biogeochemically heterogeneous in terms of a specified redox zonation. First-order degradation rates of six organic compounds (benzene, toluene, ethylbenzene, o-xylene, m/p-xylene, and naphthalene) were calculated in the methanogenic/sulfate- and Fe-reducing zones. The numerical simulations show that all compounds are anaerobically biodegraded, but at very different rates. High rates of biodegradation of most of the compounds (except benzene) were found in the Fe-reducing zone. These rates generally agree with previously published rates. Only o-xylene and toluene were significantly biodegraded in the methanogenic/sulfate-reducing environment. All rates in this redox zone are generally much lower than previously published rates.     

Reverse quantitative structure-activity relationship for modelling the sorption of esfenvalerate to dissolved organic matter. A multivariate approach

The sorption of the pyrethroid, esfenvalerate, to the dissolved and/or dispersed fraction of eight different natural humic compounds has been investigated. The dissolved organic matters (DOMs) included in this study originate from ground water, soil pore water, and surface waters. Sorption was modelled at DOM concentration levels where equilibrium partitioning of esfenvalerate between DOM and the aqueous bulk phase prevails. The inherent characteristics of the eight different humic materials, quantified in the preceding paper by Thomsen et al. (2002, this issue (PII: S0045-6535(02)00335-1)), have been used as explanatory variables for modelling this equilibrium partitioning. Using a reverse QSAR approach based on by projection-into-latent-structure regression (PLS-R) inherent sorbent properties determining for the sorption affinity of esfenvalerate to DOM were analysed. For all humic substances a decrease in the DOM-normalised equilibrium-partitioning coefficient, K_DOM, with increasing concentration of DOM was observed. Significant variations in K_DOM values, as function of the inherent characteristics of the individual humic substances, were found at DOM concentrations of 75 and 100 ppm, respectively. The latter is a strong indication of variations in sorption mechanisms of esfenvalerate to DOM of varying inherent properties. Groupings in the principal property space quantifying DOMs may indicate that separate models are needed for quantifying the equilibrium partitioning to different classes of DOM.     

A Technique for Estimating the Age of Regular/Mid-grade Gasolines Released to the Subsurface Since the Early 1970's

Investigators, regulators, and litigants having interest in gasoline hydrocarbon releases are almost always concerned with knowing when a release occurred. Gasoline releases to the subsurface have, historically, been the most difficult to age date because of their volatile nature and highly aromatic composition. Age dating of gasolines in the past has depended on the degree of weathering of the lower boiling hydrocarbons in gasoline, the use and disuse of lead, lead isotopes, the use of other additives such as methyl-tertiary-butyl ether, and major refining and formulation changes. However, these approaches are limited and many times difficult to demonstrate and apply. This paper describes a new age dating technique using gas chromatographic data. It is based on the progressive enhancement of the aromatics and the reduction of the normal alkanes (paraffins) in the manufacture of regular and mid-grade gasolines since the 1970s. The changing composition of gasoline was necessary to maintain octane ratings during the removal of lead from the gasoline and while meeting increasingly stringent air quality regulations over the past 30 years. This paper proposes the use of an index that reflects these changes in gasoline composition over time and can be correlated to when the gasoline was manufactured. The resulting curve can be used to estimate the age of release (manufacture) of gasolines. This forensic application can be successfully applied to liquid gasoline samples where the evaporation of the gasoline is less than 50%. Case histories and examples are presented to demonstrate application of the technique.     

A comparison of numerical solutions of partial differential equations with probabilistic and possibilistic parameters for the quantification of uncertainty in subsurface solute transport

Traditionally, uncertainty in parameters are represented as probabilistic distributions and incorporated into groundwater flow and contaminant transport models. With the advent of newer uncertainty theories, it is now understood that stochastic methods cannot properly represent non random uncertainties. In the groundwater flow and contaminant transport equations, uncertainty in some parameters may be random, whereas those of others may be non random. The objective of this paper is to develop a fuzzy-stochastic partial differential equation (FSPDE) model to simulate conditions where both random and non random uncertainties are involved in groundwater flow and solute transport. Three potential solution techniques namely, (a) transforming a probability distribution to a possibility distribution (Method I) then a FSPDE becomes a fuzzy partial differential equation (FPDE), (b) transforming a possibility distribution to a probability distribution (Method II) and then a FSPDE becomes a stochastic partial differential equation (SPDE), and (c) the combination of Monte Carlo methods and FPDE solution techniques (Method III) are proposed and compared. The effects of these three methods on the predictive results are investigated by using two case studies. The results show that the predictions obtained from Method II is a specific case of that got from Method I. When an exact probabilistic result is needed, Method II is suggested. As the loss or gain of information during a probability–possibility (or vice versa) transformation cannot be quantified, their influences on the predictive results is not known. Thus, Method III should probably be preferred for risk assessments.     

Diffuse source apportionment of the Po river eutrophying load to the Adriatic sea: assessment of Lombardy contribution to Po river nutrient load apportionment by means of an integrated modelling approach

The source apportionment of the annual nutrient load carried by the Po river to the Adriatic sea has been studied.

An integrated modelling approach was applied to the Lombardy plain area, which covers about 34% of the Po river watershed area and accounts for about 50% of the point sources’ loads carried by the river. To extract all the information available from direct instream measurements, two different modelling tools were alternatively used. The source apportionment was investigated considering both dry and wet weather scenarios. In order to quantify the apportionment in dry-weather conditions, the Lombardy portion of the Po river basin was modelled by using the US-EPA QUAL2E model. Such a simulation allowed to assess a significant contribution (about 50% of the total dry-weather load) of a not rain-driven diffuse pollution component (i.e. groundwater, springs, lake emissaries). Moreover, to estimate the rain-driven surface runoff contribution to the instream total load, the Lombardy plain area was also modelled by means of the US-DA SWAT model. SWAT results indicate a runoff contribution to the Po river instream total load of about 10 000 t N yr⁻¹ and 1300 t P yr⁻¹ (i.e. approximately the 10–20% of the total annual Lombardy nutrient load). At the event scale (i.e. the single rainstorm event) the runoff contribution may rise up to 30–80% of the total instream load. Finally, the total annual nitrogen load at the Po basin closure was estimated for the period 1985–2001. Out of a total annual load of 140 000 t N yr⁻¹, Lombardy accounts for 43% (point plus diffuse sources). The rain-driven diffuse sources constitute the 20% of the overall total load, the point sources account for 40%, whereas the remaining 40% is mainly constituted by “dry-weather diffuse sources” (i.e. groundwater, springs, lake emissaries).     

A theoretical model of air and steam co-injection to prevent the downward migration of DNAPLs during steam-enhanced extraction

When steam is injected into soil containing a dense volatile non-aqueous phase liquid contaminant the DNAPL vaporized within the heated soil region condenses and accumulates ahead of the steam condensation front. If enough DNAPL accumulates, gravitational forces can overcome trapping forces allowing the liquid contaminant to flow downward. By injecting air with steam, a portion of the DNAPL vapor remains suspended in equilibrium with the air, decreasing liquid contaminant accumulation ahead of the steam condensation front, and thus reducing the possibility of downward migration. In this work, a one-dimensional theoretical model is developed to predict the injection ratio of air to steam that will prevent the accumulation of volatile DNAPLs. The contaminated region is modeled as a one-dimensional homogeneous porous medium with an initially uniform distribution of a single component contaminant. Mass and energy balances are combined to determine the injection ratio of air to steam that eliminates accumulation of the contaminant ahead of the steam condensation front, and hence reduces the possibility of downward migration. The minimum injection ratio that eliminates accumulation is defined as the optimum injection ratio. Example calculations are presented for three DNAPLs, carbon tetrachloride (CCl4), trichloroethylene (TCE), and perchloroethylene (PCE). The optimum injection ratio of air to steam is shown to depend on the initial saturation and the volatility of the liquid contaminant. Numerical simulation results are presented to validate the model, and to illustrate downward migration for ratios less than optimum. Optimum injection ratios determined from numerical simulations are shown to be in good agreement with the theoretical model.     

Testing the Established Hydrogeologic Model of Source Water to the Amargosa River Basin,Inyo and San Bernardino Counties,California

The current conceptual hydrogeologic model established for source water to the Amargosa River was tested in order to help inform management decisions regarding the Amargosa River's Federal designation as Wild and Scenic through an Act of Congress. The limited availability of water in this region results in the critical need for effective management in the basin to maintain its Wild and Scenic attributes inclusive of habitat for several endangered and threatened species. The use of forensic tools and integration of multiple lines of geologic, hydrogeologic, geochemical, and stable isotopic evidence suggest that the simple historical model for primary groundwater transport through this region is incorrect and that a large supply of regional baseflow does not provide the hydrogeological foundation of the Amargosa River basin. Data collected is consistent with an alternative model requiring complex source mixing and shallow alluvial groundwater that supports river flow. This conclusion also suggests Wild and Scenic conditions in this basin are more precarious than previously understood.     

A root exudates based approach to assess the long-term phytoavailability of metals in biosolids-amended soils

Organic acids present in the rhizosphere of growing plants are widely recognized to be responsible for dissolving the solid phase metals in the soil and making them available for plant absorption. We proposed a root exudates-based model to assess the long-term phytoavailability of metals in biosolids-amended soils. The phytoavailability of biosolids-borne metals was defined in terms of a capacity factor and an intensity factor. The plant available metal pool, C₀ (capacity factor, mg kg⁻¹), can be estimated by fitting the successive organic acids extraction data to an exponential decay kinetic equation. The field metal removal rate, k (intensity factor, yr⁻¹), can be estimated from the successive extraction-based metal release rate through an effective annual organic acid production in the rhizosphere which was found to be characteristic of plant species. The protocol was successfully used to assess the long-term phytoavailability of metals in biosolids-amended soil from two biosolids land application sites.     

A new approach to quantify the degradation kinetics of linuron with UV, ozonation and UV/O3 processes

The degradation of linuron, one of phenylurea herbicides, was investigated for its reaction kinetics by different treatment processes including ultraviolet irradiation (UV), ozonation (O₃), and UV/O₃. The decay rate of linuron by UV/O₃ process was found to be around 3.5 times and 2.5 times faster than sole-UV and ozone-alone, respectively. Experimental results also indicate overall rate constants increased exponentially with pH above 9.0 while the increase of rate constants with pH below 9 is insignificant in O₃ system. All dominant parameters involved in the three processes were determined in the assistant of proposed linear models in this study. The approach was found useful in predicting the process performances through the quantification of quantum yield (rate constant for the formation of free radical HOO⁻ from ozone decomposition at high pH), rate constant of linuron with ozone (k_O3,LNR), rate constant of linuron with hydroxyl radical (k_OH,LNR), and α (the ratio of the production rate of OH and the decay rate of ozone in UV/O₃ system).     

Surface solar ultraviolet radiation: A theoretical approach of the SUVR reaching the ground in Athens, Greece

Daily total ozone observations made during 1985–1993 by both the Total Ozone Mapping Spectrometer (TOMS) flown on the Satellite Nimbus-7 and the Dobson Spectrophotometer have been used in order to investigate the fluctuations of the daily broad-band and spectral solar ultraviolet radiation reaching the ground. This investigation has been performed by employing a recently developed parametric algorithm for the estimation of the spectral and broad-band solar ultraviolet radiation which takes the total ozone variations into consideration. Total ozone reductions during the summertime from 1985 to 1993 over Athens, Greece (37.6° N, 23.4° E), cause an increase in the ultraviolet irradiance which reaches the ground of 0.54 %, 0.98 %, 2.60 % and 0.79 % per decade for the months of July at 300 nm, 312 nm, 320 nm and UVB (280-320 nm), respectively.     

A new approach to data evaluation in the non-target screening of organic trace substances in water analysis

Non-target screening via high performance liquid chromatography-mass spectrometry (HPLC-MS) has gained increasingly in importance for monitoring organic trace substances in water resources targeted for the production of drinking water. In this article a new approach for evaluating the data from non-target HPLC-MS screening in water is introduced and its advantages are demonstrated using the supply of drinking water as an example. The crucial difference between this and other approaches is the comparison of samples based on compounds (features) determined by their full scan data. In so doing, we take advantage of the temporal, spatial, or process-based relationships among the samples by applying the set operators, UNION, INTERSECT, and COMPLEMENT to the features of each sample. This approach regards all compounds, detectable by the used analytical method. That is the fundamental meaning of non-target screening, which includes all analytical information from the applied technique for further data evaluation. In the given example, in just one step, all detected features (1729) of a landfill leachate sample could be examined for their relevant influences on water purification respectively drinking water. This study shows that 1721 out of 1729 features were not relevant for the water purification. Only eight features could be determined in the untreated water and three of them were found in the final drinking water after ozonation. In so doing, it was possible to identify 1-adamantylamine as contamination of the landfill in the drinking water at a concentration in the range of 20 ng L⁻¹. To support the identification of relevant compounds and their transformation products, the DAIOS database (Database-Assisted Identification of Organic Substances) was used. This database concept includes some functions such as product ion search to increase the efficiency of the database query after the screening. To identify related transformation products the database function “transformation tree” was used.     

A biology-based dynamic approach for the reconciliation of acute and chronic toxicity tests: application to Daphnia magna

There is the need to integrate existing toxicity data in a coherent framework for extending their domain of applicability as well as their extrapolation potential. This integration would also reduce time and cost-consuming aspects of these tests and reduce animal usage. In this work, based on data extracted from literature, we have assessed the advantages that a dynamic biology-toxicant fate coupled model for Daphnia magna could provide when assessing toxicity data, in particular, the possibility to obtain from short-term (acute) toxicity test long-term (chronic) toxicity values taking into account the inherent variability of D. magna populations and the multiple sources of data. The results show that this approach overcomes some of the limitations of existing toxicity tests and that the prediction errors are considerably reduced when compared with the factor from 2 to 5 obtained using acute-to-chronic ratios.