Degassing of H/He, CFCs and SF6 by denitrification: Measurements and two-phase transport simulations

The production of N₂ gas by denitrification may lead to the appearance of a gas phase below the water table prohibiting the conservative transport of tracer gases required for groundwater dating. We used a two-phase flow and transport model (STOMP) to study the reliability of ³H/³He, CFCs and SF₆ as groundwater age tracers under agricultural land where denitrification causes degassing. We were able to reproduce the amount of degassing (R² = 69%), as well as the ³H (R² = 79%) and ³He (R² = 76%) concentrations observed in a ³H/³He data set using simple 2D models. We found that the TDG correction of the ³H/³He age overestimated the control ³He/³He age by 2.1 years, due to the accumulation of ³He in the gas phase. The total uncertainty of degassed ³H/³He ages of 6 years (± 2 σ) is due to the correction of degassed ³He using the TDG method, but also due to the travel time in the unsaturated zone and the diffusion of bomb peak ³He. CFCs appear to be subject to significant degradation in anoxic groundwater and SF₆ is highly susceptible to degassing. We conclude that ³H/³He is the most reliable method to date degassed groundwater and that two-phase flow models such as STOMP are useful tools to assist in the interpretation of degassed groundwater age tracer data.     

A detailed field-based evaluation of naphthenic acid mobility in groundwater

An anaerobic plume of process-affected groundwater was characterized in a shallow sand aquifer adjacent to an oil sands tailings impoundment. Based on biological oxygen demand measurements, the reductive capacity of the plume is considered minimal. Major dissolved components associated with the plume include HCO₃, Na, Cl, SO₄, and naphthenic acids (NAs). Quantitative and qualitative NA analyses were performed on groundwater samples to investigate NA fate and transport in the subsurface. Despite subsurface residence times exceeding 20 years, significant attenuation of NAs by biodegradation was not observed based on screening techniques developed at the time of the investigation. Relative to conservative tracers (i.e., Cl), overall NA attenuation in the subsurface is limited, which is consistent with batch sorption and microcosm studies performed by other authors. Insignificant biological oxygen demand and low concentrations of dissolved As (< 10 µg L^− 1) in the plume suggest that the potential for secondary trace metal release, specifically As, via reductive dissolution reactions driven by ingress of process-affected water is minimal. It is also possible that readily leachable As is not present in significant quantities within the sediments of the study area. Thus, for similar plumes of process-affected groundwater in shallow sand aquifers which may occur as oil sands mining expands, a reasonable expectation is for NA persistence, but minimal trace metal mobilization.     

Potential concerns related to using octadecyltrichlorosilane (OTS) in rendering soils and porous ceramics hydrophobic

The treatment of hydrophilic porous ceramics to render them hydrophobic and wetting to non-aqueous phase liquids (NAPLs) is frequently needed in multiphase flow experiments to control the flow or to measure the pressure of the NAPL. In addition, research dealing with soil wettability implies a need for hydrophobic or NAPL-wet soils. The traditional procedure, which has been widely used in literature, to render hydrophilic porous ceramics and soils hydrophobic is achieved by placing the hydrophilic solid in a 5% (by volume) octadecyltrichlorosilane (OTS) solution in ethanol followed by rinsing in ethanol. This research assesses the use of this procedure as it was found that this treatment procedure resulted in excess OTS on the surface of treated hydrophobic solids which can dissolve in an organic phase and in turn alter the wettability condition of adjacent hydrophilic soils. A modified procedure, which results in hydrophobic solids free of excess OTS, is presented.     

C60 fullerene: a powerful antioxidant or a damaging agent? The importance of an in-depth material characterization prior to toxicity assays

Since the discovery of fullerenes in 1985, these carbon nanospheres have attracted attention regarding their physico/chemical properties. Despite little knowledge about their impact on the environment and human health, the production of fullerenes has already reached an industrial scale. However, the toxicity of C₆₀ is still controversially discussed.The aim of this study was to clarify the biological effects of tetrahydrofuran (THF) suspended C₆₀ fullerene in comparison to water stirred C₆₀ fullerene suspensions. Beyond that, we analyzed the effects on the Crustacea Daphnia magna an indicator for ecotoxicological effects and the human lung epithelial cell line A549 as a simplified model for the respiratory tract.We could demonstrate that water-soluble side products which were formed in THF nC₆₀ suspension were responsible for the observed acute toxic effects, whereas fullerenes themselves had no negative effect regardless of the preparative route on either A549 cell in vitro or D. magna in vivo.     

Development and Use of a Sedimentation Risk Index for Unpaved Road‐Stream Crossings in the Choctawhatchee Watershed1

Abstract: Unpaved road‐stream crossings increase sediment yields in streams and alter channel morphology and stability. Before restoration and sedimentation reduction strategies can be implemented, a priority listing of unpaved road‐stream crossings must be created. The objectives of this study were to develop a sedimentation risk index (SRI) for unpaved road‐stream crossings and to prioritize 125 sites in the Choctawhatchee watershed (southeastern Alabama) using this model. Field surveys involved qualitative and quantitative observations of 73 metrics related to waterway conditions, crossing structures, road approaches, and roadside soil erosion. The road‐stream crossing risk analyses involved elimination of candidate metrics based on redundancy, skewness, lack of data, professional judgment, lack of nonzero values, unbalanced box plots, and limited ranges of values. A final selection of 12 metrics formed the SRI and weighed factors involving soil erodibility, road sedimentation abatement features, and stream morphology alteration. The SRI was organized into narrative categories (excellent, good, fair, poor, and very poor) based on the distribution of scores. No excellent sites (scores ≥55) were found in this study, 17 (20.7%) were good (low sedimentation risk), 37 (45.1%) were fair (moderate sedimentation risk), 26 (31.7%) were poor (high sedimentation risk), and two (2.5%) were very poor (high sedimentation risk). There was no significant difference in SRI scores among crossing structure type (round culverts, box culverts, and bridges) (H = 4.31, df = 2, p = 0.058). A future study of the Choctawhatchee watershed involving the same study sites could assess the success of restoration plans and activities based on site score improvement or decline.     

Modeling the Hydrology of Climate Change in California’s Sierra Nevada for Subwatershed Scale Adaptation1

Young, Charles A., Marisa I. Escobar‐Arias, Martha Fernandes, Brian Joyce, Michael Kiparsky, Jeffrey F. Mount, Vishal K. Mehta, David Purkey, Joshua H. Viers, and David Yates, 2009. Modeling the Hydrology of Climate Change in California’s Sierra Nevada for Subwatershed Scale Adaptation. Journal of the American Water Resources Association (JAWRA) 45(6):1409‐1423. Abstract: The rainfall‐runoff model presented in this study represents the hydrology of 15 major watersheds of the Sierra Nevada in California as the backbone of a planning tool for water resources analysis including climate change studies. Our model implementation documents potential changes in hydrologic metrics such as snowpack and the initiation of snowmelt at a finer resolution than previous studies, in accordance with the needs of watershed‐level planning decisions. Calibration was performed with a sequence of steps focusing sequentially on parameters of land cover, snow accumulation and melt, and water capacity and hydraulic conductivity of soil horizons. An assessment of the calibrated streamflows using goodness of fit statistics indicate that the model robustly represents major features of weekly average flows of the historical 1980‐2001 time series. Runs of the model for climate warming scenarios with fixed increases of 2°C, 4°C, and 6°C for the spatial domain were used to analyze changes in snow accumulation and runoff timing. The results indicated a reduction in snowmelt volume that was largest in the 1,750‐2,750 m elevation range. In addition, the runoff center of mass shifted to earlier dates and this shift was non‐uniformly distributed throughout the Sierra Nevada. Because the hydrologic model presented here is nested within a water resources planning system, future research can focus on the management and adaptation of the water resources system in the context of climate change.     

Assessment Tools for Urban Catchments: Defining Observable Biological Potential1

Abstract: Urbanization represents a strong and increasingly more prevalent impact on stream quality worldwide. One of the characteristic effects of increased urbanization is a consistent decline in biological stream condition. The characterization of this biological degradation with increasing urbanization presents a number of advantages for the study and management of urban streams and catchments. In this paper, the limitation of biological condition with urbanization, called observed biological potential, is characterized. Using an urban intensity index and a biological index developed specifically for urban systems in the Baltimore, Maryland; Cleveland, Ohio; and San Jose, California regions, two principal techniques were compared (quantile regression and bin regression) to define observed biological potential along urban gradients. Quantile regression was selected as the preferable tool for describing observed biological potential given the consistency with which it can be applied and its statistical efficiency, however, bin quantile regression performed similarly. Having identified a numeric approximation of observed biological potential, two methods for identifying factors related to distance from potential as a way of identifying critical environmental factors affecting biological condition in urban areas were explored. The results of this work can be used for identifying benchmarks for urban stream biological condition, identifying limiting catchment characteristics, and prioritizing urban stream management efforts.     

Numerical simulations on the influence of matrix diffusion to carbon sequestration in double porosity fissured aquifers

The double porosity model for fissured rocks, such as limestones and dolomites, has some features that may be relevant for carbon sequestration. Numerical simulations were conducted to study the influence of matrix diffusion on the trapping mechanisms relevant for the long-term fate of CO₂ injected in fissured rocks. The simulations show that, due to molecular diffusion of CO₂ into the rock matrix, dissolution trapping and hydrodynamic trapping are more effective in double porosity aquifers than in an equivalent porous media. Mineral trapping, although assessed indirectly, is also probably more relevant in double porosity aquifers due to the larger contact surface and longer contact time between dissolved CO₂ and rock minerals. However, stratigraphic/structural trapping is less efficient in double porosity media, because at short times CO₂ is stored only in the fissures, requiring large aquifer volumes and increasing the risk associated to the occurrence of imperfections in the cap-rock through which leakage can occur. This increased risk is also a reality when considering storage in aquifers with a regional flow gradient, since the CO₂ free-phase will move faster due to the higher flow velocities in fissured media and discharge zones may be reached sooner.     

De-novo formation of dioxins and furans and the memory effect in waste incineration flue gases

The formation of dioxin (polychlorinated-rho-dibenzodioxins - PCDD) and furan (polychlorinated dibenzofurans - PCDF) in waste incineration flyash in relation to temperature has been investigated in a bench scale reactor. The PCDD/PCDF released into the exhaust gases of the reactor and trapped in a condensation and vapour phase adsorption system were also determined. The concentrations of PCDD/PCDF in the flyash were analysed in detail for all congeners and isomers including the mono-, di- and tri-PCDD/PCDF. De-novo synthesis of PCDD/PCDF was clearly seen in the flyash with large changes in concentrations of PCDD/PCDF with only small changes in temperature. Exhaust gas PCDD/PCDF were detected at all temperatures, with the maximum emission occurring at a flyash temperature of 350 degrees C, where the equivalent of over 42 times the total dioxin/furan concentration of the original flyash was lost to the vapour phase per unit mass of initial flyash. Although the desorbed species were mainly the lower mono- to tri-congener group of dioxins and furans, the desorbed dioxin/furans had a considerable toxic equivalent value.     

Methane generation in tropical landfills: simplified methods and field results

This paper deals with the use of simplified methods to predict methane generation in tropical landfills. Methane recovery data obtained on site as part of a research program being carried out at the Metropolitan Landfill, Salvador, Brazil, is analyzed and used to obtain field methane generation over time. Laboratory data from MSW samples of different ages are presented and discussed; and simplified procedures to estimate the methane generation potential, Lo, and the constant related to the biodegradation rate, k are applied. The first order decay method is used to fit field and laboratory results. It is demonstrated that despite the assumptions and the simplicity of the adopted laboratory procedures, the values Lo and k obtained are very close to those measured in the field, thus making this kind of analysis very attractive for first approach purposes.