Laboratory evidence of natural remobilization of multicomponent DNAPL pools due to dissolution

Mixtures of dense non-aqueous phase liquids (DNAPLs) trapped in the subsurface can act as long-term sources of contamination by dissolving into flowing groundwater. In general, the components of higher solubility are removed more quickly, thus altering the composition of the remaining DNAPL, and possibly leading to changes in its physical properties. Through the development of a simple compositional model, Roy et al. [J. Contam. Hydrol. 2002 (59) 163] showed that preferential dissolution of a mixed DNAPL could potentially result in changes in density and interfacial tension that could subsequently lead to remobilization of an initially static DNAPL pool. The laboratory experiments presented in this next paper provide a proof-of-concept for the previously presented theory, demonstrating and quantifying this process of remobilization. In addition, the experiments provide a data set for evaluation of the model presented by Roy et al. [J. Contam. Hydrol. 2002 (59) 163]. In the four experiments, a DNAPL pool comprised of tetrachloroethene and benzene was created as an open pool overlying glass beads within a water-saturated 2-D flow box. Experiments included rectangular and triangular pools. In each of the experiments, remobilization (as breakthrough) was observed more than 2 weeks after formation of the initial pool. During each experiment, the pool height declined as mass was lost by dissolution, while sampling indicated a decrease in the mole fraction of benzene, the more soluble component. Small protuberances formed along the bottom of the pool as its composition changed with time and the displacement pressure was achieved for various pore throats. Eventually one of the protuberances extended further, forming a finger (breakthrough). In general, the pool emptied as the finger proceeded further into the beads. It was also shown theoretically and experimentally that remobilization will occur sooner for pools with a triangular (pointing down), rather than rectangular, shape. The experimental results were simulated using the model developed by Roy et al. [J. Contam. Hydrol. 2002 (59) 163]. The model matched the observations well, suggesting that it accurately represents the primary mechanisms involved with natural remobilization under the conditions of the study.     

Nonlinearities in source receptor relationships for sulfur and nitrogen compounds

The relationship between emissions and deposition of air pollutants, both spatially and in time forms an important focus for science and for policy makers. In practice, this relationship may become nonlinear if the underlying processes change with time, or in space. Nonlinearities may also appear due to errors in emission or deposition data, and careful scrutiny of both data sources and their relationship provides a means of picking up such deficiencies. Nonlinearities in source receptor relationships for sulfur and nitrogen compounds in Europe have been identified in measurement data for the UK. In the case of sulfur, the dry deposition process has been shown to be strongly influenced by ambient concentrations of NH3, leading to substantial increases in deposition rate as SO2 concentrations decline and the ratio SO2/NH3 decreases. The field evidence extends to measurements over three different surfaces in three countries across Europe. A mechanistic understanding of the cause of this nonlinearity has been provided. Apparent nonlinearities also exist in the sulfur deposition field through the influence of shipping emissions. The effect is clear at west coast locations, where during a period in which land-based sulfur emissions declined by 50%, no significant decline in concentrations of SO(2-) in precipitation were observed. The sites affected are primarily the coastal regions of southwestern UK, where shipping sources contribute a substantial fraction of the deposited sulfur, but the effect is not detectable elsewhere. Full quantification of the spatially disaggregated emission and their changes in time will eliminate this apparent nonlinearity in the source-receptor data. For oxidized nitrogen emission and deposition in the UK, there is strong evidence of nonlinearity in the source-receptor relationship. The concentrations and deposition of NO(3-) in precipitation have declined little following a reduction in emissions of 45% during the period 1987 to 2001. The data imply a significant decrease in the average transport distance for oxidized nitrogen and most probably an increase in the average oxidation rate. However, the net effect of changes in aerosol chemistry due to changes in sulfur emissions and less competition for the main oxidants as a consequence of reductions in sulfur emission have not been separated. A quantitative explanation of the cause of this nonlinearity is lacking and the effects are therefore identified as an important uncertainty for the development of further protocols to control acidification, eutrophication and photochemical oxidants in Europe.     

Colloid-facilitated transport of radionuclides through fractured media

The sorption of radionuclides on natural colloids may significantly modify their transport behaviour through fractured media, since radionuclides bound to colloids may not be subject to the important retardation mechanisms of matrix diffusion and sorption onto pore surfaces. This paper reports on theoretical and experimental work aimed at assessing the relevance of colloid-facilitated transport to repository safety analyses, with specific reference to the Swiss case. Transport models are presented, developed in conjunction with field- and laboratory-based studies of deep groundwater in the crystalline basement of northern Switzerland, in which colloid size distributions, compositions and sorption properties have been measured. Various potential mechanisms giving rise to both reversible and irreversible sorption are discussed. In the first case, a simple approach is examined which is based on previously reported models of colloid transport and assumes reversible, linear sorption on colloids, for which experimental data have been obtained. It is shown that transport of radionuclides would not, in general, be significantly enhanced because of this process. A more recently developed and more complex model is then described incorporating irreversible sorption, in which case the transport of radionuclides tends to be strongly dependent on the extent of colloid-fracture wall interaction.     

Measurement of effective air diffusion coefficients for trichloroethene in undisturbed soil cores

In this study, we measure effective diffusion coefficients for trichloroethene in undisturbed soil samples taken from Picatinny Arsenal, New Jersey. The measured effective diffusion coefficients ranged from 0.0053 to 0.0609 cm2/s over a range of air-filled porosity of 0.23-0.49. The experimental data were compared to several previously published relations that predict diffusion coefficients as a function of air-filled porosity and porosity. A multiple linear regression analysis was developed to determine if a modification of the exponents in Millington's [Science 130 (1959) 100] relation would better fit the experimental data. The literature relations appeared to generally underpredict the effective diffusion coefficient for the soil cores studied in this work. Inclusion of a particle-size distribution parameter, d10, did not significantly improve the fit of the linear regression equation. The effective diffusion coefficient and porosity data were used to recalculate estimates of diffusive flux through the subsurface made in a previous study performed at the field site. It was determined that the method of calculation used in the previous study resulted in an underprediction of diffusive flux from the subsurface. We conclude that although Millington's [Science 130 (1959) 100] relation works well to predict effective diffusion coefficients in homogeneous soils with relatively uniform particle-size distributions, it may be inaccurate for many natural soils with heterogeneous structure and/or non-uniform particle-size distributions.     

Development and demonstration of an explicit lumped-parameter biofilter model and design equation incorporating monod kinetics

Biofiltration is an economical air pollution control (APC) technology, particularly suitable for the treatment of air-streams having high flow rates and low concentrations of volatile organic compounds (VOCs). This technology utilizes enzymatic catalysis at ambient conditions to mineralize such pollutants to CO2, H2O, and salts. A pilot-scale study conducted for more than 4 years investigated the development of a new biofiltration technology employing trickle bed air biofilters (TBABs). Following the completion of this experimental study, additional data analysis was performed to develop a simple lumped-parameter biofilter model, assuming first-order kinetics. This model related the observed biofilter performance to the principle independent physical, thermodynamic, and biochemical parameters. The initial model has subsequently been expanded to incorporate Monod kinetics. In this paper, the development and use of the final explicit lumped-parameter biofilter model and design equation, incorporating Monod kinetics, are presented. To facilitate the application of this model, practical procedures are also presented for the determination of VOC solubility, VOC biokinetic Monod parameters, and the maximum practical biofilter inlet VOC concentration.     

Nutrient losses by surface run-off following the application of organic manures to arable land. 2. Phosphorus

Phosphorus (P) surface run-off losses were studied following organic manure applications to land, utilising a purpose-built facility on a sloping site in Herefordshire under arable tillage. Different rates and timing of cattle slurry, farm yard manure (FYM) and inorganic nitrogen (N) and P fertiliser were compared, over a 4-year period (1993-97). N losses from the same studies are reported in a separate paper. The application of cattle FYM and, especially slurry, to the silty clay loam soil increased both particulate and soluble P loss in surface water flow. Losses via subsurface flow (30 cm interflow) were consistently much lower than via surface water movement and were generally unaffected by treatment. Increased application of slurry solids increased all forms of P loss via surface run-off; the results suggested that a threshold for greatly increased risk of P losses via this route, as for N, occurred at ca. 2.5-3.0 t/ha solids loading. This approximates to the 50 m3/ha application rate limit suggested for slurry within UK 'good agricultural practice'. The studies also provided circumstantial evidence of the sealing of the soil surface by slurry solids as the major mechanism by which polluting surface run-off may occur following slurry application on susceptible soils. Losses of total and soluble P, recorded for each of the 4 years of experiments, reached a maximum of only up to 2 kg/ha total P (TP), even after slurry applications initiating run-off. Whilst these losses are insignificant in agronomic terms, peak concentrations of P (up to 30,000 micrograms/l TP) in surface water during a run-off event, could be of considerable concern in sensitive catchments. Losses of slurry P via surface run-off could make a significant contribution to accelerated eutrophication on entry to enclosed waters, particularly when combined with high concentrations of NO3(-)-N. Restricting slurry application rates to those consistent with good agronomic practice, and within the limits specified in existing guidelines on good agricultural practice, offers the simplest and most effective control measure against this potentially important source of diffuse pollution.     

Changes in soil organic carbon storage under grassland as evidenced by changes in sulphur input-output budgets

Information about temporal changes in soil organic carbon (C) pools may be obtained indirectly from changes in input-output budgets of organically combined nutrients such as sulphur (S). Sulphur budgets were therefore evaluated for Northern Ireland (NI) for the period 1940-1990, inclusive. These budgets indicated that the land or soil had acted first as a sink but then as a source for S, and that reserves of soil S built up between 1940 and 1965 were totally depleted by the mid-1980s. Pooled data from six long-term soil-monitoring sites on undisturbed grassland suggested that negative S budgets from the late-1970s onwards had been due to the net mineralization of soil organic matter and thus were indicative of net losses of organic C from surface soil horizons. There was some evidence that the decline in rainfall and fertiliser S inputs from the mid-1960s may have precipitated the breakdown of soil organic matter.     

Characterization of emissions of dioxins and furans from ethylene dichloride, vinyl chloride monomer and polyvinyl chloride facilities in the United States. Consolidated report

This is the consolidated report of emissions of PCDD/F from facilities in the organic chemical manufacturing chain leading to polyvinyl chloride. Data have been gathered from facilities in the US and Canada from a number of manufacturers and at various steps in the manufacturing process. Estimates of US emissions or transfers of PCDD/F were generated on an "Upper Bound" and "Most Likely" basis. The Most Likely estimate of US emissions of PCDD/F to the open environment, that is, air, water and land surface by facilities in this chain, based on evaluation of non-detects at one-half the detection limit is about 12 g I-TEQ per year. On this same basis, an estimated 19 g is disposed of in secure landfills.