The dissolution of benzene, toluene, m-xylene and naphthalene from a residually trapped non-aqueous phase liquid under mass transfer limited conditions

The results of dissolution experiments for benzene, toluene, m-xylene and naphthalene (BTXN) from a relatively insoluble oil phase (tridecane), residually trapped in a non-sorbing porous medium, are described. This mixture was chosen to simulate dissolution of soluble aromatic compounds from a petroleum hydrocarbon mixture, e.g., crude oil, for which a large fraction of the mixture is relatively insoluble. The experiments were carried out at a small source length to interstitial velocity ratio, L/v, so that dissolution would be mass transfer limited (MTL). When fitted to data for toluene, a multiregion mass transfer model was found to predict the experimental data satisfactorily for the other components without adjustment of the mass transfer rate parameters. These results indicate that the dissolution process can be generalized for various hydrophobic organic compounds present in a multicomponent non-aqueous phase liquid (NAPL) when mass transfer limitations are present. This also suggests that dissolution data obtained for one compound can be useful for predicting the dissolution histories for other compounds from petroleum hydrocarbon mixtures.     

Assessing tungsten transport in the vadose zone: from dissolution studies to soil columns

This study investigates the dissolution, sorption, leachability, and plant uptake of tungsten and alloying metals from canister round munitions in the presence of model, well characterized soils. The source of tungsten was canister round munitions, composed mainly of tungsten (95%) with iron and nickel making up the remaining fraction. Three soils were chosen for the lysimeter studies while four model soils were selected for the adsorption studies. Lysimeter soils were representatives of the typical range of soils across the continental USA; muck-peat, clay-loamy and sandy-quartzose soil. Adsorption equilibrium data on the four model soils were modeled with Langmuir and linear isotherms and the model parameters were obtained. The adsorption affinity of soils for tungsten follows the order: Pahokee peat > kaolinite > montmorillonite > illite. A canister round munition dissolution study was also performed. After 24 d, the measured dissolved concentrations were: 61.97, 3.56, 15.83 mg L⁻¹ for tungsten, iron and nickel, respectively. Lysimeter transport studies show muck peat and sandy quartzose soils having higher tungsten concentration, up to 150 mg kg⁻¹ in the upper layers of the lysimeters and a sharp decline with depth suggesting strong retardation processes along the soil profile. The concentrations of tungsten, iron and nickel in soil lysimeter effluents were very low in terms of posing any environmental concern; although no regulatory limits have been established for tungsten in natural waters. The substantial uptake of tungsten and nickel by ryegrass after 120 d of exposure to soils containing canister round munition suggests the possibility of tungsten and nickel entering the food chain.     

Mass flux from a non-aqueous phase liquid pool considering spontaneous expansion of a discontinuous gas phase

The partitioning of non-aqueous phase liquid (NAPL) compounds to a discontinuous gas phase results in the repeated spontaneous expansion, snap-off, and vertical mobilization of the gas phase. This mechanism has the potential to significantly affect the mass transfer processes that control the dissolution of NAPL pools by increasing the vertical transport of NAPL mass and increasing the total mass transfer rate from the surface of the pool. The extent to which this mechanism affects mass transfer from a NAPL pool depends on the rate of expansion and the mass of NAPL compound in the gas phase. This study used well-controlled bench-scale experiments under no-flow conditions to quantify for the first time the expansion of a discontinuous gas phase in the presence of NAPL. Air bubbles placed in glass vials containing NAPL increased significantly in volume, from a radius of 1.0 mm to 2.0 mm over 215 days in the presence of tetrachloroethene (PCE), and from a radius of 1.2 mm to 2.3 mm over 22 days in the presence of trans-1,2-dichloroethene (tDCE). A one-dimensional mass transfer model, fit to the experimental data, showed that this expansion could result in a mass flux from the NAPL pool that was similar in magnitude to the mass flux expected for the dissolution of a NAPL pool in a two-fluid (NAPL and water) system. Conditions favouring the significant effect of a discontinuous gas phase on mass transfer were identified as groundwater velocities less than ~0.01 m/day, and a gas phase that covers greater than ~10% of the pool surface area and is located within ~0.01 m of the pool surface. Under these conditions the mass transfer via a discontinuous gas phase is expected to affect, for example, efforts to locate NAPL source zones using aqueous concentration data, and predict the lifetime and risk associated with NAPL source zones in a way that is not currently included in the common conceptual models used to assess NAPL-contaminated sites.     

The influence of hot particle contamination on Sr and Cs transfers to milk and on time-integrated ingestion doses

Most models for transfers of radionuclides through the food chain typically assume that the radioactivity is initially deposited in chemically available forms. It is known, however, that releases of radionuclides in the form of hot particles may significantly influence their environmental transfers and uptake to the food chain. This study presents models for time changes in ⁹⁰Sr and ¹³⁷Cs in milk which incorporate hot particle contamination using observed rates of hot particle dissolution following the Chernobyl accident. A general equation is presented for the influence of hot particles on overall ingestion doses. As expected from previous work, fallout of hot particles significantly influences time changes in radionuclide activity concentrations in foodstuffs. It is also shown that incorporation of radionuclides in hot particles influences time-integrated ingestion doses. For a situation in which a large proportion (90–100%) of fallout is in slowly dissolving hot particles, time-integrated ingestion doses from ⁹⁰Sr and ¹³⁷Cs are reduced by a factor of approximately two compared to the case where all radioactivity is deposited in bioavailable forms. However, the influence of rapidly dissolving hot particles on time-integrated ingestion doses is relatively minor. Remaining significant uncertainties in dose estimates are discussed.     

DNAPL source depletion: linking architecture and flux response

The relationship between dense non-aqueous phase liquid (DNAPL) mass reduction and contaminant mass flux was investigated experimentally in four model source zones. The flow cell design for the experiments featured a segmented extraction well that allowed for analysis of spatially resolved flux information. This flux information was coupled with image analysis of the NAPL spatial distribution to investigate the relationship between flux and the up-gradient NAPL architecture. Results indicate that in the systems studied, the relationship between DNAPL mass reduction and contaminant mass flux was primarily controlled by the NAPL architecture. A specific definition of NAPL architecture was employed where the source zone is resolved into a collection of streamtubes with spatial variability in NAPL saturation along each streamtube integrated and transformed into an effective NAPL content for each streamtube. The distribution of NAPL contents among the streamtubes (NAPL architecture) controlled dissolution dynamics. Two simplified models, a streamtube model and an effective Damkohler number model, were investigated for their ability to simulate dissolution dynamics.     

Dissolution kinetics of high explosives particles in a saturated sandy soil

Solid phase high explosive (HE) residues from munitions detonation may be a persistent source of soil and groundwater contamination at military training ranges. Saturated soil column tests were conducted to observe the dissolution behavior of individual components (RDX, HMX, and TNT) from two HE formulations (Comp B and C4). HE particles dissolved readily, with higher velocities yielding higher dissolution rates, higher mass transfer coefficients, and lower effluent concentrations. Effluent concentrations were below solubility limits for all components at superficial velocities of 10-50 cm day(-1). Under continuous flow at 50 cm day(-1), RDX dissolution rates from Comp B and C4 were 34.6 and 97.6 microg h(-1) cm(-2) (based on initial RDX surface area), respectively, significantly lower than previously reported dissolution rates. Cycling between flow and no-flow conditions had a small effect on the dissolution rates and effluent concentrations; however, TNT dissolution from Comp B was enhanced under intermittent-flow conditions. A model that includes advection, dispersion, and film transfer resistance was developed to estimate the steady-state effluent concentrations.     

Water chemistry influences on long-term dissolution kinetics of CdSe/ZnS quantum dots

Widespread usage of engineered metallic quantum dots(QDs) within consumer products has evoked a need to assess their fate within environmental systems.QDs are mixed-metal nanocrystals that often include Cd~(2+)which poses a health risk as a nanocrystal or when leached into water.The goal of this work is to study the long-term metal cation leaching behavior and the factors affecting the dissolution processes of mercaptopropionic acid(MPA) capped CdSe/ZnS QDs in aphotic conditions.QD suspensions were prepared in different water conditions,and release of Zn2+and Cd~(2+) cations were monitored over time by size exclusion chromatography-inductively coupled plasm a-mass spectrometry.In most conditions with dissolved 02 present,the ZnS shell degraded fairly rapidly over～1 week,while some of the CdSe core remained up to 80 days.Additional MPA,Zn~(2+),and Cd2+temporarily delayed dissolution,indicating a moderate role for capping agent detachment and mineral solubility.The presence of H_2 O_2 and the ligand ethylenediaminetetraacetate accelerated dissolution,while NOM had no kinetic effect.No dissolution of CdSe core was observed when 02 was absent or when QDs formed aggregates at higher concentrations with 02 present.The shrinking particle model with product layer diffusion control best describes Zn2+and Cd~(2+) dissolution kinetics.The longevity of QDs in their nanocrystal form appears to be partly controlled by environmental conditions,with anoxic,aphotic environments preserving the core mineral phase,and oxidants or complexing ligands promoting shell and core mineral dissolution.     

DNAPL remediation with in situ chemical oxidation using potassium permanganate. II. Increasing removal efficiency by dissolving Mn oxide precipitates

In situ chemical oxidation (ISCO) schemes using MnO4- have been effective in destroying chlorinated organic solvents dissolved in ground water. Laboratory experiments and field pilot tests reveal that the precipitation of Mn oxide, one of the reaction products, causes a reduction of permeability, which can lead to flow bypassing and inefficiency of the scheme. Without a solution to this problem of plugging, it is difficult to remove DNAPL from the subsurface completely. In a companion paper, we showed with batch experiments that Mn oxide can be dissolved rapidly with certain organic acids. This study utilizes 2-D flow-tank experiments to examine the possibility of nearly complete DNAPL removal by ISCO with MnO4-, when organic acids are used to remove Mn oxide. The experiments were conducted in a small 2-D glass flow tank containing a lenticular silica-sand medium. Blue-dyed trichloroethylene (TCE) provided residual, the perched and pooled DNAPL. KMnO4 at 200 mg/l was flushed through the DNAPL horizontally. Once plugging reduced permeability and prevented further delivery of the oxidant, citric or oxalic acids were pumped into the flow tank to dissolve the Mn oxide precipitates. Organic ligands removed the Mn oxide precipitates relatively quickly, and permitted another cycle of MnO4- flooding. Cycles of MnO4-/acid flooding continued until all of the visible DNAPL was removed. The experiments were monitored with chemical analysis and visualization. A mass-balance calculation indicated that by the end of the experiments, all the DNAPL was removed. The results show also how heterogeneity adds complexity to initial redistribution of DNAPL, and to the efficiency of the chemical flooding.     

Fuel particles in the Chernobyl cooling pond: current state and prediction for remediation options

During the coming years, a management and remediation strategy for the Chernobyl cooling pond (CP) will be implemented. Remediation options include a controlled reduction in surface water level of the cooling pond and stabilisation of exposed sediments. In terrestrial soils, fuel particles deposited during the Chernobyl accident have now almost completely disintegrated. However, in the CP sediments the majority of ⁹⁰Sr activity is still in the form of fuel particles. Due to the low dissolved oxygen concentration and high pH, dissolution of fuel particles in the CP sediments is significantly slower than in soils. After the planned cessation of water pumping from the Pripyat River to the Pond, significant areas of sediments will be drained and exposed to the air. This will significantly enhance the dissolution rate and, correspondingly, the mobility and bioavailability of radionuclides will increase with time. The rate of acidification of exposed bottom sediments was predicted on the basis of acidification of similar soils after liming. Using empirical equations relating the fuel particle dissolution rate to soil and sediment pH allowed prediction of fuel particle dissolution and ⁹⁰Sr mobilisation for different remediation scenarios. It is shown that in exposed sediments, fuel particles will be almost completely dissolved in 15–25 years, while in parts of the cooling pond which remain flooded, fuel particle dissolution will take about a century.