In recent years there has been growing environmental concern regarding ‘microplastics’: microscopic plastic granules, fibres and fragments, categorised as <1 or <5 mm diameter. Microplastics are manufactured to be of a microscopic size, or derive from the photo- and mechanical degradation and subsequent fragmentation of larger plastic litter. Microplastics debris has been identified in the water column and sediments of marine and freshwater ecosystems across the globe, although difficulties in sampling and isolating smaller particulates has resulted in the abundance of <333 µm microplastics being under-reported. Microplastics are bioavailable to a range of aquatic organisms, including fish, seabirds and benthic invertebrates, and can be trophically transferred. The consumption of plastic debris can result in gut blockages, heightened immune response and a loss of lipid reserves. The potential risk to food security, and thereby human health, has led regulators to call for better understanding of the fate and effects of microplastic debris on marine life. Here I tested the hypothesis that microplastics can be ingested by and may negatively impact upon zooplankton. Zooplankton encompass a range of aquatic animals that form a key trophic link between primary producers and the rest of the marine food web. I used a suite of feeding experiments, bio-imaging techniques and ecotoxicological studies to explore the interactions and impacts of polystyrene microplastics on marine zooplankton. My results demonstrate that a range of filter-feeding zooplankton taxa, including copepods and bivalve and decapod larvae, have the capacity to ingest microplastics. Microplastics significantly reduced algal feeding in the copepods Centropages typicus and Calanus helgolandicus. With prolonged microplastic exposure C. helgolandicus produced smaller eggs with reduced hatching success, and had reduced survival owing to declining energetic reserves. Microplastics egested by copepods significantly altered the properties and sinking rates of faecal pellets, with potential repercussions for marine nutrient flux. This investigative work highlights that microplastics pose a significant risk to the health of animals at the base of the marine food web.

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Experiments exploring transport and bio-containment of contaminants in fractured rock were completed using fractured-limestone samples obtained in eastern Ontario, Canada. Three single-fracture samples, a fracture-intersection sample and a fracture-network sample were set into vertical flow systems. Three phases of experiments focused on the transport and hydraulic properties of each sample, the effects of biobarriers on diffusion processes in fracture rock, and methods of improving biobarrier stability and survivability. Hydraulic apertures were determined from constant-flow measurements and transport properties were interpreted from Lissamine and KBr tracer experiments with velocities of up to 8500 m/d for all five samples. At Re > 16, linear to non-linear transitions were observed in enlarged single fracture A and the fracture intersection samples. Reversible increases in aperture were observed at Reynolds numbers (Re) of 7, 4, and 3 for single fractures A and B, and the fracture-network, respectively. Non-linear effects were not observed in these samples over the range of velocities studied (up to Re = 20). Results from the 1-D analytical transport model overestimated values of matrix porosity, suggesting that diffusion from dead zones and slow-flowing regions are also contributing to observed breakthrough curves. Methods of improving biobarrier stability in fractured rock were studied in two single-fracture samples and the fracture-network sample by stimulating naturally-occurring groundwater bacteria. Survivability was improved with successive cycles of feeding and starving and stimulating growth at lower temperatures. Modeled values of matrix porosity decreased by up to 50%, indicating that diffusion processes are strongly influenced by biofilm development. Back diffusion of Lissamine was measured using one single-fracture sample and the fracture-intersection sample. Lissamine was allowed to diffuse into the matrix of each sample and, following a suitable loading period, the back-diffusion of residual Lissamine concentrations were measured from the outflow. This was done in the presence and absence of biofilm, and following the introduction of biofilm onto the fracture surfaces, diffusion was no longer a governing process affecting transport and only advective transport was observed. Experiments were interpreted using a 3-D finite difference model with a three-layer porosity approach, and indicated a decrease in aperture and porosity following biostimulation. / Thesis (Ph.D, Civil Engineering) -- Queen's University, 2012-11-22 11:23:24.065

The purpose of this project is to gain an improved understanding of the transformations that occur in the subsurface downstream of on-site wastewater disposal systems and septic systems. These systems are used widely throughout the United States to treat and discharge wastewater effluent. The approach involved the collection of samples from a septic research center in Cape Cod, MA, and analysis of these samples for nitrogen, phosphorus, dissolved oxygen, pH, alkalinity, suspended solids, metals, and other water quality parameters. Inverse modeling was used to compare samples collected upstream and downstream of subsurface “leaching” fields consisting of sand beds. This approach provided a basis to identify key reactions occurring in the subsurface downstream of the discharge. In addition, a reactive transport software package, based on the PHREEQC and Hydrus-1d models, was used to model the transport in these sand beds and identify possible reactions and changes in contaminant concentrations with depth. To understand the implications of the discharges, an additional field study was completed in an area where septic systems have impacts on surface waters. Samples collected from a stream provided an indication of the loads entering the stream as a result of septic system discharges. Combining the results from the modeling with the results of this field investigation provided an approach to estimate the transport of nutrients and other contaminants entering the surface waters from septic system discharges. The results provide a basis for understanding the impacts of septic systems on surface waters, and develop better approaches for reducing the impacts of these discharges.

Research Doctorate - Doctor of Philosophy (PhD) / Consolidation of clayey contaminant barriers, such as are employed as landfill liners, has been postulated as a cause of accelerated transit of contaminants and hence their earlier than expected appearance in secondary leachate. This proposition is theoretically investigated in this thesis using a novel large-deformation, one-dimensional continuum model of coupled mechanical consolidation and solute transport. The model is a generalization of existing coupled consolidation and solute transport models described in the literature. It takes into account both non-linearities in geometry as well as material constitutive relations. The latter relate the compressibility, hydraulic conductivity and effective diffusion coefficient to the deformation of the soil. In addition to providing details of the governing equations and constitutive relations, a detailed derivation of the three classical one-dimensional consolidation boundary conditions, i.e. undrained top and drained bottom, drained top and undrained bottom, drained top and bottom is also given. From the continuum model formulation, a numerical model was developed using proprietary finite element software – FEMLAB 2.3. The numerical model is verified by comparing results with those produced from other recently developed consolidation – transport models. In the course of conducting these comparisons, some results from a recent modelling investigation indicating that a twenty-fold reduction in the transit time of contaminants across a composite soil – geomembrane barrier may be possible were re-examined. This comparison reveals some apparent errors in the original analysis and indicates that the predicted large acceleration of contaminant transport induced by consolidation is probably unrealistic. The model is subsequently applied to a case study of a clay liner and geomembrane system. Results obtained are compared with those from various simplified models, including a “diffusion-only” (i.e. a rigid soil) model traditionally used in contaminant barrier design. For barriers incorporating low compressibility soils (such as well compacted clays), there is little difference between contaminant transit times predicted by the two models. However, for contaminant barriers incorporating more compressible soils, consolidation is shown to be capable of accelerating transport. These results indicate the potential importance of accounting for the effects of soil consolidation and they highlight some limitations of existing models when modelling solute transport through composite barriers utilizing soft soils. Based on these limited results, a way of taking into account soil consolidation using simplified models is suggested. In the penultimate chapter of this thesis, an extensive parametric sensitivity analysis of coupled consolidation and solute transport in composite contaminant barrier systems is presented. The analysis incorporates results of more than 3000 simulations for various combinations of barrier thickness, waste loading rate, initial void ratio, compression index, hydraulic conductivity and dispersion coefficient. Results are succinctly presented using dimensionless plots, which allow the comparison of results for a large number of parameter values, and hence, the clear identification of the most important factors affecting contaminant transport through a consolidating composite barrier system. The results demonstrate that there exists a pessimum rate of consolidation for which the contaminant transit time is minimised. In cases of extremely high barrier compressibility it is shown that an order of magnitude reduction in contaminant transit time may arise due to coupling between solute transport and consolidation. For barriers of low compressibility and porosity, such as well-engineered composite compacted clay landfill liners, it is found that the contaminant transit time is far less affected, though it may still be reduced by up to 30%. In general, the results suggest that the use of a coupled consolidation–contaminant transport model may be required for informed and conservative contamiant barrier design, especially if relatively compressible earthen components are utilised.

Contamination of soils by munitions constituents is pervasive on Department of Defense operational ranges. Low-order detonations result in the heterogeneous distribution of explosives residues (ER) at shallow depths. At a limited number of ranges ER contamination of groundwater has been observed. Previous studies have shown that the downward migration of colloid-sized contaminants can significantly impact groundwater quality. The goal of this study was to investigate if colloid transport plays a role in the migration of ER contaminants. Our primary objective was to determine the transport potential of fine (<5>um) ER particles under ideal conditions for colloid transport. A secondary objective was to develop a direct detection method for the identification and quantitative analysis of particulate ER. A series of saturated transport experiments were conducted in columns (2x20 cm) packed with clean sand. 2,6- Dinitrotoluene was used as a surrogate for explosives chemicals. Experiments were conducted with both particulate and dissolved-phase DNT. Bromide and microspheres tracers were also used to characterize nonreactive transport. Particulate tracers were applied to the columns, either suspended in the influent solution, or directly to the top layer of sand, in order to more realistically replicate field conditions. Experimental results indicate that DNT movement through the columns occurred as a combination of solid and dissolved phase transport. Concentration differences between unfiltered and filtered samples indicate that particulate DNT accounted up to 30% of the total mass recovered in the effluent.

Mobilization of colloidal particulate matter (most important, clay particles) from a soil matrix in the subsurface environment is an important environmental process. As many contaminants tend to adsorb onto various colloidal mineral particles, co-transport of contaminants in association with mobilized particles could contribute significantly to the migration of these contaminants in the environment. Numerous studies have observed the effects of pH on colloid mobilization but have overlooked the possible direct role of acidity. This study looked at the role of acidity with H⁺ as a chemical agent. Through cyclic elution of a natural sand column with a weak acid and base solution, there was an increase in mobilized clay colloids. It was found that low concentrations of organic acids could assist in detaching surface clays through lysing of labile Ca²⁺ and Mg²⁺ ions. The H⁺ ions sever the chemical bonds between the grain surface and the colloidal surface by being substituted for the interstitial Ca and Mg ions. This substitution has been found to release over 1 kg of surface clay per 1 mole of H⁺ consumed. It was postulated that pH oscillation addition to proton dynamics could play a major role in subsurface colloid transport. The results from this study could help improve predicting of subsurface contaminant fronts and aid in managing contaminant transport in the soil water environments.

Semiconductor wafer manufacturing facilities (fab) must maintain extremely clean air environments to minimize the number of wafers scrapped due to contamination which would result in reduced yields. The fab air is cleaned bypassing it through either HEPA or ULPA filters. A number of airborne fab contaminants may be hygroscopic causing them to exist as a solid or a liquid when in equilibrium with their environment's relative humidity. The effect of relative humidity on such contaminants is poorly documented whether they were to be captured in a filter or deposited on a wafer. The work presented here experimentally characterizes NaCl evolution within HEPA filters when exposed to humidity fluctuations and the effect of humidity on NH4Cl corrosiveness when deposited on cobalt coated wafers with a TiN layer. Successive deliquescence and efflorescence fluctuations were imposed on particles captured on a glass fiber HEPA filter. Scanning Electron Microscopy (SEM) and Environmental SEM (ESEM) studies of the filters showed that the NaCl, under humidity excursions, did not penetrate deep into the filter but deliquesced and effloresced near the top surface of the filter. Pressure drop measurements for filters containing NaCl particles showed differences in pressure drop associated with relative humidity changes. These pressure drop changes suggested some redistribution particle properties. When exposed to a relative humidity of 20%, the NH4Cl particles did not corrode the cobalt wafer beyond the location of the initial deposit. At 61% relative humidity, the surrounding areas of the particles were corroded with a solid artifact left at the original location. At 76% relative humidity the NH4Cl particles were observed to have deliquesced, which is below the expected deliquescence relative humidity. The corrosion of the cobalt wafer was most extensive when the NH4Cl particles had deliquesced. / text

Multicomponent nonaqueous phase liquids (NAPL) contaminating the subsurface can significantly inhibit remediation. One method of enhancing the rate of remediation of NAPL constituents, compared to pump-and-treat, involves source zone treatment with enhanced solubilization agents (ESAs) including cyclodextrins. Equilibrium cyclodextrin enhanced solubilization of simple 1, 2, and 3 component NAPL mixtures was examined to evaluate the applicability of Raoult's Law. The results suggest that Raoult's Law may be used to estimate equilibrium and early-time dynamic concentrations in contact with ideal NAPL mixtures, and Raoult's Law may be used to estimate cyclodextrin enhanced groundwater concentrations for ideal NAPL mixtures. Solubility enhancement of NAPL compounds was dependent on the cyclodextrin concentration and independent of NAPL composition. Column experiments and numerical modeling were used to evaluate the dissolution behavior of the NAPL mixtures in water and a cyclodextrin solution to estimate mass transfer rates. The aqueous multicomponent dissolution followed Raoult's Law, and the model-estimated lumped rate coefficients were independent of the NAPL composition. Addition of the cyclodextrin enhanced the dissolution and removal of compounds from residual NAPL due to an increase in the driving force (i.e. concentration gradient) and the mass transfer coefficient. The model results suggest that Raoult's Law is applicable for ideal NAPL mixture dissolution in water, but potential nonideality was observed and caused the model simulation to deviate from the dissolution behavior for NAPL mixture cyclodextrin experiments. The cyclodextrin dissolution experiments were less rate-limited than aqueous dissolution, and the mass transfer coefficients were quantified with the model. The results of the model suggest that NAPL mixture nonideality and intra-NAPL diffusion may also impact enhanced dissolution behavior. Additionally, the importance of NAPL mixture characterization was illustrated by evaluation of a mixture of PCE (tetrachloroethene) and diesel fuel collected from a site in Tucson, Arizona. A sample from the site was used to create mixtures with increasing PCE in the NAPL. Chemical evaluation of the complex NAPL was conducted, and physical property and phase partitioning testing was performed, which demonstrated the effect of NAPL composition on its distribution, interphase mass transfer, and potential mobilization.

Hydraulic conductivity (K) is a key parameter required for the accurate prediction of contaminant transport in an aquifer. Traditionally, pump tests, slug tests, grain size analysis and, to a lesser extent, tracer tests have been employed to estimate the K of an aquifer. These methods have disadvantages in respect to assessing the K of a contaminated aquifer, for example, pumping tests generate large quantities of potentially contaminated water, slug tests interrogate only a small portion of aquifer to generate K values, and tracer tests are costly to perform. The recirculating well pair (RWP) system, assessed in this study, attempts to minimise these disadvantages while producing accurate estimates of K. The RWP system uses two wells, each screened in two positions; one screen injects water and the other extracts water from the aquifer. One well extracts water from the lower screen and injects it into the aquifer via the upper screen, whereas the second well extracts water from the upper screen and injects it through the lower screen. When these two wells are pumped in tandem a recirculation system is created within the aquifer. No water is lost or gained from the aquifer in this system. Hydraulic conductivity can be estimated from a RWP system by either the multi dipole or the fractional flow methods. The multi dipole method estimates K by measuring steady state hydraulic heads, whereas the fractional flow method uses a tracer test to obtain steady state concentrations at the four screens to estimate K. Both methods utilise a 3D flow model to simulate the aquifer system. Inverse modelling in conjunction with a genetic algorithm simulate the hydraulic head values obtained from the multi dipole experiments or the tracer steady state values obtained from the fractional flow method. Hydraulic ii conductivity estimates are obtained by matching the simulated and observed steady state hydraulic head, or tracer steady state values. An investigation of the accuracy of the two RWP methods, when system parameters are varied, in estimating K values was undertaken. Five multi dipole experiments were undertaken with varying dipole flow rates to assess the effect of altering dipole flow rate on estimates of K. Two experiments were also undertaken to assess the effect of altering the pumping well incidence angle as compared to the regional flow on the accuracy of K estimates. Five fractional flow experiments were conducted, four to assess the effect of changing dipole pumping rates and one to assess the influence of altering the incidence angle of the pumping wells on estimation of K. All experiments were undertaken in an artificial aquifer that allowed control of hydraulic parameters and accurate measurement of aquifer K by independent methods. Experimental results were modelled with the two RWP methods. Results indicate that both the multi dipole and fractional flow methods provide accurate estimates of the K of the artificial aquifer (5 % to 57% greater than the actual K and -14% to 17% of the actual K, respectively). Altering the ratio between the pumping well and regional aquifer flow rates had no effect on the estimated K results in both methods. Although preliminary results were positive, further work needs to be undertaken to determine if changing the orientation of the well pairs affects the estimation of K.