Environmental applications of nanoparticles (NP) increasingly result in widespread NP distribution within porous media where they are subject to various concurrent transport mechanisms including irreversible deposition, attachment/detachment (equilibrium or kinetic), agglomeration, physical straining, site-blocking, ripening, and size exclusion. Fundamental research in NP transport is typically conducted at small scale, and theoretical mechanistic modeling of particle transport in porous media faces challenges when considering the simultaneous effects of transport mechanisms. Continuum modeling approaches, in contrast, are scalable across various scales ranging from column experiments to aquifer. They have also been able to successfully describe the simultaneous occurrence of various transport mechanisms of NP in porous media such as blocking/straining or agglomeration/deposition/detachment. However, the diversity of model equations developed by different authors and the lack of effective approaches for their validation present obstacles to the successful robust application of these models for describing or predicting NP transport phenomena. This review aims to describe consistently all the important NP transport mechanisms along with their representative mathematical continuum models as found in the current scientific literature. Detailed characterizations of each transport phenomenon in regards to their manifestation in the column experiment outcomes, i.e., breakthrough curve (BTC) and residual concentration profile (RCP), are presented to facilitate future interpretations of BTCs and RCPs. The review highlights two NP transport mechanisms, agglomeration and size exclusion, which are potentially of great importance in controlling the fate and transport of NP in the subsurface media yet have been widely neglected in many existing modeling studies. A critical limitation of the continuum modeling approach is the number of parameters used upon application to larger scales and when a series of transport mechanisms are involved. We investigate the use of simplifying assumptions, such as the equilibrium assumption, in modeling the attachment/detachment mechanisms within a continuum modelling framework. While acknowledging criticisms about the use of this assumption for NP deposition on a mechanistic (process) basis, we found that its use as a description of dynamic deposition behavior in a continuum model yields broadly similar results to those arising from a kinetic model. Furthermore, we show that in two dimensional (2-D) continuum models the modeling efficiency based on the Akaike information criterion (AIC) is enhanced for equilibrium vs kinetic with no significant reduction in model performance. This is because fewer parameters are needed for the equilibrium model compared to the kinetic model. Two major transport regimes are identified in the transport of NP within porous media. The first regime is characterized by higher particle-surface attachment affinity than particle-particle attachment affinity, and operat...

SummaryWe demonstrate a novel experimental arrangement for measuring wind turbulence-induced gas transport in dry porous media under controlled conditions. This equipment was applied to assess the effect of wind turbulence on gas transport (quantified as a dispersion coefficient) as a function of distance to the surface of the porous medium exposed to wind. Two different strategies for the measurement of wind-induced gas transport were compared. Experiments were carried out with O 2 and CO 2 as tracer gases with average vertical wind speeds of 0.02-1.06 m s −1 . Oxygen breakthrough curves as a function of distance to the wind-exposed surface of the porous medium were analysed numerically with a finite-difference-based model to assess gas transport. We showed that wind turbulence-induced gas transport is an important transport mechanism that can be 20-70 times larger than molecular diffusion-induced transport. Wind conditions and properties of the porous medium had strong controlling effects on this relationship. Importantly, we show that even though wind-induced gas transport is greatest near to the wind-exposed surface, it can have marked effects on the variation in gas concentration at much greater depths. Highlights• We explored the effect of atmospheric wind turbulence on gas transport in porous media.• We measured the depth relation of wind-induced dispersion in porous media for real wind conditions.• Wind-induced gas dispersion coefficients were 20-70 times larger than molecular diffusion.• Wind turbulence can potentially have a considerable effect on gas transport in porous media.

Irvine-Fynn, T. D. L., Bridge, J. W., Hodson, A. J. (2011). In situ quantification of supraglacial cryoconite morphodynamics using time-lapse imaging: an example from Svalbard. Journal of Glaciology, 57 (204), 651-657.There is growing recognition of the significance of biologically active supraglacial dust (cryoconite) for glacial mass balance and ecology. Nonetheless, the processes controlling the distribution, transport and fate of cryoconite particles in the glacial system remain somewhat poorly understood. Here, using a 216 hour time series of plot-scale (0.04 m2) images, we quantify the small-scale dynamics of cryoconite on Longyearbreen, Svalbard. We show significant fluctuations in the apparent cryoconite area and dispersion of cryoconite over the plot, within the 9 day period of observations. However, the net movement of cryoconite across the ice surface averaged only 5.3 mm d?1. High-resolution measurements of cryoconite granule motion showed constant, random motion but weak correlation with meteorological forcing factors and no directional trends for individual particle movement. The high-resolution time-series data suggest that there is no significant net transport of dispersed cryoconite material across glacier surfaces. The areal coverage and motion of particles within and between cryoconite holes appears to be a product of differential melting leading to changes in plot-scale microtopography, local meltwater flow dynamics and weather-dependent events. These subtle processes of cryoconite redistribution may be significant for supraglacial albedo and have bearing on the surface energy balance at the glacier scale.Peer reviewe

We demonstrate noninvasive quantitative imaging of colloid and solute transport at millimeter to decimeter (meso-) scale. Ultraviolet (UV) excited fluorescent solute and colloid tracers were independently measured simultaneously during co-advection through saturated quartz sand. Pulse-input experiments were conducted at constant flow rates and ionic strengths 10(-3), 10(-2) and 10(-1) M NaCl. Tracers were 1.9 microm carboxylate latex microspheres and disodium fluorescein. Spatial moments analysis was used to quantify relative changes in mass distribution of the colloid and solute tracers over time. The solute advected through the sand at a constant velocity proportional to flow rate and was described well by a conservative transport model (CXTFIT). In unfavorable deposition conditions increasing ionic strength produced significant reduction in colloid center of mass transport velocity over time. Velocity trends correlated with the increasing fraction of colloid mass retained along the flowpath. Attachment efficiencies (defined by colloid filtration theory) calculated from nondestructive retained mass data were 0.013 +/- 0.03, 0.09 +/- 0.02, and 0.22 +/- 0.05 at 10(-3), 10(-2), and 10(-1) M ionic strength, respectively, which compared well with previously published data from breakthrough curves and destructive sampling. Mesoscale imaging of colloid mass dynamics can quantify key deposition and transport parameters based on noninvasive, nondestructive, spatially high-resolution data.

Despite aggregation's crucial role in controlling the environmental fate of nanoparticles (NP), the extent to which current models can describe the progressive stages of NP aggregation/sedimentation is still unclear. In this paper, 24 model combinations of two population-balance models and various collision frequency and settling velocity models are used to analyze spatiotemporal variations in the size and concentration of hydroxyapatite (HAp) NP. The impact of initial conditions and variability in attachment efficiency, α, with aggregate size are investigated. Although permeability models perform well in calculating collision frequencies, they are not appropriate for describing settling velocity because of their negative correlation or insensitivity in respect to fractal dimension. Considering both early and late stages of aggregation, both experimental and model data indicate overall mass removal peaks at an intermediate ionic strength (5 mM CaCl) even though the mean aggregate size continued to increase through higher ionic strengths (to 10 mM CaCl). This trend was consistent when different approaches to the initial particle size distribution were used and when a variable or constant α was used. These results point to the importance of accurately considering different stages of aggregation in modeling NP fate within various environmental conditions.