Favorable and unfavorable attachment of colloids in a discrete sandstone fracture.

The transport of cationic amine-modified latex (AML) and anionic carboxylate-modified latex (CML) microspheres through a discrete sandstone fracture with mineralogical heterogeneity and roughness was studied. Two microsphere sizes (200 nm and 1000 nm), two ionic strengths (5 mM and 10 mM), and two specific discharges (0.35 mm.s-1 and 0.70 mm.s-1) were tested to observe the impact on transport under favorable and unfavorable conditions. The difference in retention between AML (net favorable) and CML (net unfavorable) microsphere attachment was 25% for the 200 nm microspheres and 13% for the 1000 nm microspheres. Less than 50% of the AML microspheres were retained in the fracture, postulated to be due to the effects of mineralogical heterogeneity and fracture surface roughness. The effect of an increase in ionic strength in increasing retention was significant for unfavorable attachment, but was not significant for favorable attachment conditions. The effect of specific discharge was minor for all but the 200 nm CML microspheres at 10 mM ionic strength. When flushing the fracture first with cationic microspheres, then with anionic microspheres, the recovery of anionic microspheres resembled favorable attachment presumably due to interaction with cationic microspheres that remained attached to the sandstone surface. Colloid breakthrough curves could be fit well with a two site attachment model, with reversible and irreversible sites.

Transport of polymer stabilized nano-scale zero-valent iron in porous media.

This study presents a set of laboratory-scale transport experiments and numerical simulations evaluating carboxymethyl cellulose (CMC) polymer stabilized nano-scale zero-valent iron (nZVI) transport. The experiments, performed in a glass-walled two-dimensional (2D) porous medium system, were conducted to identify the effects of water specific discharge and CMC concentration on nZVI transport and to produce data for model validation. The transport and movement of a tracer lissamine green B® (LGB) dye, CMC, and CMC-nZVI were evaluated through analysis of the breakthrough curves (BTCs) at the outlets, the time-lapsed images of the plume, and retained nZVI in the sandbox. The CMC mass recovery was >95% when injected alone and about 65% when the CMC-nZVI mixture was used. However, the mean residence time of CMC was significantly higher than that of LGB. Of significance for field implementation, viscous fingering was observed in water displacement of previously injected CMC and CMC-nZVI. The mass recovery of nZVI was lower (<50%) than CMC recovery due to attachment onto sand grain surfaces. Consecutive CMC-nZVI injections showed higher nZVI recovery in the second injection, a factor to be considered in field trials with successive CMC-nZVI injections. Transport of LGB, CMC, and nZVI were modeled using a flow and transport model considering LGB and CMC as solutes, and nZVI as a colloid, with variable solution viscosity due to changes in CMC concentrations. The simulation results matched the experimental observations and provided estimates of transport parameters, including attachment efficiency, that can be used to predict CMC stabilized nZVI transport in similar porous media, although the extent of viscous fingering may be underpredicted. The experimental and simulation results indicated that increasing specific discharge had a greater effect on decreasing CMC-nZVI attachment efficiency (corresponding to greater possible travel distances in the field) than increasing CMC concentration.

Evaluation of peat and sawdust as permeable reactive barrier materials for stimulating in situ biodegradation of trichloroethene.

Two low cost solid organic materials, sawdust and peat, were tested in laboratory batch microcosm and flow-through column experiments to determine their suitability for application in permeable reactive barriers (PRBs) supporting biodegradation of trichloroethene (TCE). In microcosms with peat, TCE (∼30µM) was sequentially and completely degraded to cis-dichloroethene (cDCE), vinyl chloride, and ethene through reductive dechlorination. In microcosms with sawdust, reductive dechlorination of TCE stopped at cDCE and high methane production (up to 3000µM) was observed. 16S rRNA gene copy numbers of Dehalobacter and Archaea were higher (1000 and 10 times, respectively) in sawdust microcosms than those in peat microcosms. Dehalococcoides and vcrA gene copy numbers were 10 times higher in peat microcosms than in sawdust microcosms. These gene copy number differences are consistent with the extent of TCE degradation and production of methane in the microcosms. Flow-through column experiments showed that hydraulic conductivity reduction with time was consistently greater in the sawdust column compared to the peat column. The greater conductivity reduction was likely due to biofouling and methane gas bubble formation. The experimental observations indicate that peat has potential to be a better solid organic material than sawdust to support reductive dechlorination of TCE in PRB applications.

Colloid transport in dolomite rock fractures: effects of fracture characteristics, specific discharge, and ionic strength.

The effects of fracture characteristics, specific discharge, and ionic strength on microsphere transport in variable-aperture dolomite rock fractures were studied in a laboratory-scale system. Fractures with different aperture distributions and mineral compositions were artificially created in two dolomite rock blocks. Transport tests were conducted with bromide and carboxylate-modified latex microspheres (20, 200, and 500 nm diameter). Under overall unfavorable attachment conditions, there was significant retention of the 20 nm microsphere and minimal retention of the 500 nm microsphere for all conditions examined. Aperture variability produced significant spatial variation in colloid transport. Flushing with low ionic strength solution (1 mM) following microsphere transport at 12 mM ionic strength solution produced a spike in effluent microsphere concentrations, consistent with retention of colloids in secondary energy minima. Surface roughness and charge heterogeneity effects may have also contributed to the effect of microsphere size on retention. Matrix diffusion influenced bromide transport but was not a dominant factor in transport for any microsphere size. Calibrated one-dimensional, two-site kinetic model parameters for colloid transport in fractured dolomite were sensitive to the physical and chemical properties of both the fractured dolomite and the colloids, indicating the need for mechanistic modeling for accurate prediction.