Influence of hydrogeochemical processes on zero-valent iron reactive barrier performance: a field investigation.

Geochemical and mineralogical changes were evaluated at a field Fe0-PRB at the Oak Ridge Y-12 site concerning operation performance during the treatment of U in high NO3- groundwater. In the 5-yr study period, the Fe0 remained reactive as shown in pore water monitoring data, where increases in pH and the removal of certain ionic species persisted. However, coring revealed varying degrees of cementation. After 3.8-yr treatment, porosity reduction of up to 41.7% was obtained from mineralogical analysis on core samples collected at the upgradient gravel-Fe0 interface. Elsewhere, Fe0 filings were loose with some cementation. Fe0 corrosion and pore volume reduction at this site are more severe due to the presence of NO3- at a high level. Tracer tests indicate that hydraulic performance deteriorated: the flow distribution was heterogeneous and under the influence of interfacial cementation a large portion of water was diverted around the Fe0 and transported outside the PRB. Based on the equilibrium reductions of NO3- and SO4(2-) by Fe0 and mineral precipitation, geochemical modeling predicted a maximum of 49% porosity loss for 5 yr of operation. Additionally, modeling showed a spatial distribution of mineral precipitate volumes, with the maximum advancing from the interface toward downgradient with time. This study suggests that water quality monitoring, coupled with hydraulic monitoring and geochemical modeling, can provide a low-cost method for assessing PRB performance.

Influence of hydrogeochemical processes on zero-valent iron reactive barrier performance: a field investigation.

Geochemical and mineralogical changes were evaluated at a field Fe0-PRB at the Oak Ridge Y-12 site concerning operation performance during the treatment of U in high NO3- groundwater. In the 5-year study period, the Fe0 remained reactive as shown in pore-water monitoring data, where increases in pH and the removal of certain ionic species persisted. However, coring revealed varying degrees of cementation. After 3.8-year treatment, porosity reduction of up to 41.7% was obtained from mineralogical analysis on core samples collected at the upgradient gravel-Fe0 interface. Elsewhere, Fe0 filings were loose with some cementation. Fe0 corrosion and pore volume reduction at this site are more severe due to the presence of NO3- at a high level. Tracer tests indicate that hydraulic performance deteriorated: the flow distribution was heterogeneous and under the influence of interfacial cementation a large portion of water was diverted around the Fe0 and transported outside the PRB. Based on the equilibrium reductions of NO3- and SO4(2-) by Fe0 and mineral precipitation, geochemical modeling predicted a maximum of 49% porosity loss for 5 years of operation. Additionally, modeling showed a spatial distribution of mineral precipitate volumes, with the maximum advancing from the interface toward downgradient with time. This study suggests that water quality monitoring, coupled with hydraulic monitoring and geochemical modeling, can provide a low-cost method for assessing PRB performance.

Identification and quantification of mineral precipitation in Fe0 filings from a column study.

Thermogravimetric analysis (TGA) combined with X-ray diffraction (XRD) was used to identify mineral phases and determine corrosion rates of granular iron samples from a 2-yr field column study. Similar to other studies, goethite, magnetite, aragonite, and calcite were found to be the major precipitated minerals, with Fe2(OH)2CO3 and green rust as minor phases. Based on TGA-mass spectrometry (MS) analysis, Fe0 corrodes at rates of 0.5-6.1 mmol kg(-1) d(-1) in the high NO3- (up to 13.5 mM) groundwater; this rate is significantly higher than previously reported. Porosity reduction was 40.6%-45.1% for the inlet sand/Fe0 interface and 7.4%-25.6% for effluent samples of two test columns. Normalized for treatment volumes, porosity loss values are consistent with studies that use high levels of SO4(2-) but are higher than those using low levels of corrosive species. Aqueous mass balance calculations yield corrosion rates similar to the TGA-MS method, providing an alternative to coring and mineralogical analysis. A severely corroded iron sample from the column simulating a 17-yr treatment throughput showed >75% porosity loss. Extensive porosity loss due to high levels of corrosive species in groundwater will have significant impact on long-term performance of permeable reactive barriers.

Hydrate composite particles for ocean carbon sequestration: field verification.

This paper reports on the formation and dissolution of CO2/seawater/CO2 hydrate composite particles produced during field experiments in Monterey Bay, CA using a CO2 injector system previously developed in the laboratory. The injector consisted of a coflow reactor wherein water was introduced as a jet into liquid CO2, causing vigorous mixing of the two immiscible fluids to promote the formation of CO2 hydrate that is stable at ambient pressures and temperatures typical of ocean depths greater than approximately 500 m. Using flow rate ratios of water and CO2 of 1:1 and 5:1, particulate composites of CO2 hydrate/liquid CO2/seawater phases were produced in seawater at depths between 1100 and 1300 m. The resultant composite particles were tracked by a remotely operated vehicle system as they freely traveled in an imaging box that had no bottom or top walls. Results from the field experiments were consistent with laboratory experiments, which were conducted in a 70 L high-pressure vessel to simulate the conditions in the ocean at intermediate depths. The particle velocity and volume histories were monitored and used to calculate the conversion of CO2 into hydrate and its subsequent dissolution rate after release into the ocean. The dissolution rate of the composite particles was found to be higher than that reported for pure CO2 droplets. However, when the rate was corrected to correspond to pure CO2, the difference was very small. Results indicate that a higher conversion of liquid CO2 to CO2 hydrate is needed to form negatively buoyant particles in seawater when compared to freshwater, due primarily to the increased density of the liquid phase but also due to processes involving brine rejection during hydrate formation.

CO2 hydrate composite for ocean carbon sequestration.

Rapid CO2 hydrate formation was investigated with the objective of producing a negatively buoyant CO2-seawater mixture under high-pressure and low-temperature conditions, simulating direct CO2 injection at intermediate ocean depths of 1.0-1.3 km. A coflow reactor was developed to maximize CO2 hydrate production by injecting water droplets (e.g., approximately 267 microm average diameter) from a capillary tube into liquid CO2. The droplets were injected in the mixing zone of the reactor where CO2 hydrate formed at the surface of the water droplets. The water-encased hydrate particles aggregated in the liquid CO2, producing a paste-like composite containing CO2 hydrate, liquid CO2, and water phases. This composite was extruded into ambient water from the coflow reactor as a coherent cylindrical mass, approximately 6 mm in diameter, which broke into pieces 5-10 cm long. Both modeling and experiments demonstrated that conversion from liquid CO2 to CO2 hydrate increased with water flow rate, ambient pressure, and residence time and decreased with CO2 flow rate. Increased mixing intensity, as expressed by the Reynolds number, enhanced the mass transfer and increased the conversion of liquid CO2 into CO2 hydrate. Using a plume model, we show that hydrate composite particles (for a CO2 loading of 1000 kg/s and 0.25 hydrate conversion) will dissolve and sink through a total depth of 350 m. This suggests significantly better CO2 dispersal and potentially reduced environmental impacts than would be possible by simply discharging positively buoyant liquid CO2 droplets. Further studies are needed to address hydrate conversion efficiency, scale-up criteria, sequestration longevity, and impact on the ocean biota before in-situ production of sinking CO2 hydrate composite can be applied to oceanic CO2 storage and sequestration.