Decomposition of nitrous oxide on pillared clays

Alumina-pillared smectites have been found to abate nitrous oxide in the presence of methane. The results indicate that the yield of the reaction (N20 --> N2 + (1/2)O2) increases when pillared clays are exchanged with transition metals, single-pass conversion rates of >70% being attainable. In particular, when double exchanged (calcium and subsequently copper) alumina pillared montmorillonite/beidellite is used as a catalyst, de-N2O activity reaches a maximum, which is maintained even after 4 h of work at a space velocity of 5.5 h(-1). A mechanism for the reaction is suggested, which implies that N2O is first adsorbed by the catalyst and then decomposes through two different paths: catalyst oxidation and catalyst reduction. Such a redox process explains the kinetic data.     

Air distribution in the Borden aquifer during in situ air sparging

A field experiment was conducted at Canadian Forces Base Borden (CFB Borden) to assess the air distribution from a single in situ air sparging injection point. This aquifer consists of fine to medium sand deposited in horizontal layers. The permeability at the study location varied from 10(-10) to 10(-14) m2 and distinct low permeability horizons were present at approximately 1.2, 2.0, and 2.9 m below the water table. Prior to air injection, a 15x15-m portion of the vadose zone was excavated to the water table (approximately 1 m below ground surface) in order to visually observe air release distribution at the water table. The water table was actively maintained 5 cm above the excavated surface. The sparging system operated for a period of 7 days with an injection flow rate of 200 m3/days (5 scfm). The resulting subsurface air distribution was assessed using a variety of techniques including neutron logging, borehole and surface ground penetrating radar, piezometric head measurements, surface visualization, and hydraulic testing. Through this combination of tests, it was demonstrated that variations in permeability and, hence, capillary pressure at the site were sufficient to cause the injected air to spread laterally, forming stratigraphically trapped air pockets beneath the low permeability horizons. The formation of these air pockets eventually resulted in a buildup of capillary pressure that exceeded the air entry pressure and allowed some air to migrate up through the lower permeability layers. Each of the assessment techniques employed generated information at different spatial scales that prevented a direct comparison of the results from the various techniques; however, the results from all techniques proved to be critical in the interpretation of the experimental data. As a consequence, the different assessment techniques should not be viewed as alternatives, but rather as complimentary techniques.     

Modelling the effects of ‘coastal’ acidification on copper speciation

We present here a copper speciation model that accounts for the long-term (‘coastal-acidification’) and short-term (daily and seasonal variation) variability in water pH and water temperature. The developed model is applied to a sub-tropical estuary (Moreton Bay, Australia) at a one hundred year time scale so that outputs are consistent with climate change projections. The model predicts that the mean cupric ion concentration (Cu²⁺) in the estuary will increase by 115% over the next 100 years as a result of the projected decrease in pH and increase in water temperature. Through calibration, the estimated concentration of copper-complexing dissolved organic matter (DOM) in the estuary is found to be 22.5 nM. An increase in the concentration of Cu²⁺, which is the most toxic and bioavailable form of copper, has implications for ecosystem health and may have a negative effect on the detoxifying capacity of DOM. Models that provide a framework for coupling biological, chemical and physical processes are important for providing a holistic perspective of coastal systems, especially for better understanding a system within the context of climatic and non-climatic drivers.