Kinetics of urease mediated calcite precipitation and permeability reduction of porous media evidenced by magnetic resonance imaging

The enzyme urease drives the hydrolysis of urea leading to the release of ammonium ions and bicarbonate; in the presence of calcium, the rise in pH leads to increased calcium carbonate saturation and the subsequent precipitation of calcite. Although such alkalinizing ureolysis is widespread in nature, most studies have focussed on bacteria (i.e. indigenous communities or urease-active Sporosarcina pasteurii) for calcite precipitation technologies. In this study, urease-active jack bean meal (from the legume Canavalia ensiformis) was used to drive calcite precipitation. The rates of ureolysis (k _urea ), determined from measured NH₄ ⁺, enabled a direct comparison to microbial ureolysis rates reported in literature. It is also demonstrated that a simple single reaction model approach can simulate calcite precipitation very effectively (3–6 % normalised root-mean-square deviation). To investigate the reduction of permeability in porous media, jack bean meal (0.5 g L^?1) and solutions (400 mM urea and CaCl₂) were simultaneously pumped into a borosilicate bead column. One-dimensional magnetic resonance profiling techniques were used, non-invasively, for the first time to quantify the porosity changes following calcite precipitation. In addition, two-dimensional slice selective magnetic resonance images (resolution of ~0.5 × 1.0 mm) revealed that the exact location of calcite deposition was within the first 10 mm of the column. Column sacrifice and acid digestion also confirmed that 91.5 % of calcite was located within the first 14 mm of the column. These results have important implications for the design of future calcite precipitation technologies and present a possible alternative to the well known bacterial approaches.     

An X-ray excited optical luminescence study of a zoned quartz crystal from an emerald-bearing quartz vein,Hiddenite, North Carolina,USA

The optical luminescence excited with synchrotron radiation along a preferential orientation of a quartz crystal has been investigated. It is found that the crystal is composed of two distinct regions, only one of which luminesces upon X-ray excitation. This luminescence is generally uniform and exhibits emission bands in the blue (470 nm with a shoulder at 522 nm) and in the UV (340 nm) regions of the spectrum. The branching ratio for the intensity of these bands is sensitive to the excitation energy across the Si K-edge. XANES spectra collected by partial luminescence yield (PLY) suggest that both emission bands originate from the de-excitation of Si atoms in the quartz. The possible defect sites within the crystal structure that could account for the observed luminescence are investigated and discussed. Additional experiments are proposed to verify this assignment of the optical emission bands.     

Couplings of watersheds and coastal waters: Sources and consequences of nutrient enrichment in Waquoit Bay,Massachusetts

Human activities on coastal watersheds provide the major sources of nutrients entering shallow coastal ecosystems. Nutrient loadings from watersheds are the most widespread factor that alters structure and function of receiving aquatic ecosystems. To investigate this coupling of land to marine systems, we are studying a series of subwatersheds of Waquoit Bay that differ in degree of urbanization and hence are exposed to widely different nutrient loading rates. The subwatersheds differ in the number of septic tanks and the relative acreage of forests. In the area of our study, groundwater is the major mechanism that transports nutrients to coastal waters. Although there is some attenuation of nutrient concentrations within the aquifer or at the sediment-water interface, in urbanized areas there are significant increases in the nutrient content of groundwater arriving at the shore’s edge. The groundwater seeps or flows through the sediment-water boundary, and sufficient groundwater-borne nutrients (nitrogen in particular) traverse the sediment-water boundary to cause significant changes in the aquatic ecosystem. These loading-dependent alterations include increased nutrients in water, greater primary production by phytoplankton, and increased macroaglal biomass and growth (mediated by a suite of physiological responses to abundance of nutrients). The increased macroalgal biomass dominates the bay ecosystem through second- or third-order effects such as alterations of nutrient status of water columns and increasing frequency of anoxic events. The increases in seaweeds have decreased the areas covered by eelgrass habitats. The change in habitat type, plus the increased frequency of anoxic events, change the composition of the benthic fauna. The data make evident the importance of bottom-up control in shallow coastal food webs. The coupling of land to sea by groundwater-borne nutrient transport is mediated by a complex series of steps; the cascade of processes make it unlikely to find a one-to-one relation between land use and conditions in the aquatic ecosystem. Study of the process and synthesis by appropriate models may provide a way to deal with the complexities of the coupling.     

Mass Discharge in a Tracer Plume: Evaluation of the Theissen Polygon Method

A tracer plume was created within a thin aquifer by injection for 299 d of two adjacent “sub‐plumes” to represent one type of plume heterogeneity encountered in practice. The plume was monitored by snapshot sampling of transects of fully screened wells. The mass injection rate and total mass injected were known. Using all wells in each transect (0.77 m well spacing, 1.4 points/m² sampling density), the Theissen Polygon Method (TPM) yielded apparently accurate mass discharge (M_d) estimates at three transects for 12 snapshots. When applied to hypothetical sparser transects using subsets of the wells with average spacing and sampling density from 1.55 to 5.39 m and 0.70 to 0.20 points/m², respectively, the TPM accuracy depended on well spacing and location of the wells in the hypothesized transect with respect to the sub‐plumes. Potential error was relatively low when the well spacing was less than the widths of the sub‐plumes (>0.35 points/m²). Potential error increased for well spacing similar to or greater than the sub‐plume widths, or when less than 1% of the plume area was sampled. For low density sampling of laterally heterogeneous plumes, small changes in groundwater flow direction can lead to wide fluctuations in M_d estimates by the TPM. However, sampling conducted when flow is known or likely to be in a preferred direction can potentially allow more useful comparisons of M_d over multiyear time frames, such as required for performance evaluation of natural attenuation or engineered remediation systems.