Estimating Reaction Rate Coefficients Within a Travel‐Time Modeling Framework

A generalized, efficient, and practical approach based on the travel‐time modeling framework is developed to estimate in situ reaction rate coefficients for groundwater remediation in heterogeneous aquifers. The required information for this approach can be obtained by conducting tracer tests with injection of a mixture of conservative and reactive tracers and measurements of both breakthrough curves (BTCs). The conservative BTC is used to infer the travel‐time distribution from the injection point to the observation point. For advection‐dominant reactive transport with well‐mixed reactive species and a constant travel‐time distribution, the reactive BTC is obtained by integrating the solutions to advective‐reactive transport over the entire travel‐time distribution, and then is used in optimization to determine the in situ reaction rate coefficients. By directly working on the conservative and reactive BTCs, this approach avoids costly aquifer characterization and improves the estimation for transport in heterogeneous aquifers which may not be sufficiently described by traditional mechanistic transport models with constant transport parameters. Simplified schemes are proposed for reactive transport with zero‐, first‐, nth‐order, and Michaelis‐Menten reactions. The proposed approach is validated by a reactive transport case in a two‐dimensional synthetic heterogeneous aquifer and a field‐scale bioremediation experiment conducted at Oak Ridge, Tennessee. The field application indicates that ethanol degradation for U(VI)‐bioremediation is better approximated by zero‐order reaction kinetics than first‐order reaction kinetics.     

GeoPT2. International Proficiency Test for Analytical Geochemistry Laboratories - Report on Round 2

Results from sixty laboratories participating in GeoPT2, the international proficiency testing programme for analytical geochemistry laboratories, are reported. Compared with 71.3% in the last round, 74.6% of the reported data complied with the laboratories' selected fitness for purpose criteria.     

Marsh expansion at Calaveras Point Marsh, South San Francisco Bay, California

Studies of shoreline progradation along low-energy vegetated shorelines have been limited, as these environments are generally experiencing erosion rather than deposition, with extreme erosion rates frequently found. This study examined yearly changes along a vegetated shoreline at Calaveras Point Marsh, South San Francisco Bay, California, using aerial photography, to determine the roles of climatic, watershed, and coastal process in driving shoreline changes. In addition, sediment accumulation was monitored on a yearly basis at 48 locations across the marsh to determine the role of geomorphic factors in promoting accumulation. Calaveras Point Marsh was found to have expanded from 49.26 ± 5.2 to 165.7 ± 4.7 ha between 1975 and 2005. Although the rate of marsh expansion was not positively correlated with yearly variability in precipitation, local streamflow, delta outflow, water level observations, population growth, or ENSO indices, marsh growth was greater during years of higher than average temperatures. Warmer temperatures may have promoted the recruitment and growth of Spartina foliosa, a C₄ grass known to be highly responsive to temperature. Other factors, such as the formation of a coastal barrier, a recent change in the location of the mouth of the Guadalupe River, and channel readjustment in response to diking are credited with driving the bulk of the marsh expansion. Sediment accumulation was found to be high closest to channels and to the shoreline, at low elevations and in recently vegetated marsh. Globally, the pace of sea level rise exerts the primary control on wetland development and persistence. However, at local geographic scales, factors such as tectonic events, modifications to natural sediment transport pathways or land use changes may overwhelm the effects of regional sea level rise, and allow for wetlands to develop, expand and persist despite rapid sea level rise.     

Time structure of the extensive air shower front

The GREX/COVER_PLASTEX experiment has measured the temporal and spatial fine structure of the EAS disc at sea level in a new and original way, using resistive plate counter detectors for direct measurements of the arrival time of each particle crossing the detector. Data were taken at EAS core distances up to 100 m for shower size N > 10⁵ (PeV energy range). Arrival times of shower particles were measured with nanosecond accuracy. More than 450000 air shower events have been included in this analysis.     

Li diffusion in zircon

Diffusion of Li under anhydrous conditions at 1 atm and under fluid-present elevated pressure (1.0–1.2 GPa) conditions has been measured in natural zircon. The source of diffusant for 1-atm experiments was ground natural spodumene, which was sealed under vacuum in silica glass capsules with polished slabs of zircon. An experiment using a Dy-bearing source was also conducted to evaluate possible rate-limiting effects on Li diffusion of slow-diffusing REE⁺³ that might provide charge balance. Diffusion experiments performed in the presence of H₂O–CO₂ fluid were run in a piston–cylinder apparatus, using a source consisting of a powdered mixture of spodumene, quartz and zircon with oxalic acid added to produce H₂O–CO₂ fluid. Nuclear reaction analysis (NRA) with the resonant nuclear reaction ⁷Li(p,γ)⁸Be was used to measure diffusion profiles for the experiments. The following Arrhenius parameters were obtained for Li diffusion normal to the c-axis over the temperature range 703–1.151°C at 1 atm for experiments run with the spodumene source:

Apatite and phosphorus in mantle source regions: An experimental study of apatite/melt equilibria at pressures to 25 kbar

The solubility of fluorapatite in a wide variety of basic magmatic liquids was experimentally determined over a range of upper mantle P-T conditions (8–25 kbar, 1275–1350°C). Fluorapatite is stable over the entire range of conditions investigated, but its solubility in melts is variable, depending negatively on SiO₂ content of the melt and positively upon temperature, with relatively little sensitivity to pressure above 8 kbar. At upper mantle pressures and a temperature of 1250°C, molten basalt (50% SiO₂) will dissolve 3–4 wt.% P₂O₅ before saturation in apatite is reached. For a magma 100°C cooler or containing 10 wt.% more SiO₂, apatite saturation occurs at less than 2 wt.% dissolved P₂O₅. The observed high solubility of apatite in basic magmas at their normal near-liquidus temperatures virtually precludes the occurrence of residual apatite in mantle source regions. If relatively low-temperature melting conditions prevail (e.g., 1100°C), as might be possible in H₂O-bearing regions of the upper mantle, apatite could remain in the residue, but only in amounts too small to have significant effects on the rare earth patterns of the liquids.Because of the high solubility of apatite in basic magmas, phosphorus can be confidently treated as an incompatible element in peridotite melting models. Such models, in combination with observed characteristics of basic lavas, indicate that the upper mantle contains ～200 ppm of phosphorus, much less than the chondritic abundance of ～900 ppm.     

Infill sampling criteria to locate extremes

Three problem-dependent meanings for engineering extremes are motivated, established, and translated into formal geostatistical (model-based) criteria for designing infill sample networks. (1) Locate an area within the domain of interest where a specified threshold is exceeded, if such areas exist. (2) Locate the maximum value in the domain of interest. (3) Minimize the chance of areas where values are significantly different from predicted values. An example application on a simulated dataset demonstrates how such purposive design criteria might affect practice.     

Calibrations to estimate absolute numbers of New Zealand fur seal (Arctocephalus forsteri) pups from direct counts

Annual direct counts of seal pups can indicate long‐term trends in population size, but mark‐recapture estimates are needed to deduce absolute numbers. A calibration between results from these two methods would facilitate the use of direct counts to estimate absolute numbers, an outcome that is relatively quick, cheap and minimises disturbance of animals. Mark‐recapture estimates for the numbers of New Zealand fur seal (Arctocephalus forsteri) pups in 2003 at 10 colonies at Otago, southeastern New Zealand, were compared with independent single counts at the same colonies. A single ratio to estimate absolute numbers (y) from direct counts x was not statistically significant. Instead, two ratios were deduced, based on differences in habitat among colonies: y = 1.51x for colonies with hiding places for pups and y = 0.96x for colonies without hiding places. Application of these calibrations and their 95% prediction intervals produce estimates and ranges for the absolute numbers of pups from single annual counts.     

Diffusion in fluid-bearing and slightly-melted rocks: experimental and numerical approaches illustrated by iron transport in dunite

Bulk diffusion of iron in synthetic dunites containing 1–6 vol.% fluid or melt at 10 kbar (1 GPa) and 900°–1300° C was examined by encapsulating the samples in platinum, which served as a sink for iron. The rate of iron loss from the dunite was found to depend strongly upon the identity of the fluid, which was varied from CO₂ and H₂O to melts of basaltic and sodium carbonate composition. Carbon dioxide in amounts up to 4 vol.% has no effect upon bulk iron diffusion because it exists in the dunite are isolated pores. The interconnected nature of H₂O, basaltic melt, and carbonate melt, on the other hand, results in marked enhancement of bulk-rock Fe diffusion that is correlated with the diffusivity and solubility of olivine components in the fluid. At 1300° C, 4–5 vol.% of either water or basaltic melt increases the effective bulk diffusivity from the fluidabsent value of 10^-10 cm²/s to 10^-8 cm²/s. A single experiment involving a similar volume fraction of carbonate melt yielded a minimum bulk diffusivity of 10^-7–10^-6 cm²/s. This remarkably high value is attributable to the concurrent high diffusivity and high solubility of olivine components in molten carbonate H₂O has a high diffusivity, estimated at 10^-4 cm²/s in this study, and basaltic melt can dissolve large amounts of olivine, but neither possesses these two qualities in combination. Bulk transport of Fe in dunite containing <2 vol.% of pure H₂O is independent of olivine grain size for samples having an average grain diameter of <10 m to 60 m. This is probably because bulk diffusion specifically in these H₂O-bearing samples is ratelimited by the flux (which is proportional to concentration) of olivine components in the fluid. Given a constant fluid volume fraction, the effect of reducing the grain size is to increase the number of fluid-filled channels, but at the same time to decrease their average aperture, thus keeping constant the cross-sectional area through which the diffusional flux occurs. (Independence of bulk diffusivity from grain size is not anticipated for rocks containing melt, in which the silicate components are much more soluble.) In numerical (finite difference) simulations of selected laboratory experiments, the bulk Fe transport process was modeled as diffusion in fluid-filled tubules of triangular cross-section that are supplied by volume diffusion from contacting olivine grains with which they are in surface equilibrium. Applying a tortuosity factor of 1.7 brings the numerically computed diffusional loss profiles for experiments containing basaltic melt into near-coincidence with the experimentally-determined curves. This success in reproducing the experimental results lends credence to the interpretation of the bulk diffusional loss profiles as composites of gradients due to volume, grain-boundary and fluid-phase diffusion.