Implementation and evaluation of permeability-porosity and tortuosity-porosity relationships linked to mineral dissolution-precipitation

Changes of porosity, permeability, and tortuosity due to physical and geochemical processes are of vital importance for a variety of hydrogeological systems, including passive treatment facilities for contaminated groundwater, engineered barrier systems (EBS), and host rocks for high-level nuclear waste (HLW) repositories. Due to the nonlinear nature and chemical complexity of the problem, in most cases, it is impossible to verify reactive transport codes analytically, and code intercomparisons are the most suitable method to assess code capabilities and model performance. This paper summarizes model intercomparisons for six hypothetical scenarios with generally increasing geochemical or physical complexity using the reactive transport codes CrunchFlow, HP1, MIN3P, PFlotran, and TOUGHREACT. Benchmark problems include the enhancement of porosity and permeability through mineral dissolution, as well as near complete clogging due to localized mineral precipitation, leading to reduction of permeability and tortuosity. Processes considered in the benchmark simulations are advective-dispersive transport in saturated media, kinetically controlled mineral dissolution-precipitation, and aqueous complexation. Porosity changes are induced by mineral dissolution-precipitation reactions, and the Carman-Kozeny relationship is used to describe changes in permeability as a function of porosity. Archie’s law is used to update the tortuosity and the pore diffusion coefficient as a function of porosity. Results demonstrate that, generally, good agreement is reached amongst the computer models despite significant differences in model formulations. Some differences are observed, in particular for the more complex scenarios involving clogging; however, these differences do not affect the interpretation of system behavior and evolution.

Dissolution rate spectra data of calcite single crystal and micrite material

The large discrepancy between field and laboratory measurements of mineral reaction rates is a long-standing problem in earth sciences, often attributed to factors extrinsic to the mineral itself. Nevertheless, differences in reaction rate are also observed within laboratory measurements, raising the possibility of intrinsic variations as well. Critical insight is available from analysis of the relationship between the reaction rate and its distribution over the mineral surface. This analysis recognizes the fundamental variance of the rate. The resulting anisotropic rate distributions are completely obscured by the common practice of surface area normalization. In a simple experiment using a single crystal and its polycrystalline counterpart, we demonstrate the sensitivity of dissolution rate to grain size, results that undermine the use of "classical" rate constants. Comparison of selected published crystal surface step retreat velocities (Jordan and Rammensee, 1998) as well as large single crystal dissolution data (Busenberg and Plummer, 1986) provide further evidence of this fundamental variability. Our key finding highlights the unsubstantiated use of a single-valued "mean" rate or rate constant as a function of environmental conditions. Reactivity predictions and long-term reservoir stability calculations based on laboratory measurements are thus not directly applicable to natural settings without a probabilistic approach. Such a probabilistic approach must incorporate both the variation of surface energy as a general range (intrinsic variation) as well as constraints to this variation owing to the heterogeneity of complex material (e.g., density of domain borders). We suggest the introduction of surface energy spectra (or the resulting rate spectra) containing information about the probability of existing rate ranges and the critical modes of surface energy.

Foraminiferal abundance, carbonat concentration and dissolution index of sediment core W9903B-51GC

In order to investigate the paleoceanographic record of dissolution of calcium carbonate (CaCO3) in the central equatorial Pacific Ocean, we have studied the relationship between three indices of foraminiferal dissolution and the concentration and accumulation of CaCO3, opal, and Corg in Core WEC8803B-GC51 (1.3°N, 133.6°W; 4410 m). This core spans the past 413 kyr of deposition and moved in and out of the lysoclinal transition zone during glacial-interglacial cycles of CaCO3 production and dissolution. The record of dissolution intensity provided by foraminiferal fragmentation, the proportion of benthic foraminifera, and the foraminiferal dissolution index consistently indicates that the past corrosion of pelagic CaCO3 in the central equatorial Pacific does not vary with the observed sedimentary concentration of CaCO3. Although there is a weak low-frequency variation (~100 kyr) in dissolution intensity, it is unrelated to sedimentary CaCO3 concentration. There are many shorter-lived episodes where high CaCO3 concentration is coincident with poor foraminiferal preservation, and where, conversely, low CaCO3 concentration is coincident with superb foraminiferal preservation. Spectral analyses indicate that dissolution maxima consistently lagged glacial maxima (manifest by the SPECMAP delta18O stack) in the 100-kyr orbital band. Additionally, there is no relationship between dissolution and the accumulation of biogenic opal or Corg or between dissolution and the burial ratio of Corg/CINorg (calculated from Corg and CaCO3). Because previous studies of this core strongly suggest that surface water productivity varied closely with CaCO3 accumulation, both the mechanistic decoupling of carbonate dissolution from CaCO3 concentration (and from biogenic accumulation) and the substantial phase shift between dissolution and global glacial periodicity effectively obscure any simple link between export production, CaCO3 concentration, and dissolution of sedimentary CaCO3.

Dissolution index and shell weights of planktonic foraminifera

Finding the ideal deep-sea CaCO3 dissolution proxy is essential for quantifying the role of the marine carbonate system in regulating atmospheric pCO2 over millennia. We explore the potential of using the Globorotalia menardii fragmentation index (MFI) and size-normalized foraminifer shell weight (SNSW) as complementary indicators of deep-sea CaCO3 dissolution. MFI has strong correlations with bottom water [CO3]2-, modeled estimates of percent CaCO3 dissolved, and Mg/Ca in Pulleniatina obliquiloculata in core top samples along a depth transect on the Ontong Java Plateau (OJP) where surface ocean temperature variation is minimal. SNSW of P. obliquiloculata and Neogloboquadrina dutertrei have weak correlations with MFI-based percent dissolved, Mg/Ca in P. obliquiloculata shells and bottom water [CO3]2- on the OJP. In core top samples from the eastern equatorial Pacific (EEP), SNSW of P. obliquiloculata has moderate to strong correlations with both MFI-based percent CaCO3 dissolved estimates and surface ocean environmental parameters. SNSW of N. dutertrei shells shows a latitudinal distribution in the EEP and a moderately strong correlation with MFI-based percent dissolved estimates when samples from the equatorial part of the region are excluded. Our results suggest that there may potentially be multiple genotypes of N. dutertrei in the EEP which may be reflected in their shell weight. MFI-based percent CaCO3 dissolved estimates have no quantifiable relationship with any surface ocean environmental parameter in the EEP. Thus MFI acts as a reliable quantitative CaCO3 dissolution proxy insensitive to environmental biases within calcification waters of foraminifers.

Exposure to pesticides, ill health and averting behaviour : costs and determining the relationship

Farmers' exposure to pesticides is high in developing countries. As a result many farmers suffer from ill-health, both short and long term. Deaths are not uncommon. This paper addresses this issue. Field survey data from Sri Lanka are used to estimate farmers' expenditure on defensive behavior (DE) and to determine factors that influence DE. The avertive behavior approach is used to estimate costs. Tobit regression analysis is used to determine factors that influence DE. Field survey data show that farmers' expenditures on DE are low. This is inversely related to high incidence of ill health among farmers using pesticides.

Visitor Relationship Management (VRM) - Repeat Visitation Opportunities for Destination Marketing Organisations

In competitive tourism markets the consumer-traveller is spoilt by choice of available destinations. Successfully differentiating a destination and getting noticed at decision time is arguably the focus of activities by destination marketing organisations (DMOs). In pursuit of differentiation, three emergent themes in the marketing literature during the past decade have been branding, integrated marketing communications (IMC), and customer relationship management (CRM) a fundamental goal of each being stimulating customer loyalty. However there has been little attention given to destination loyalty in the tourism literature. The purpose of this paper is to report an exploratory investigation of visitor relationship management (VRM) by DMOs. Based on interviews with the management of 11 regional tourism organisations (RTO) in Queensland, Australia, the opportunities for, and immediate challenges of, VRM are discussed. While each RTO recognised the potential for VRM, none had yet been able to develop a formal approach to engage in meaningful dialogue with previous visitors from their largest market.