Coupled modeling of cement/claystone interactions and radionuclide migration

The interactions between cement and a clayey host-rock of an underground repository for intermediate-level radioactive waste are studied with the reactive transport code HYTEC for supporting performance assessment. Care is taken in using relevant time scales (100,000 years) and dimensions. Based on a literature review, three hypotheses are considered with respect to the mineralogical composition of the claystone and the neo-formed phases. In the long term, the pH is buffered for all hypotheses and important mineral transformations occur both in cement and the host-rock. The destruction of the primary minerals is localized close to the cement/claystone interface and is characterized by the precipitation of secondary phases with retention properties (illite, zeolite). However, beyond the zone of intense mineral transformations, the pore water chemistry is also disturbed over a dozen meters due to an attenuated but continuous flux of hydroxyl, potassium and calcium ions. Four interdependent mechanisms control the profile in the whole system: diffusion of the alkaline plume, mineralogical buffering, ion exchange and clogging of the pore space at the cement/claystone interface. The migration of a selected group of radionuclides (Cs, Ra, Tc and U) is explicitly integrated in the simulations of the strongly coupled system. Theoretical profiles of distribution coefficient (Kd) and solubility limit values are derived from the simulations, and their sensitivity with respect to the system evolution is estimated.     

Cascading ecological effects of low-level phosphorus enrichment in the Florida everglades

Few studies have examined long-term ecological effects of sustained low-level nutrient enhancement on wetland biota. To determine sustained effects of phosphorus (P) addition on Everglades marshes we added P at low levels (5, 15, and 30 microg L(-1) above ambient) for 5 yr to triplicate 100-m flow-through channels in pristine marsh. A cascade of ecological responses occurred in similar sequence among treatments. Although the rate of change increased with dosing level, treatments converged to similar enriched endpoints, characterized most notably by a doubling of plant biomass and elimination of native, calcareous periphyton mats. The full sequence of biological changes occurred without an increase in water total P concentration, which remained near ambient levels until Year 5. This study indicates that Everglades marshes have a near-zero assimilative capacity for P without a state change, that ecosystem responses to enrichment accumulate over time, and that downstream P transport mainly occurs through biota rather than the water column.     

Electron affinity coefficients of nitrogen oxides and biodegradation kinetics in denitrification of contaminated stream water

During the dry season in Korea, rivers become more vulnerable to contamination by biochemical oxygen demand (BOD) and nitrogen. It is hypothesized that the natural characteristics of the streams in Korea allow the contaminated water to be treated at the tributaries. Down-stream river water quality in Korea may be improved by spraying the contaminated stream water from the tributaries over the surrounding floodplains. The consequent water filtration through the soil could remove the contaminants through aerobic and denitrifying reactions. In this study, the kinetics parameters of the denitrifying reaction in floodplain filtration were determined using contaminated stream water. For the electron donor the Monod kinetics was used, while the competitive Michaelis-Menten model was employed for the electron acceptors. The parameters to the competitive Michaelis-Menten model were found using continuous denitrifying reactions, instead of the batch reactions employed in previous studies, to match the conditions needed to apply the competitive Michaelis-Menten kinetics. From the result, it was found that continuous reactions as well as batch reactions could be used to determine the affinity coefficients in denitrification. The results of this study also showed that the affinity coefficient of NO2, using continuous reactions, was similar to that of other studies in the literature found via batch reactions, whereas the affinity coefficient of N2O was much larger than that acquired with batch reactions. The parameters obtained in this study will be used in future work to simulate the contaminant behaviors during floodplain filtration using a mathematical model.     

Role of active floodplains for nutrient retention in the river Rhine

We evaluated the importance of floodplains for nutrient retention in two distributaries of the river Rhine (Waal and IJssel) by monitoring N and P retention in a body of water during downstream transport. We hypothesized that (i) retention of P is much larger than retention of N and (ii) nutrient retention increases with an increasing amount of the discharge flowing through floodplains (QF). The second hypothesis was tested by comparing retention between the rivers Waal (low QF) and IJssel (high QF), as well as at different discharges. Total nitrogen (TN) did not decrease significantly during downstream transport in both rivers, whereas 20 to 45% of total phosphorus (TP) disappeared during transport in the river IJssel. This difference between N and P retention-supporting the first hypothesis-was probably caused by differences in sedimentation through a much lower proportion of N adsorbed to particles than of P (2-3% of N vs. 50-70% of P). Phosphorus retention was only observed in the IJssel and not in the Waal, and absolute P retention (g P s(-1) km(-1)) in the IJssel increased with increasing QF. The second hypothesis was, nevertheless, not fully supported, because the percentage P retention (% of P load) decreased (instead of increased) with increasing QF. The percentage P retention increased with decreasing river depth and flow velocity; it seemed related to the efficiency of sediment trapping.     

Significance of anion exchange in pentachlorophenol sorption by variable-charge soils

Sorption data and subsequent predictive models for evaluating acidic pesticide behavior on variable-charge soils are needed to improve pesticide management and environmental stewardship. Previous work demonstrated that sorption of pentachlorophenol (PCP), a model organic acid, was adequately modeled by accounting for pH-and pKa-dependent chemical speciation and using two organic carbon-normalized sorption coefficients; one each for the neutral and anionic species. Such models do not account for organic anion interaction to positively charged surface sites, which can be significant for variable-charge minerals present in weathered soils typical of tropical and subtropical regions. The role of anion exchange in sorption of ionizable chemicals by variable-charge soils was assessed by measuring sorption of PCP by several variable-charge soils from aqueous solutions of CaCl2, CaSO4, Ca(H2PO4)2 as a function of pH. Differences in sorption from phosphate and chloride electrolyte solutions were attributed to pentachlorophenolate interactions with anion exchange sites. Suppression of PCP sorption by phosphate ranged from negligible in a soil with essentially no positively charge sites, as measured by negligible anion exchange capacity, to as much as 69% for variable-charge soils. Pentachlorophenolate exchange correlated well with the ratio of pH-dependent anion exchange capacity to net surface charge. Sorption reversibility of PCP by both CaCl2 and Ca(H2PO4)2 solutions was also demonstrated. Results for PCP clearly demonstrate that sorption to anion exchange sites in variable-charge soils should be considered in assessing pesticide mobility and that phosphate fertilizer application may increase the mobility of acidic pesticides.     

Assessment of spiking procedures for the introduction of a phenanthrene-LNAPL mixture into field-wet soil

Laboratory based studies on the fate of organic contaminants in soil typically requires the test compound(s) to be spiked into the test medium. Consequently, such studies are inherently dependent on the homogeneity of the contaminant within the spiked soil. Three blending methods were compared for the addition of a phenanthrene-transformer oil mixture into field-wet soil. Spiking homogeneity, reproducibility and artefacts were assessed based on dichloromethane and hydroxypropyl-beta-cyclodextrin chemical extractability, and bacterial mineralization. Spiking using a stainless-steel spoon, consistently produced good spike homogeneity as determined by sample oxidation, chemical extraction and mineralization, and was consistently more reliable than either the Waring blender or modified bench drill. Overall, neither transformer oil-concentration nor blending method influenced chemical extractability or mineralization of the PAH following 1 day equilibration. In general, spiking procedures require validation prior to use, as homogeneity cannot be assured.     

Formulation of resource depletion index

A resource depletion index can serve as a quantitative tool to evaluate the level of depletion for natural resources. This study introduces two types of resource depletion indices, the global resource depletion index and the local resource depletion index. Global resource depletion index mainly concerns global reserves and the annual consumption rate of these resources. The local resource depletion index not only considers global reserves and their annual consumption rate, but also considers the local factors such as local reserves, local recycling rates, and local resource import characteristics. This study considers the local resource characteristics of Taiwan and develops calculations for local resource depletion indexes for the resources of cobalt, molybdenum, tungsten, copper, aluminum, lead and zinc.     

LAKE ONTARIO REGULATION UNDER TRANSPOSED CLIMATES1

ABSTRACT: The implications of Lake Ontario regulation under transposed climates with changed means and variability are presented for seasonal and annual time scales. The current regulation plan is evaluated with climates other than the climate for which it was developed and tested. This provides insight into potential conflicts and management issues, development of regulation criteria for extreme conditions, and potential modification of the regulation plan. Transposed climates from the southeastern and south central continental United States are applied to thermodynamic models of the Great Lakes and hydrologic models of their watersheds; these climates provide four alternative scenarios of water supplies to Lake Ontario. The scenarios are analyzed with reference to the present Great Lakes climate. The responses of the Lake Ontario regulation plan to the transposed climate scenarios illustrate several key issues: (1) historical water supplies should no longer be the sole basis for testing and developing lake regulation plans; (2) during extreme supply conditions, none of the regulation criteria can be met simultaneously, priority of interests may change, and new interests may need to be considered, potentially requiring substantial revision to the Boundary Waters Treaty of 1909; (3) revised regulation criteria should be based on ecosystem health and socio-economic benefits for a wider spectrum of interests and not on frequencies and ranges of levels and flows of the historical climate; and (4) operational management of the lake should be improved under the present climate, and under any future climate with more variability, through the use of improved water supply forecasts and monitoring of current hydrologic conditions.     

Protection policy for Hawaii's native wildlife during geothermal energy development

Hawaii possesses abundant geothermal resources and rare native wildlife. Geothermal energy development has not posed a threat to native wildlife in the past, but development potential has recently reached a level at which concern for native wildlife is warranted.Potential geothermal resource areas in Hawaii intersect important native forest and endangered species habitat. The ability of existing laws to constrain development in these areas is in question. State and federal endangered species and environmental reporting laws have little ability to constrain geothermal development on private land. Hawaii's Land Use Law had been viewed by conservationists as protecting natural areas important to native wildlife, but recent decisions of the state Land Board sharply challenge this view.While this dispute was being resolved in the courts, the state legislature passed the Geothermal Subzone Act of 1983. Wildlife value was assessed in the geothermal subzone designation process mandated by this act, but the subzones designated primarily reflected inappropriate developer influence. All areas in which there was developer interest received subzone designation, and no area in which there was no developer interest was subzoned. This overriding emphasis on developer interest violated the intent of the sub-zone act, and trivialized the importance of other assessment criteria, among them native wildlife values.