A comparative study of the modelling of cement hydration and cement-rock laboratory experiments

The use of cement and concrete as fracture grouting or as tunnel seals in a geological disposal facility for radioactive wastes creates potential issues concerning chemical reactivity. From a long-term safety perspective, it is desirable to be able model these interactions and changes quantitatively. The ‘Long-term Cement Studies’ (LCS) project was formulated with an emphasis on in situ field experiments with more realistic boundary conditions and longer time scales compared with former experiments. As part of the project programme, a modelling inter-comparison has been conducted, involving the modelling of two experiments describing cement hydration on one hand and cement-rock reaction on the other, with teams representing the NDA (UK), Posiva (Finland), and JAEA (Japan).This modelling exercise showed that the dominant reaction pathways in the two experiments are fairly well understood and are consistent between the different modelling teams, although significant differences existed amongst the precise parameterisation (e.g. reactive surface areas, dependences of rate upon pH, types of secondary minerals), and in some instances, processes (e.g. partition of alkali elements between solids and liquid during cement hydration; kinetic models of cement hydration). It was not conclusive if certain processes such as surface complexation (preferred by some modellers, but not by others) played a role in the cement-rock experiment or not. These processes appear to be more relevant at early times in the experiment and the evolution at longer timescales was not affected. The observed permeability profile with time could not be matched. The fact that no secondary minerals could be observed and that the precipitated mass calculated during the simulations is minor might suggest that the permeability reduction does not have a chemical origin, although a small amount of precipitates at pore throats could have a large impact on permeability.The modelling exercises showed that there is an interest in keeping the numerical models as simple as possible and trying to obtain a reasonable fit with a minimum of processes, minerals and parameters. However, up-scaling processes and model parameterisation to the timescales appropriate to repository safety assessment are of considerable concern. Future modelling exercises of this type should focus on a suitable natural or industrial analogue that might aid assessing mineral-fluid reactions at these longer timescales.     

Temporal evolution and compositional signatures of two supervolcanic systems recorded in zircons from Mangakino volcanic centre,New Zealand

Mangakino, the oldest rhyolitic caldera centre delineated in the Taupo Volcanic Zone of New Zealand, generated two very large (super-sized) ignimbrite eruptions, the 1.21 ± 0.04 Ma >500 km³ Ongatiti and ~1.0 Ma ~1,200 km³ Kidnappers events, the latter of which was followed after a short period of erosion by the ~200 km³ Rocky Hill eruption. We present U/Pb ages and trace-element analyses on zircons from pumice clasts from these three eruptions by Secondary Ion Mass Spectrometry (SIMS) using SHRIMP-RG instruments to illustrate the evolution of the respective magmatic systems. U–Pb age spectra from the Ongatiti imply growth of the magmatic system over ~250 kyr, with a peak of crystallisation around 1.32 Ma, ~100 kyr prior to eruption. The zircons are inferred to have then remained stable in a mush with little crystallisation and/or dissolution before later rejuvenation of the system at the lead-in to eruption. The paired Kidnappers and Rocky Hill eruptions have U–Pb zircon ages and geochemical signatures that suggest they were products of a common system grown over ~200 kyr. The Kidnappers and Rocky Hill samples show similar weakly bimodal age spectra, with peaks at 1.1 and 1.0 Ma, suggesting that an inherited antecrystic population was augmented by crystals grown at ages within uncertainty of the eruption age. In the Kidnappers, this younger age peak is dominantly seen in needle-shaped low U grains with aspect ratios of up to 18. In all three deposits, zircon cores show larger ranges and higher absolute concentrations of trace elements than zircon rims, consistent with zircon crystallisation from evolving melts undergoing crystal fractionation involving plagioclase and amphibole. Abundances and ratios of many trace elements frequently show variations between different sectors within single grains, even where there is no visible sector zoning in cathodoluminescence (CL) imaging. Substitution mechanisms, as reflected in the molar (Sc + Y + REE³⁺)/P ratio, differ in the same growth zone between the sides (along a-axis and b-axis: values approaching 1.0) and tips (c-axis: values between 1.5 and 5.0) of single crystals. These observations have implications for the use of zircons for tracking magmatic processes, particularly in techniques where CL zonation within crystals is not assessed and small analytical spot sizes cannot be achieved. These observations also limit applicability of the widely used Ti-in-zircon thermometer. The age spectra for the Ongatiti and Kidnappers/Rocky Hill samples indicate that both magmatic systems were newly built in the time-breaks after respective previous large eruptions from Mangakino. Trace element variations defining three-component mixing suggest that zircons, sourced from multiple melts, contributed to the population in each system.     

Mineralized and unmineralized calderas in Spain; Part II, evolution of the Rodalquilar caldera complex and associated gold-alunite deposits

The Rodalquilar caldera complex is located in the western part of the Cabo de Gata volcanic field in southeastern Spain and is the first documented example of epithermal gold-alunite mineralization within a caldera in Europe. The Rodalquilar caldera is an oval collapse structure having a maximum diameter of 8 km and formed at 11 Ma from eruption of the Cinto ash-flow tuff. The oval Lomilla caldera, with a diameter of 2 km, is nested within the central resurgent dome of the older Rodalquilar caldera. The Lomilla caldera resulted from the eruption of the Lazaras ash-flow tuff which was ponded within the moat of the Rodalquilar caldera. The last phase of volcanic activity in the caldera complex was the emplacement of hornblende andesite flows and intrusions. This magmatic event resulted in structural doming of the caldera, opening of fractures and faults, and provided the heat source for the large hydrothermal systems which deposited quartz-alunite type gold deposits and base metal vein systems. The gold-alunite deposits are enclosed in areas of intense acid sulfate alteration and localized in ring and radial faults and fractures present in the east wall of the Lomilla caldera. Like other acid-sulfate type deposits, the Rodalquilar gold-alunite deposits are closely related in time and space to porphyritic, intermediate composition magma emplaced along caldera structures but unrelated to the caldera forming magmatic system.     

Reconciling approaches to climate change adaptation for Colombian agriculture

The projected impact of climate change on agro-ecological systems is considered widespread and significant, particularly across the global tropics. As in many other countries, adaptation to climate change is likely to be an important challenge for Colombian agricultural systems. In a recent study, a national-level assessment of the likely future impacts of climate change on agriculture was performed (Ramirez-Villegas et al. Clim Chang 115:611–628, 2012, RV2012). The study diagnosed key challenges directly affecting major crops and regions within the Colombian agricultural system and suggested a number of actions thought to facilitate adaptation, while refraining from proposing specific strategies at local scales. Further insights on the study were published by Feola (2013) (F2013), who stressed the need for transformative adaptation processes to reduce vulnerability particularly of resource-limited farmers, and the benefits of a predominantly stakeholder-led approach to adaptation. We clarify that the recommendations outlined in RV2012 were not intended as a recipe for multi-scale adaptation, but rather a set of actions that are required to diagnose and develop adaptation actions particularly at governmental levels in coordination with national and international adaptation initiatives. Such adaptation actions ought to be, ideally, a product of inclusive sub-sectorial assessments, which can take different forms. We argue that Colombian agriculture as a whole would benefit from a better outlining of adaptation needs across temporal scales in sub-sectorial assessments that take into account both RV2012 and F2013 orientations to adaptation. We conclude with two case studies of research on climate change impacts and adaptation developed in Colombia that serve as examples of realistic, productive sectorial and sub-national assessments.     

The Influences of NAO and the Hudson Bay sea-ice on the climate of eastern Canada

Sea-ice cover over the Hudson Bay (HB) exhibits large variability in the freeze-up season normally starting in November. Its influence on the climate over eastern Canada has been studied with the Canadian Regional Climate Model (CRCM) in three steps. First, a 30-year continuous simulation from 1970 to 1999 was performed as a control run to evaluate the simulated climate variability over eastern Canada, in particularly variability associated with the North Atlantic oscillation (NAO). Then, 50 additional 1 month experiments were performed with modified sea-surface conditions prescribed over the HB. These integrations allowed us to quantify the contribution of HB sea-ice anomalies versus large scale NAO atmospheric variability (as defined by prescribed lateral boundary conditions) in inducing climate variability over eastern Canada. Results show that the NAO is the dominant factor controlling climate variability over eastern Canada. The contribution of HB sea-ice anomalies is significant only in the immediate coastal region. Under the influence of different phases of NAO, HB sea-ice anomalies do co-vary with temperature and precipitation anomalies downstream of the HB over eastern Canada. The ultimate cause of this co-variability is NAO variability which forces variability in both HB sea-ice cover as well as temperature/precipitation over eastern Canada.     

Platinum and palladium mobility in supergene environment: The residual origin of the Pirogues River mineralization, New Caledonia

Eluvial concentration of platinum-group minerals (PGM) has developed in the south of New Caledonia, from the weathering of a mafic and ultramafic cumulate. The platinum/palladium (Pt/Pd) ratio evolution from the bottom to the top of the weathering profile indicates a chemical mobilization of Pd in supergene environment. The examination by scanning electron microscopy of the residual PGM collected in the weathering profile and their chemical characterization by electronic microprobe show a preservation of the structure and chemical signature (in the core of the grains) of the fresh PGM. This clearly demonstrates that the PGM studied here are residual and are affected by dissolution process.     

Mixing and differentiation in the Oruanui rhyolitic magma, Taupo, New Zealand: evidence from volatiles and trace elements in melt inclusions

Large pyroclastic rhyolites are snapshots of evolving magma bodies, and preserved in their eruptive pyroclasts is a record of evolution up to the time of eruption. Here we focus on the conditions and processes in the Oruanui magma that erupted at 26.5 ka from Taupo Volcano, New Zealand. The 530 km³ (void-free) of material erupted in the Oruanui event is comparable in size to the Bishop Tuff in California, but differs in that rhyolitic pumice and glass compositions, although variable, did not change systematically with eruption order. We measured the concentrations of H₂O, CO₂ and major and trace elements in zoned phenocrysts and melt inclusions from individual pumice clasts covering the range from early to late erupted units. We also used cathodoluminescence imaging to infer growth histories of quartz phenocrysts. For quartz-hosted inclusions, we studied both fully enclosed melt inclusions and reentrants (connecting to host melt through a small opening). The textures and compositions of inclusions and phenocrysts reflect complex pre-eruptive processes of incomplete assimilation/partial melting, crystallization differentiation, magma mixing and gas saturation. ‘Restitic’ quartz occurs in seven of eight pumice clasts studied. Variations in dissolved H₂O and CO₂ in quartz-hosted melt inclusions reflect gas saturation in the Oruanui magma and crystallization depths of ∼3.5–7 km. Based on variations of dissolved H₂O and CO₂ in reentrants, the amount of exsolved gas at the beginning of eruption increased with depth, corresponding to decreasing density with depth. Pre-eruptive mixing of magma with varying gas content implies variations in magma bulk density that would have driven convective mixing. Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

A two-dimensional analytical solution of groundwater responses to tidal loading in an estuary and ocean

Previous studies on tidal dynamics of coastal aquifers have focussed on the inland propagation of oceanic tides in the cross-shore direction, a configuration that is essentially one-dimensional. Aquifers at natural coasts can also be influenced by tidal waves in nearby estuaries, resulting in a more complex behaviour of head fluctuations in the aquifers. We present an analytical solution to the two-dimensional depth-averaged groundwater flow equation for a semi-infinite aquifer subject to oscillating head conditions at the boundaries. The solution describes the tidal dynamics of a coastal aquifer that is adjacent to a cross-shore estuary. Both the effects of oceanic and estuarine tides on the aquifer are included in the solution. The analytical prediction of the head fluctuations is verified by comparison with numerical solutions computed using a standard finite-difference method. An essential feature of the present analytical solution is the interaction between the cross- and along-shore tidal waves in the aquifer area near the estuary’s entry. As the distance from the estuary or coastline increases, the wave interaction is weakened and the aquifer response is reduced, respectively, to the one-dimensional solution for oceanic tides or the solution of Sun (Sun H. A two-dimensional analytical solution of groundwater response to tidal loading in an estuary, Water Resour Res 1997;33:1429–35) for two-dimensional non-interacting tidal waves.     

Survivorship and growth of Fucus gardneri after transplant to an acid mine drainage-polluted area

Acid mine drainage (AMD) from an abandoned copper mine at Britannia Beach, British Columbia, Canada, enters the marine environment through Britannia Creek. The surrounding intertidal zone is devoid of rockweed, Fucus gardneri Silva, a seaweed that dominates nearby shores. Rockweed plants were transplanted to the intertidal zone near Britannia Creek and monitored for changes in percent cover, survivorship, growth rate and Cu content. Autumn and winter transplants to within 100 m of Britannia Creek resulted in negative growth rates and high mortality within 57 days of exposure to AMD, with Cu levels in rockweed surpassing 2,300 ppm in dry tissue. Summer transplants to sites 300-700 m from Britannia Creek showed no consistent differences between AMD-exposed rockweed and control plants, possibly because the plants were stressed by desiccation. The results are consistent with ecological effects observed in other studies, and provide strong evidence for the role of AMD in excluding rockweed from the shores near Britannia Creek.