Solubility and near-equilibrium dissolution rates of quartz in dilute NaCl solutions at 398-473 K under alkaline conditions

The dissolution-precipitation of quartz controls porosity and permeability in many lithologies and may be the best studied mineral-water reaction. However, the rate of quartz-water reaction is relatively well characterized far from equilibrium but relatively unexplored near equilibrium. We present kinetic data for quartz as equilibrium is approached from undersaturation and more limited data on the approach from supersaturated conditions in 0.1 molal NaCl + NaOH + NaSiO(OH)₃ solutions with pH 8.2-9.7 at 398, 423, 448, and 473 K. We employed a potentiometric technique that allows precise determination of solution speciation within 2 kJ mol⁻¹ of equilibrium without the need for to perturb the system through physical sampling and chemical analysis. Slightly higher equilibrium solubilities between 423 and 473 K were found than reported in recent compilations. Apparent activation energies of 29 and 37 kJ mol⁻¹ are inferred for rates of dissolution at two surface sites with different values of connectedness: dissolution at Q¹ or Q² silicon sites, respectively. The dissolution mechanism varies with ΔG such that reactions at both sites control dissolution up until a critical free energy value above which only reactions at Q¹ sites are important. When our near-equilibrium dissolution rates are extrapolated far from equilibrium, they agree within propagated uncertainty at 398 K with a recently published model by Bickmore et al. (2008). However, our extrapolated rates become progressively slower than model predictions with increasing temperature. Furthermore, we see no dependence of the postulated Q¹ reaction rate on pH, and a poorly-constrained pH dependence of the postulated Q² rate. Our slow extrapolated rates are presumably related to the increasing contribution of dissolution at Q³ sites far from equilibrium. The use of the potentiometric technique for rate measurement will yield both rate data and insights into the mechanisms of dissolution over a range of chemical affinity. Such measurements are needed to model the evolution of many natural systems quantitatively.     

Prediction of open stope hangingwall stability using random forests

Natural Hazards - The prediction of open stope hangingwall (HW) stability is a crucial task for underground mines. In this paper, a relatively novel technique, the random forest (RF) algorithm, is...     

Changes and patterns of origin regions of international tourism

The dramatic political and economic changes in Europe, Asia, and the Middle East during the early 1990s have had a dramatic impact on international tourism. Between 1974 and 1990 there have been significant shifts in international tourist originations. The purpose of this paper is to describe and analyze the changing patterns and to compare the two time periods. A key component of the study is the construction of a Population-Adjusted Travel Index which assesses the capability of a country to generate tourists relative to population characteristics. Findings indicate that Europe is still the leader in trips generated, even though the proportion from this region is declining over time. Asian countries exhibited the most marked improvement due primarily to the tremendous economic expansion taking place on the Pacific Rim. In contrast countries of the Middle East have declined in importance relative to international tourism. This is due to political and economic instability in the region.     

Strontium isotopes as tracers of airborne fly ash from coal-fired power plants

Fly ash generated by coal-fired power plants is in part collected by filters in the emission stacks while a small portion is vented into the atmosphere. Since many of the coalfired power plants in the western United States are located in the desnrt, the ability to monitor fly ash emissions requires a chemical tracer that utilizes desert soil and plant interactions with the fly ash deposited in the desert environment. This investigation presents the results of a controlled greenhouse experiment in which a native desert plant, the brittlebush (Encelia farinosa), was grown on admixtures of desert soils and fly ash. The fly ash is strongly enriched in Sr and the brittlebush is a Sr accumulator. The data demonstrate that (1) the brittlebush isotopically equilibrates with desert soils whose fly ash components are as low as 0.25% by weight, (2) the fly ash Sr is apparently more available to the plant, than Sr derived from the soils, and (3) the difference between the⁸⁷Sr/⁸⁶Sr ratio of the fly ash (0.70807) and soils (0.71097 to 0.71117) warrants further investigations in the natural environment to determine the practicality of this method as a natural tracer of fly ash in the environment.     

Paleoenvironmental records of water level and climatic changes from the middle to late Holocene at a Lake Erie coastal wetland, Ontario, Canada

Pollen and diatom assemblages, and peat stratigraphies, from a coastal wetland on the northern shore of Lake Erie were used to analyze water level and climatic changes since the middle Holocene and their effects on wetland plant communities. Peat deposition began 4700 cal yr B.P. during the Nipissing II transgression, which was driven by isostatic rebound. At that time, a diatom-rich wild rice marsh existed at the site. Water level dropped at the end of the Nipissing rise at least 2 m within 200 yr, leading to the development of shallower-water plant communities and an environment too dry for most diatoms to persist. The sharp decline in water level was probably driven primarily by outlet incision, but climate likely played some role. The paleoecological records provide evidence for post-Nipissing century-scale transgressions occurring around 2300, 1160, 700 and 450 cal yr B.P. The chronology for these transgressions correlates with other studies from the region and implies climatic forcing. Peat inception in shallow sloughs across part of the study area around 700 cal yr B.P. coincides with the Little Ice Age. These records, considered alongside others from the region, suggest that the Little Ice Age may have resulted in a wetter climate across the eastern Great Lakes region.     

A review of the metallogeny and tectonics of the Lachlan Orogen

Future mineral exploration within eastern Australia will be enhanced by resolving the tectonic evolution of the Lachlan Orogen to establish the spatial and temporal terrane distribution of the various mineral deposits. The Lachlan Orogen, from north-eastern Tasmania through to central and eastern New South Wales, is host to a number of major mineral deposit styles—including orogenic gold (e.g. Stawell, Ballarat, Bendigo), volcanic-hosted massive sulphide (e.g. Woodlawn, Currawong), sediment-hosted Cu–Au (e.g. Cobar Basin deposits), porphyry Au–Cu (e.g. Cadia, Parkes, Cowal) and granite-related Sn (e.g. Ardlethan, Beechworth). Each of these mineral deposit styles is a sensitive and diagnostic indicator of the prevalent tectonic environment during their formation. In this review, we briefly summarise the deposit- to large-scale factors that define the diverse metallogenic evolution of the Lachlan Orogen. This overview is intended to “set the scene” for subsequent specialist papers published in this thematic issue on the metallogeny and tectonics of the Lachlan Orogen in south-east Australia.     

Lipid distribution in a subtropical southern China stalagmite as a record of soil ecosystem response to paleoclimate change

Lipid extracts from a 61.7-cm-long subtropical stalagmite in southern China, spanning the period of ca. 10,000–21,000 yr ago as constrained by U–Th dating, were analyzed using gas chromatography–mass spectrometry. The higher plants and microorganisms in the overlying soils contribute a proportion of n-alkanes identified in the stalagmite. The occurrence of LMW (lower molecular weight) n-alkanols and n-alkan-2-ones in the stalagmite was mainly related to the soil microorganisms. We suggest that HMW (higher molecular weight) n-alkanols and n-alkan-2-ones identified in the stalagmite originate from soil organics and reflect input from contemporary vegetation. Shifts in the ratio of LMW to HMW n-alkanols or n-alkan-2-ones indicative of the variation of soil ecosystems (e.g., microbial degradation of organic matter and/or the relative abundance of soil microorganisms to higher plants) are comparable with the subtropical alkenone-SST (sea surface temperature) record of the same period. The similar trends seen in the δ¹³C data and the lipid parameters in this stalagmite imply that the overlying soil ecosystem response to climate might be responsible for the variation of δ¹³C values.     

Provincialism and correlations between some properties of vitrinites

Optical and chemical properties for hand-picked samples of vitrinite from a number of British coalfields are correlated and the correlations compared with previously published data. The form of the relationship found for the properties of British vitrinites is generally similar to that exhibited by a number of other sets of analyses, but some significant differences also exist in several of the correlations. For maximum reflectance as a function of carbon content, the present data indicate that at medium and low ranks, maximum reflectance is lower than the level suggested by most previous studies. The relationships of volatile-matter yield to reflectance and carbon content suggest that at low ranks, volatile-matter yield is strongly dependent upon the nature of the coalification history of the vitrinite. Furthermore, these correlations are likely to show provincialism, in that correlations which hold for one coalfield may not be representative of the relationship in other coalfields. Similarly, major differences in relationships involving bireflectance are associated with the tectonic setting at the time of effective coalification. The data presented here indicate that for low-rank coals at least, correlations between properties of vitrinites must take account of provincialism if they are to be sufficiently reliable to be useful. The measurement of a number of rank-sensitive variables can yield additional information about rank, as compared with the use of a single rank-sensitive variable.     

Devolution, the governance of regional development and the Trade Union Congress in the North East region of England

The devolution and regionalisation of political and administrative structures following the election of New Labour in 1997 have changed the nature of the state and territorial development and governance in the UK. A regional and sub-national tier has opened up within the existing multi-layered governance system operating at the supra-national, national and local scales. This ‘new institutional space’ is increasingly open to the participation of social institutions--including trade unions--in economic and social governance. Drawing upon empirical analysis of the experience of the Northern Trade Union Congress (NTUC) in the North East region of England, the paper argues that the NTUC--in contrast to its national organisation--is beginning to engage with the emergent institutional structures but its role is inhibited by the centralised strategy and structure of the TUC nationally, its own need for upgrading, capacity building and greater financial resources and the interaction between the North East’s particular legacy of tripartite corporatism and the more pluralist modes of regional development governance emerging in the English regions. Unless such issues are addressed regional trade union centres--such as the NTUC--risk remaining relatively junior partners in the emergent regional governance structures.     

Simulating flow in karst aquifers at laboratory and sub-regional scales using MODFLOW-CFP

Groundwater flow in a well-developed karst aquifer dominantly occurs through bedding planes, fractures, conduits, and caves created by and/or enlarged by dissolution. Conventional groundwater modeling methods assume that groundwater flow is described by Darcian principles where primary porosity (i.e. matrix porosity) and laminar flow are dominant. However, in well-developed karst aquifers, the assumption of Darcian flow can be questionable. While Darcian flow generally occurs in the matrix portion of the karst aquifer, flow through conduits can be non-laminar where the relation between specific discharge and hydraulic gradient is non-linear. MODFLOW-CFP is a relatively new modeling program that accounts for non-laminar and laminar flow in pipes, like karst caves, within an aquifer. In this study, results from MODFLOW-CFP are compared to those from MODFLOW-2000/2005, a numerical code based on Darcy’s law, to evaluate the accuracy that CFP can achieve when modeling flows in karst aquifers at laboratory and sub-regional (Woodville Karst Plain, Florida, USA) scales. In comparison with laboratory experiments, simulation results by MODFLOW-CFP are more accurate than MODFLOW 2005. At the sub-regional scale, MODFLOW-CFP was more accurate than MODFLOW-2000 for simulating field measurements of peak flow at one spring and total discharges at two springs for an observed storm event.