Geochemical and mineralogical impacts of H2SO4 on clays between pH 5.0 and −3.0

Natural and constructed clay liners are routinely used to contain waste and wastewater. The impact of acidic solutions on the geochemistry and mineralogy of clays has been widely investigated in relation to acid mine drainage systems at pH > 1.0. The impact of H₂SO₄ leachate characterized by pH < 1.0 and potentially negative pH values on the geochemistry and mineralogy of clays is, however, not clear. Thus, laboratory batch experiments were conducted on three natural clay samples with different mass ratios of smectite, illite and kaolinite to investigate the impact of H₂SO₄ on the geochemistry and mineralogy of aluminosilicates from pH 5.0 to −3.0. Batch testing was conducted at seven pH treatments (5.0, 3.0, 1.0, 0.0, −1.0, −2.0 and −3.0) using standardized H₂SO₄ solutions for four exposure periods (14, 90, 180, and 365 d). Aqueous geochemical and XRD analyses showed: increased dissolution of aluminosilicates with decreasing pH and increasing exposure period, that smectite was more susceptible to dissolution than illite and kaolinite, precipitation of an amorphous silica phase occurred at pH ? 0.0, and anhydrite precipitated in Ca-rich clays at pH ? −1.0. In addition, global dissolution rates were calculated for the clays and showed good agreement to literature smectite, illite and kaolinite dissolution rates, which suggests global dissolution rates for complex clays could be determined from monomineralic studies. A stepwise conceptual model of the impact of H₂SO₄ on aluminosilicate geochemistry and mineralogy between pH 5.0 and −3.0 is proposed.     

Comparison of fish and macroinvertebrate use of<Emphasis Type="Italic">Typha angustifolia,Phragmites australis</Emphasis>, and treated<Emphasis Type="Italic">Phragmites</Emphasis> marshes along the lower Connecticut River

Since 1965 large areas of lower Connecticut River tidelands have been converted from high diversity brackish meadow andTypha angustifolia marsh to near monocultures ofPhragmites australis. This study addresses the impact ofPhragmites invasion on fish and crustacean use of oligohaline high marsh. During spring tides from early June through early September 2000, fishes and crustaceans leaving flooded marsh along 3 km of the Lieutenant River, a lower Connecticut River tributary, were captured with Breder traps at 90 sites, equally distributed amongPhragmites, Typha, and treated (herbicide and mowing)Phragmites areas. Pit traps, 18 per vegetation type in 2000 and 30 each inPhragmites andTypha in 2001, caught larvae and juveniles at distances of up to 30 m into the marsh interior. There were no significant differences in fish species compositions or abundances among the vegetation types. Size distributions, size specific biomasses, and diets ofFundulus heteroclitus, the numerically dominant fish, were also similar. The shrimpPalaemonetes pugio was more abundant inPhragmites than in other types of vegetation, whereas the fiddler crabUca minax was least numerous inPhragmites. Mean numbers ofF. heteroclitus andP. pugio caught per site event were positively correlated with increasing site hydroperiod. Significantly moreF. heteroclitus were captured along the upper reach of the river where marsh elevations were lower than farther downstream. MoreF. heteroclitus and fewerP. pugio andU. minax were captured during the day than at night. A relatively small number of larval and juvenileFundulus sp. were captured in pit traps, but consistently fewer inPhragmites than inTypha, suggesting thatTypha and brackish meadow marshes may provide better nursery habitat. Vegetation was sampled along a 30 m transect at each trap site in 2000. Plant species diversity was greatest in treatedPhragmites areas and lowest inPhragmites sites.     

Turbulence statistics of a Kelvin–Helmholtz billow event observed in the night-time boundary layer during the Cooperative Atmosphere–Surface Exchange Study field program

An apparent shear flow instability occurred in the stably stratified night-time boundary layer on 6 October 1999 over the Cooperative Atmosphere–Surface Exchange Study (CASES-99) site in southeast Kansas. This instability promoted a train of billows which appeared to be in different stages of evolution. Data were collected by sonic anemometers and a high-frequency thermocouple array distributed on a 60 m tower at the site, and a high resolution Doppler lidar (HRDL), situated close to the tower. Data from these instruments were used to analyze the characteristics of the instability and the billow event. The instability occurred in a layer characterized by a minimum Richardson number Ri0.13, and where an inflection in the background wind profile was also documented. The billows, which translated over the site for approximately 30 min, were approximately L320 m in length and, after billow evolution they were contained in a layer depth H30 m. Their maximum amplitude, determined by HRDL data, occurred at a height of 56 m. Billow overturns, responsible for mixing of heat and momentum, and high-frequency intermittent turbulence produce kurtosis values above the Gaussian value of 3, particularly in the lower part of the active layer.     

Use of ultrasonically modulated electron resonance to study S-state ions in mineral crystals: Mn2+, Fe3+, in tremolite

The use of ultrasonically modulated electron resonance (UMER) to study S-state ions in substitutional sites of mineral single crystals is discussed. Mn²⁺ and Fe³⁺ in natural single crystals of tremolite are used as examples. Combined electron paramagnetic resonance (EPR) and UMER measurements establish almost certainly that Mn²⁺ enters predominantly into the distorted M4 sites occupied by Ca²⁺ in the ideal tremolite structure and only to a minor extent into the M1, M2 and M3 sites normally occupied by Mg²⁺. Fe³⁺ in tremolite gives rise to the well known high spin resonance with g _eff?4.3 but there is considerable uncertainty as to the site of the impurity ion.     

Formation,history and energetics of cores in the terrestrial planets

The cores of the terrestrial planets Earth, Moon, Mercury, Venus and Mars differ substantially in size and in history. Though no planet other than the Earth has a conclusively demonstrated core, the probable cores in Mercury and Mars and Earth's core show a decrease in relative core size with solar distance. The Moon does not fit this sequence and Venus may not. Core formation must have been early (prior to ～4 · 10⁹ yr. ago) in the Earth, by virtue of the existence of ancient rock units and ancient paleomagnetism and from UPb partitioning arguments, and in Mercury, because the consequences of core infall would have included extensional tectonic features which are not observed even on Mercury's oldest terrain. If a small core exists in the Moon, still an open question, completion of core formation may be placed several hundred million years after the end of heavy bombardment on tectonic and thermal grounds. Core formation time on Mars is loosely constrained, but may have been substantially later than for the other terrestrial planets. The magnitude and extent of early heating to drive global differentiation appear to have decreased with distance from the sun for at least the smaller bodies Mercury, Moon and Mars.Energy sources to maintain a molten state and to fuel convection and magnetic dynamos in the cores of the terrestrial planets include principally gravitational energy, heat of fusion, and long-lived radioactivity. The gravitational energy of core infall is quantifiable and substantial for all bodies but the Moon, but was likely spent too early in the history of most planets to prove a significant residual heat source to drive a present dynamo. The energy from inner core freezing in the Earth and in Mercury is at best marginally able to match even the conductive heat loss along an outer core adiabat. Radioactive decay in the core offers an attractive but unproven energy source to maintain core convection.     

Geochemical fingerprints of dolomitization in Bahamian carbonates: Evidence from sulphur,calcium, magnesium and clumped isotopes

In an effort to constrain the mechanism of dolomitization in Neogene dolomites in the Bahamas and improve understanding of the use of chemostratigraphic tracers in shallow‐water carbonate sediments the δ³⁴S, Δ₄₇, δ¹³C, δ¹⁸O, δ^44/40Ca and δ²⁶Mg values and Sr concentrations have been measured in dolomitized intervals from the Clino core, drilled on the margin of Great Bahama Bank and two other cores (Unda and San Salvador) in the Bahamas. The Unda and San Salvador cores have massively dolomitized intervals that have carbonate associated sulphate δ³⁴S values similar to those found in contemporaneous seawater and δ^44/40Ca, δ²⁶Mg values, Sr contents and Δ₄₇ temperatures (25 to 30°C) indicating relatively shallow dolomitization in a fluid‐buffered system. In contrast, dolomitized intervals in the Clino core have elevated values of carbonate associated sulphate δ³⁴S values indicating dolomitization in a more sediment‐buffered diagenetic system where bacterial sulphate reduction enriches the residual in ³⁴S, consistent with high sediment Sr concentrations and low δ^44/40Ca and high δ²⁶Mg values. Only dolomites associated with hardgrounds in the Clino core have carbonate associated δ³⁴S values similar to seawater, indicating continuous flushing of the upper layers of the sediment by seawater during sedimentary hiatuses. This interpretation is supported by changes to more positive δ^44/40Ca values at hardground surfaces. All dolomites, whether they formed in an open fluid‐buffered or closed sediment‐buffered diagenetic system have similar δ²⁶Mg values suggesting that the HMC transformed to dolomite. The clumped isotope derived temperatures in the dolomitized intervals in Clino yield temperatures that are higher than normal, possibly indicating a kinetic isotope effect on dolomite Δ₄₇ values associated with carbonate formation through bacterial sulphate reduction. The findings of this study highlight the utility of applying multiple geochemical proxies to disentangle the diagenetic history of shallow‐water carbonate sediments and caution against simple interpretations of stratigraphic variability in these geochemical proxies as indicating changes in the global geochemical cycling of these elements in seawater.     

Corporate knowledge transfer via interlocking directorates: a network analysis approach

This paper explores spatial changes to knowledge transfer by Canadian and American corporate networks from 1976 to 1996. Results support facets of a World Cities approach for Canada. Toronto lies at the top of the hierarchy, while Montreal, Calgary, and Vancouver fall into a third tier of specialized regional cities. The American knowledge network also possesses facets of the world cities approach. The world city, New York, lies at the top of the hierarchy. Further down, Chicago is a specialized national city, while a number of regional centers have emerged to play a larger role over the twenty-year study period. A third tier of cities has emerged to play the critical role of specialized regional cities. This geographical phenomenon can be explained in terms of industry, headquarters locations, and network maturity. Finance, insurance and real estate, as well as “other manufacturing” are three sectors of the economy that are prominent in the network. In Canada, these sectors have increasingly centralized in Toronto while decentralizing in the United States. Similarly, the headquarters location of American firms is decentralizing from New York and Chicago, while Canadian headquarters continue to be centralized in Toronto. Finally, results indicate that the potential for knowledge transfer depends upon maturity of the system under investigation. The mature US network with a large pool of qualified business individuals is better suited for knowledge transfer at the regional level. The Canadian network is less developed and not appropriate for regional systems of knowledge transfer. The result is a Canadian corporate knowledge threshold that encompasses the entire country while a number of much smaller corporate knowledge thresholds appear across the United States.     

Secular cooling of the Earth as a source of intraplate stress

As a result of secular cooling and contraction of the Earth, an increasingly extensional horizontal stress is imposed on the central portions of the plates. While the rate of increase of this stress is small in most situations, it is enhanced for large plates and during any episodes of accelerated global cooling. This source of stress may have contributed to the rifting and breakup of long-lived supercontinental plates.     

Microvariability in the early stages of cobble weathering by microenvironment on a glacier foreland,Storbreen, Jotunheimen,Norway

The initial stages of cobble weathering, measured as increasing percentage porosity, were calculated for sets of cobbles taken from the foreland of Storbreen, a cirque glacier in the Jotunheimen, Norway. Cobbles were taken from in front of the 1998 glacier snout, from the 1928, 1870, 1810 and 1750 moraine crests and from the ～10 000‐year‐old land surface beyond the Neoglacial foreland limit. Three microenvironments were examined within each site: (1) lichen‐free surfaces from exposed cobbles, (2) lichen‐covered surfaces from exposed cobbles and (3) buried cobbles taken from a soil depth of ～40 cm. Percentage porosity within plagioclase minerals was calculated using backscatter electron images of prepared thin sections. Porosity was calculated from five depth profiles into each cobble. Depth profiles were subdivided into a sequence of 50 µm × 50 µm rectangles running to at least a nominal depth of 500 µm within each cobble. Three cobbles from each dated land surface were sampled, except for the 1750 surface, which had five cobbles. Statistical analysis was by analysis of variance of rank‐order transformed data. Findings indicate that cobbles close to the glacier snout are largely unweathered; also, weathering is generally weak in the 1928, 1870 and 1810 positions, but statistically significantly higher in the 1750‐ and 10 000‐year‐old positions. Weathering of buried cobbles always exceeded weathering of exposed cobbles and may possibly reach a value beyond which it cannot progress while retaining surface cohesion. The degree of weathering on lichen‐free and lichen‐covered cobble surfaces is not initially distinguishable, but diverges sharply after ～250 years, when lichen‐covered surfaces experience significantly higher totals. Overall, the weathering trend in cobbles matches that found in soils at the same sites. Copyright © 2007 John Wiley & Sons, Ltd.