Temperature effects on non-bridging oxygen and aluminum coordination number in calcium aluminosilicate glasses and melts

Configurational changes with temperature are important for the thermodynamic and transport properties of most aluminosilicate melts, but in general are not well understood. Here, we present high-resolution ²⁷Al and ¹⁷O NMR data on several calcium aluminosilicate glasses prepared with varying quench rates and thus with fictive temperatures that span ranges up to about 200 K. In all compositions the content of five-coordinated aluminum increases with fictive temperature, in agreement with recent high temperature NMR data on melts. In a glass of CaAl₂Si₂O₈ (“anorthite”) composition, the content of non-bridging oxygens also increases with temperature; however this effect was not observed in a sample with a much higher CaO/Al₂O₃ ratio. We present a consistent notation for reactions among structural species in these systems that clarify why in some cases, high-coordinated network cations may appear on the same side of the reaction, while in others they occur on the opposite sides: the key difference is in accounting for all coordination changes for oxygens. Mixing of non-bridging oxygens and of high-coordinated aluminum make significant contributions to the overall configurational entropy and heat capacity of the melts, as does the mixing of various bridging oxygens and of tetrahedral network cations. Other, less well known, types of increase in disorder with temperature may be important as well.     

Diurnal variation in rates of calcification and carbonate sediment dissolution in Florida Bay

Water quality and criculation in Florida Bay (a shallow, subtropical estuary in south Florida) are highly dependent upon the development and evolution of carbonate mud banks distributed throughout the Bay. Predicting the effect of natural and anthropogenic perturbations on carbonate sedimentation requires an understanding of annual, seasonal, and daily variations in the biogenic and inorganic processes affecting carbonate sediment precipitation and dissolution. In this study, net calcification rates were measured over diurnal cycles on 27 d during summer and winter from 1999 to 2003 on mud banks and four representative substrate types located within basins between mud banks. Substrate types that were measured in basins include seagrass beds of sparse and intermediate densityThalassia sp., mud bottom, and hard bottom communities. Changes in total alkalinity were used as a proxy for calcification and dissolution. On 22 d (81%), diurnal variation in rates of net calcification was observed. The highest rates of net carbonate sediment production (or lowest rates of net dissolution) generally occurred during daylight hours and ranged from 2.900 to −0.410 g CaCO₃ m⁻²d⁻¹. The lowest rates of carbonate sediment production (or net sediment dissolution) occurred at night and ranged from 0.210 to −1.900 g CaCO₃ m⁻² night⁻¹. During typical diurnal cycles, dissolution during the night consumed an average of 29% of sediment produced during the day on banks and 68% of sediment produced during the day in basins. Net sediment dissolution also occurred during daylight, but only when there was total cloud cover, high turbidity, or hypersalinity. Diurnal variation in calcification and dissolution in surface waters and surface sediments of Florida Bay is linked to cycling of carbon dioxide through photosynthesis and respiration. Estimation of long-term sediment accumulation rates from diurnal rates of carbonate sediment production measured in this study indicates an overall average accumulation rate for Florida Bay of 8.7 cm 1000 yr⁻¹ and suggests that sediment dissolution plays a more important role than sediment transport in loss of sediment from Florida Bay.     

New Mexico structural zone—an analogue of the Colorado mineral belt

Updated aeromagnetic maps of New Mexico together with current knowledge of the basement geology in the northern part of the state (Sangre de Cristo and Sandia–Manzano Mountains)—where basement rocks were exposed in Precambrian-cored uplifts—indicate that the northeast-trending Proterozoic shear zones that controlled localization of ore deposits in the Colorado mineral belt extend laterally into New Mexico. The shear zones in New Mexico coincide spatially with known epigenetic precious- and base-metal ore deposits; thus, the mineralized belts in the two states share a common inherited basement tectonic setting. Reactivation of the basement structures in Late Cretaceous–Eocene and Mid-Tertiary times provided zones of weakness for emplacement of magmas and conduits for ore-forming solutions. Ore deposits in the Colorado mineral belt are of both Late Cretaceous–Eocene and Mid-Tertiary age; those in New Mexico are predominantly Mid-Tertiary in age, but include Late Cretaceous porphyry-copper deposits in southwestern New Mexico.The mineralized belt in New Mexico, named the New Mexico structural zone, is 250-km wide. The northwest boundary is the Jemez subzone (or the approximately equivalent Globe belt), and the southeastern boundary was approximately marked by the Santa Rita belt. Three groups (subzones) of mineral deposits characterize the structural zone: (1) Mid-Tertiary porphyry molybdenite and alkaline-precious-metal deposits, in the northeast segment of the Jemez zone; (2) Mid-Tertiary epithermal precious-metal deposits in the Tijeras (intermediate) zone; and (3) Late Cretaceous porphyry-copper deposits in the Santa Rita zone. The structural zone was inferred to extend from New Mexico into adjacent Arizona. The structural zone provides favorable sites for exploration, particularly those parts of the Jemez subzone covered by Neogene volcanic and sedimentary rocks.     

Consequences of diffuse and channelled porous melt migration on uranium series disequilibria

Magmas erupted at mid-ocean ridges (MORB) result from decompression melting of upwelling mantle. However, the mechanism of melt transport from the source region to the surface is poorly understood. It is debated whether melt is transported through melt-filled conduits or cracks on short time scales (<∼ 10³ yrs), or whether there is a significant component of slow, equilibrium porous flow on much longer time scales (>∼ 10³-10⁴ yrs). Radiogenic excess ²²⁶Ra in MORB indicates that melt is transported from the melting region on time scales less than the half life of ²²⁶Ra (∼1600 yrs), and has been used to argue for fast melt transport from the base of the melting column. However, excess ²²⁶Ra can be generated at the bottom of the melt column, during the onset of melting, and at the top of the melt column by reactive porous flow. Determining the depth at which ²²⁶Ra is generated is critical to interpreting the rate and mechanism of magma migration. A recent compilation of high quality U-series isotope data show that in many young basalts, ²²⁶Ra excess in MORB is negatively correlated with ²³⁰Th excess. The data suggest that ²²⁶Ra excess is generated independently of ²³⁰Th excess, and cannot be explained by “dynamic” or fractional melting, where observed radiogenic excesses are all generated at the base of the melt column. One explanation is that the negative correlation of activity ratios is a result of mixing of slow moving melt that has travelled through reactive, low-porosity pathways and relatively fast moving melt that has been transported in unreactive high-porosity channels. We investigate this possibility by calculating U-series disequilibria in a melting column in which high-porosity, unreactive channels form within a low-porosity matrix that is undergoing melting. The results show that the negative correlation of ²²⁶Ra and ²³⁰Th excesses observed in MORB can be produced if ∼60% of the total melt flux travels through the low-porosity matrix. This melt maintains ²²⁶Ra excesses via chromatographic fractionation of Ra and Th during equilibrium transport. Melt that travels through the unreactive, high-porosity channels is not able to maintain significant ²²⁶Ra excesses because Ra and Th are not fractionated from each other during transport and the transport time for melt in the channels to reach the top of the melt column is longer than the time scale for ²²⁶Ra excesses to decay. Mixing of melt from the high porosity channels with melt from the low-porosity matrix at the top of the melting column can produce a negative correlation of ²²⁶Ra and ²³⁰Th excesses with the slope and magnitude observed in MORB. This transport process can also account for other aspects of the geochemistry of MORB, such as correlations between La/Yb, α_Sm/Nd, and Th/U and ²²⁶Ra and ²³⁰Th excess.     

Kimberlite metasomatism at Murowa and Sese pipes, Zimbabwe

Metasomatism accompanying kimberlite emplacement is a worldwide phenomenon, although infrequently described or recognised. At the Cambrian-aged Murowa and Sese kimberlite clusters located within the Archean Zimbabwe Craton just north of the boundary with the Limpopo Mobile Zone in southern central Zimbabwe, the metasomatism is intense and well exposed and the processes can be readily studied. Dykes, sills and the root zones of pipes are exposed at the current erosion level. Kimberlite lithologies present are hypabyssal macrocrystic kimberlite (“HMK”), HMK breccia, and tuffisitic kimberlite breccia (“TKB”) including minor lithic tuffisitic kimberlite breccia (“LTKB”). Country rocks are 2.6 Ga Chibi and Zimbabwe granite batholiths emplaced into 2.6–2.9 Ga or earlier Archean tonalitic gneiss and greenstones. During initial metasomatism, the granites become spotted with green chlorite, needles of alkaline amphiboles (winchite, riebeckite, arfvedsonite) and pyroxenes (aegirine–augite) with minor carbonate and felts of talc. Oligoclase feldspar becomes converted to albite, extensively altered, dusted and reddened with hematite, whereas K-feldspar remains unaffected. The granites become converted to syenite through removal of quartz. More intense metasomatism at Murowa and Sese results in veins of green metasomatite which cut and disrupt the granite. Progressive disruption entrains granite blocks, breaking down the granite still further, spalling off needle-like granite slivers, and so giving rise to LTKB. This process of disruption and entrainment appears to be the manner of initial development of the pipe structure. The chemistry of the metasomatite is intermediate between granite and kimberlite. Compared to granite country rock it has markedly higher Mg, Cr, Ni, CO₂ and H₂O+, higher Ca, Mn, Nb, Sr, P, Fe³⁺/Fe²⁺ ratio, U, Co, and Cu, approximately equal TiO₂, K₂O, Na₂O, La, Ta, Rb, Zr, Zn and resultant lower SiO₂, Al₂O₃, Ga and Y. The metasomatite Na₂O/K₂O ratio is slightly higher than that of the granite. The metasomatic process is broadly analogous to fenitisation of granitic wall rock accompanying carbonatite complex emplacement. The metasomatism at Murowa and Sese was caused by fluids from the rising but confined proto-kimberlite melt penetrating into cracks and matrix of granite country rock and reacting with it. These fluids were CO₂-rich, hydrous, oxidising, enhanced in ultramafic elements and carried low levels of Na.     

Assessing the effects of catchment‐scale urban green infrastructure retrofits on hydrograph characteristics

Run‐off from impervious surfaces has pervasive and serious consequences for urban streams, but the detrimental effects of urban stormwater can be lessened by disconnecting impervious surfaces and redirecting run‐off to decentralized green infrastructure. This study used a before–after‐control‐impact design, in which streets served as subcatchments, to quantify hydrologic effectiveness of street‐scale investments in green infrastructure, such as street‐connected bioretention cells, rain gardens and rain barrels. On the two residential treatment streets, voluntary participation resulted in 32.2% and 13.5% of parcels having green infrastructure installed over a 2‐year period. Storm sewer discharge was measured before and after green infrastructure implementation, and peak discharge, total run‐off volume and hydrograph lags were analysed. On the street with smaller lots and lower participation, green infrastructure installation succeeded in reducing peak discharge by up to 33% and total storm run‐off by up to 40%. On the street with larger lots and higher participation, there was no significant reduction in peak or total stormflows, but on this street, contemporaneous street repairs may have offset improvements. On the street with smaller lots, lag times increased following the first phase of green infrastructure construction, in which streetside bioretention cells were built with underdrains. In the second phase, lag times did not change further, because bioretention cells were built without underdrains and water was removed from the system, rather than just delayed. We conclude that voluntary green infrastructure retrofits that include treatment of street run‐off can be effective for substantially reducing stormwater but that small differences in design and construction can be important for determining the level of the benefit. Copyright © 2015 John Wiley & Sons, Ltd.     

Contents of Volume 46

Volume Contents

Contents of Volume 46