Complete chemical analyses of metamorphic hornblendes: implications for normalizations,calculated H2O activities,and thermobarometry

Twenty-two hornblendes separated from amphibolites and granulites of the Grenville Orogen of Ontario have been quantitatively analyzed for major and minor elements by electron microprobe, for FeO/Fe₂O₃ by wet chemistry, and for H₂O by manometric measurement as H₂. Hornblende formulae were calculated on the basis of 24O+OH+Cl+F. Most samples are magnesio-hornblendes, ferroan pargasitic hornblendes and ferroan hastingsitic hornblendes, with weight fractions of Fe³⁺/(Fe²⁺+Fe³⁺) ranging from 0.15 to 0.50. An oxy-amphibole component of 0–25 mol%, with an average value of 17 mol%, is obtained for these complete analyses. When compared with structural formulae determined solely from microprobe data, normalization based on 13=Si+Ti+Al+Fe+Mn+Mg cations provides the best approximation to hornblende formulae calculated from the complete analyses. Less satisfactory agreement is obtained from a normalization scheme based on 15=Si+Ti+Al+Fe+Mn+Mg+Ca, while worst agreement is obtained from normalization to 23 oxygens assuming all Fe is Fe²⁺. No normalization scheme based on microprobe data alone consistently replicates the measured FeO, Fe₂O₃, and H₂O; accurate determination of these values requires complete chemical analysies. Ionic solution models previously have been proposed to evaluate the activity of Ca₂Mg₅Si₈ O₂₂(OH)₂(a _Trem) in hornblende for use in equilibria that constrain the activity of H₂O (a _{H 2}O) in igneous and metamorphic rocks. Application of ionic models to typical hornblendes produces low a _Trem (usually<0.01), consequetly yielding extremely low a _{H 2}O. If an oxy-amphibole component is present, the calculated a _Trem and H₂O is further reduced. An oxy-amphibole component of 25% reduces the calculated H₂O activity and that of any hydroxyl-amphibole component by 50% below that calculated with simplified assumptions regarding X _OH in the hydroxyl site (i.e., X _OH=1, or X _OH=1–X _Cl–X _f). Thus, methods of amphibole normalizations appear to have a substantial effect on calculated amphibole and H₂O activites. Before quantitative hornblende thermobarometry can be calibrated and applied, the amounts of FeO, Fe₂O₃ and H₂O must be measured in order to fully characterize hornblende solid solutions.Contribution No. 478 from the Mineralogical Laboratory, University of Michigan     

Mid-holocene climate change in Lake Bosumtwi, Ghana

Lake Bosumtwi is one of the most widely studied palaeoclimate archives in West Africa. Results from numerous AMS ¹⁴C dates of samples from four piston cores from Lake Bosumtwi show that an abrupt sedimentary transition from a mid-Holocene sapropel to calcareous laminated muds occurred at about 3200 cal yr B.P. High-resolution analyses of the nitrogen isotopic composition of organic matter across this transition confirm its abrupt nature, and suggest that the change may signal a step toward increased aridity and intensified surface winds that affected western equatorial Africa from Ghana to the Congo basin. Northern and Eastern Africa experienced a similar abrupt shift toward aridity during the late Holocene, but at about 5000 cal yr B.P., a difference in timing that illustrates the regional nature of climate changes during the Holocene and the importance of feedback mechanisms in regulating Holocene climate variability. Furthermore, an abrupt change at about 3000 cal yr B.P. occurs at several sites adjacent to the tropical and subtropical Atlantic, which may hint at major changes in the surface temperatures of the tropical Atlantic and/or Pacific at this time.     

Organic carbon isotope and molecular fossil records of vegetation evolution in central Loess Plateau since 450 kyr

Significant uncertainties remain regarding the temporal evolution of natural vegetation during the Quaternary, and drivers of past vegetation change, on the Chinese Loess Plateau (CLP). This study presents analyses of total organic carbon isotopic composition (TOC) and n-alkane ratios (C31/C27) from the Lingtai loess-palaeosol sequence on the central CLP over the last 450 kyr. The results demonstrate that the vegetation in this region comprised a mix of C₃ and C₄ plants of herb and woody growth-form. C₃ plants dominated for most of the last 450 kyr, but this did not lead to extensive forest. C₃ woody plants were more abundant in MIS9 (S3 period) and MIS5 (S1 period) during warm and humid climate conditions. Herbs increased in the region since 130 kyr, possibly as a result of increased aridity. On the orbital timescales, there was a reduction of C₃ herbal plants in MIS11 (S4) than in MIS12 (L5), and in Holocene than in the last glacial period. Our isotope and n-alkane proxy records are in agreement with Artemisia pollen changes in the region, which is/was the dominant species in this area and varying due to different heat and water conditions between glacial and interglacial periods. Though the climate in MIS1 (S0) was similar to that in MIS11 (S4), a significant increase in woody plants during the Holocene suggests the impact of human activities and ecological effects of changes in fire activity.     

The Great Lakes diversion at Chicago and its implications for climate change

In 1900 the city of Chicago began diverting sizable amounts of water from Lake Michigan to move its sewage down the Illinois River. This diversion launched a series of continuing legal controversies involving Illinois as a defendant against claims by the federal government, various lake states, and Canada who wanted the diversion stopped or drastically reduced. During the past 96 years extended dry periods have lowered the lake levels. Using these dry periods as surrogates for future conditions, their effects on the past controversies were examined as analogs for what might occur as a result of climate change from an enhanced Greenhouse effect. The results reveal that changing socioeconomic factors including population growth will likely cause increased water use, and Chicago will seek additional water from the Great Lakes. New priorities for water use will emerge as in the past. Drier future conditions will likely lead to enhanced diversions from the Great Lakes to serve interests in and outside the basin. Future lower lake levels (reflecting a drier climate) will lead to conflicts related to existing and proposed diversions, and these conflicts would be exacerbated by the consequences of global warming. In any event, a warmer, drier climatic regime will challenge existing laws and institutions for dealing with Great Lakes water issues.     

Stratospheric ozone: Impact of human activity

Current knowledge of the chemistry of the stratosphere is reviewed using measurements from the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment to test the accuracy of our treatment of processes at mid-latitudes, and results from the Airborne Antarctic Ozone Experiment (AAOE) to examine our understanding of processes for the polar environment. It is shown that, except for some difficulties with N₂O₅ and possibly ClNO₃, gas phase models for nitrogen and chlorine species at 30°N in spring are in excellent agreement with the data from ATMOS. Heterogeneous processes may have an influence on the concentrations of NO₂, N₂O₅, HNO₃, and ClNO₃ for the lower stratosphere at 48°S in fall. Comparison of model and observed concentrations of O₃ indicate good agreement at 30°N, with less satisfactory results at 48°S. The discrepancy between the loss rate of O₃ observed over the course of the AAOE mission in 1987 and loss rates calculated using measured concentrations of ClO and BrO is found to be even larger than that reported by Anderson et al. (1989, J. geophys. Res. 94, 11480). There appear to be loss processes for removal of O₃ additional to the HOC1 mechanism proposed by Solomon et al. (1986, Nature 321, 755), the ClO-BrO scheme favored by McElroy et al. (1986, Nature 321, 759), and the ClO dimer mechanism introduced by Molina and Molina (1987, J. phys. Chem. 91, 433). There is little doubt that industrial halocarbons have a significant impact on stratospheric O₃. Controls on emissions more stringent than those defined by the Montreal Protocol will be required if the Antarctic Ozone Hole is not to persist as a permanent feature of the stratosphere.     

Towards a detailed distal tephrostratigraphy in the Central Mediterranean: The last 20,000 yrs record of Lago Grande di Monticchio

A detailed compilation of distal tephrostratigraphy comprising the last 20,000 yrs is given for the Central Mediterranean region. A total of 47 distinct ash layers identified in the maar lake sediments of Lago Grande di Monticchio (Basilicata, Southern Italy) are compared with proximal and distal terrestrial-marine tephra deposits in the circum-central Mediterranean region. The results of these studies provide valuable information for reconstructing the Late Pleistocene and the Holocene dispersal of pyroclastic deposits from south Italian explosive volcanoes, in particular Somma-Vesuvius, the Campi Flegrei caldera, Ischia Island and Mount Etna. Prominent tephras are discussed with respect to their reliability as dating and correlation tools in sedimentary records. Ashes from Plinian eruptions of Somma-Vesuvius (i.e. Avellino, Mercato, Greenish, Pomici di Base), for instance, are well-defined by their distribution patterns and their unique composition. The widespread Y-1 tephra from Mount Etna, on the other hand, derived most likely from two distinct Plinian events with changing wind conditions, and therefore becomes a less reliable stratigraphic marker. Statistical–numerical calculations are presented in order to discriminate between Holocene tephras from the Campi Flegrei caldera (i.e. Astroni 1–3, Agnano Monte Spina, Averno 1, Lagno Amendolare), since these ashes are characterized by an almost indistinguishable chemical fingerprint. As a highlight, numerous Campanian eruptions of proposed low-intensity have been identified in the distal site of Monticchio suggesting a revision of existing tephra dispersal maps and re-calculation of eruptive conditions. In summary, the tephra record of Monticchio is one of the key successions for linking both, terrestrial records from Central-southern Italy and marine sequences from the Tyrrhenian, Adriatic and Ionian Seas.     

Range imaging: a new method for high‐resolution topographic measurements in small‐ and medium‐scale field sites

Topographic measurements are essential for the study of earth surface processes. Three‐dimensional data have been conventionally obtained through terrestrial laser scanning or photogrammetric methods. However, particularly in steep and rough terrain, high‐resolution field measurements remain challenging and often require new creative approaches. In this paper, range imaging is evaluated as an alternative method for obtaining surface data in such complex environments. Range imaging is an emerging time‐of‐flight technology, using phase shift measurements on a multi‐pixel sensor to generate a distance image of a surface. Its suitability for field measurements has yet not been tested. We found ambient light and surface reflectivity to be the main factors affecting error in distance measurements. Low‐reflectivity surfaces and strong illumination contrasts under direct exposure to sunlight lead to noisy distance measurements. However, regardless of lighting conditions, the accuracy of range imaging was markedly improved by averaging multiple images of the same scene. For medium ambient lighting (shade) and a light‐coloured surface the measurement uncertainty was approximately 9 mm. To further test the suitability of range imaging for field applications we measured a reach of a steep mountain stream with a horizontal resolution of approximately 1 cm (in the focal plane of the camera), allowing for the interpolation of a digital elevation model on a 2 cm grid. Comparison with an elevation model obtained from terrestrial laser scanning for the same site revealed that both models show similar degrees of topographic detail. Despite limitations in measurement range and accuracy, particularly at bright ambient lighting, range imaging offers three‐dimensional data in real time and video mode without the need of post‐processing. Therefore, range imaging is a useful complement or alternative to existing methods for high‐resolution measurements in small‐ to medium‐scale field sites. Copyright © 2012 John Wiley & Sons, Ltd.     

Experimental study of igneous and sedimentary apatite dissolution: Control of pH, distance from equilibrium, and temperature on dissolution rates

Apatite dissolution experiments were conducted using both a fluidized bed and stirred tank reactor over a range of pH, temperature, solution saturation state, and on non-carbonated and carbonated apatite compositions: igneous fluorapatite (FAP) and sedimentary carbonate fluorapatite (CFA), respectively. From 2 <pH <6, the rate of release from dissolution of all apatite components [calcium (Ca), phosphorus (P), and fluoride (F)] increased with decreasing pH for FAP. From 6 < pH < 8.5, the FAP dissolution rate is pH independent. Measuring apatite dissolution rates at pH > 8.5 were not possible due to detection limits of the analytical techniques used in this study and the high insolubility of FAP. For the CFA compositions studied, the dissolution rate decreased with increasing pH from 4 < pH < 7. During early stages of the dissolution reaction for both FAP and CFA, mineral components were released in non-stoichiometric ratios with reacted solution ratios of dissolved Ca:P and Ca:F being greater than mineral stoichiometric ratios, suggesting that Ca was preferentially released compared to P and F from the mineral structure during the early stages of dissolution. An increase in reacted solution pH accompanies this early elevated release of Ca. As the dissolution reaction proceeded to steady state, dissolution became congruent. When normalized to BET measured surface area, FAP dissolved faster from 4 < pH < 7 compared to CFA. The apparent Arrhenius activation energy (E_a) of FAP dissolution over the temperature range of 25-55°C at pH = 3.0, I = 0.1, and pCO₂ = 0 is 8.3 ± 0.2 kcal mol⁻¹. Both the apparent exchange of solution H⁺ for solid-bound Ca at low pH in the early stage of dissolution and the E_a of dissolution suggest a surface and not a diffusion controlled dissolution reaction for FAP and CFA. The degree of undersaturation of the solution, ΔG_R, with respect to FAP was important in determining the dissolution rate. At pH = 3.0, I = 0.1, and pCO₂ = 0, the dissolution rate of FAP was ∼ 5× greater in the far-from-equilibrium region compared to the near-equilibrium slope region.A simple apatite weathering model incorporating the experimental results from this study was constructed, and numerical calculations suggest that during the Phanerozoic both the surface area of igneous rock available for weathering and the average global temperature were important factors in determining the P weathering flux from apatite dissolution. It is possible that elevated global temperatures coupled with relatively high surface area of igneous rock during the early- to mid-Paleozoic resulted in elevated P weathering fluxes, which along with climatic evolutionary pressures of the Neoproterozoic, facilitated the radiation of multicellular organisms, large-scale phosphorite deposition, and abundance of calcium phosphate shelled organisms during the early Cambrian.     

Textural characteristics of sediments along the southern Red Sea coastal areas,Saudi Arabia

A lack of understanding exists of the origin and textural characteristics of Saudi Arabian Red Sea coastal sediments. This paper concerns the southern coastline of Jizan on the Saudi Red Sea. It is some 160 km long characterised by either narrow rocky headlands with intermittent pocket beaches or wide low-lying beaches dissected by wadis. Granulometric testing of samples from 135 locations showed that beach sand size was mainly very fine to medium grained (M _z = 3.93 Ø), sorting ranged from 1.65 to 0.41 and skewness values from ?051 to 0.39, being mainly negative; dune sands were medium to fine grained (M _z = 1.13 Ø; average sorting 2.8), while skewness variations within dune samples indicated symmetrical to fine skewed values (б _Ι = 0.55 to 0.89). Most foreshore samples were derived from wadis. Wadi mud levels can be high, e.g. Baysh (84%), and wadi Samrah (90%) with mean grain size ranging from very fine to medium sand (M _z = 3.9 Ø), sorting being well to poor (0.45 to 1.52) due to sediment influxes. Sabkha had a wide range of sand/mud and significantly higher carbonate percentages than other environments. Sediment source differences and littoral reworking contributed to grain size variation. The carbonate content varied between 1.5 and 31.5% due to hinterland contributions, and spatial analysis showed increasing quantities of carbonate minerals towards the south. On the wider geographical front, findings from Jizan are similar to those of the Northern United Arab Emirates (UAE), including sabkhas, being composed of sand, skeletal carbonate, fine fluvial material and wind-blown silt and clay components of wadi origin. Further work on the northeastern Red Sea edge can hopefully confirm these findings.     

On the use of X-ray and γ-ray telescopes for identifying the origin of electrons and positrons observed by ATIC, Fermi, and PAMELA

X-ray and γ-ray observations can help understand the origin of the electron and positron signals reported by ATIC, PAMELA, PPB-BETS, and Fermi. It remains unclear whether the observed high-energy electrons and positrons are produced by relic particles, or by some astrophysical sources. To distinguish between the two possibilities, one can compare the electron population in the local neighborhood with that in the dwarf spheroidal galaxies, which are not expected to host as many pulsars and other astrophysical sources. This can be accomplished using X-ray and γ-ray observations of dwarf spheroidal galaxies. Assuming the signal detected by Fermi and ATIC comes from dark matter and using the inferred dark matter profile of the Draco dwarf spheroidal galaxy as an example, we calculate the photon spectrum produced by electrons via inverse Compton scattering. Since little is known about the magnetic fields in dwarf spheroidal galaxies, we consider the propagation of charged particles with and without diffusion. Extending the analysis of Fermi collaboration for Draco, we find that for a halo mass ∼10⁹ M_⊙, even in the absence of diffusion, the γ-ray signal would be above the upper limits. This conclusion is subject to uncertainties associated with the halo mass. If dwarf spheroidal galaxies host local magnetic fields, the diffusion of the electrons can result in a signal detectable by future X-ray telescopes.