Estimation of drag coefficient over the western desert sector of the Indian summer monsoon trough

In the estimation of momentum fluxes over land surfaces by the bulk aerodynamic method, no unique value of the drag coefficient (C _D) is found in the literature. The drag coefficient is generally estimated from special observations at different parts of the world. In this study an attempt is made to estimate drag coefficient over the western desert sector of India using data sets of Monsoon Trough Boundary Layer Experiment (MONTBLEX) during the summer monsoon season of 1990. For this purpose, the fast and slow response data sets obtained simultaneously from a 30 m high micro-meteorological tower at Jodhpur are used. All the observations used in this study are confined to a wind speed regime of 2.5–9.0 ms⁻¹. A comparison of momentum fluxes computed by eddy correlation (direct estimation) with profile and bulk aerodynamic (C _D = 3.9 × 10⁻³, Garratt, 1977) methods revealed that though the nature of variation of the fluxes by all these methods is almost similar, both the indirect methods give an under-estimated value of the fluxes. The drag coefficient is estimated as a function of wind speed and surface stability by a multiple regression approach. An average value of the estimated drag coefficient is found to be of the order of 5.43 × 10⁻³. The estimated value ofC _D is validated with a set of independent observations and found to be quite satisfactory. The recomputed momentum fluxes by bulk aerodynamic method using the estimated drag coefficient are in close agreement with the directly estimated fluxes.     

Diffusion compensation in natural silicates

The temperature dependence of diffusion is usually found to follow the Arrhenius law: D = D₀e^?E/RT Winchell (1969) showed that there is commonly an inter-dependence between D₀ and E (for diffusion in silicate glasses), such that diffusion of different species show a positive correlation on a log D₀ vs E plot. A similar effect was noted by Hofmann (1980) for cation diffusion in basalt. This implies that diffusion rates of different species tend to converge at a particular temperature; this effect is known as the ‘compensation effect’. I will show that this effect is also present for diffusion in feldspars and olivines. The equations for the compensation lines (with E given in kcal/mol) are: basalt—E = 50 + 7.5 log D₀ feldspar—E = 50.7 + 3.4 log D₀ olivine—E = 78.0 + 7.5 log D₀ The convergence, or crossover, temperatures for diffusion in various materials are: obsidian—3400°C basalt—1370°C olivine—1360°C feldspar—460°C Compensation plots are useful for evaluating and comparing experimental diffusion data (though of limited usefulness in a predictive sense) and for understanding ‘closure temperatures’ for diffusion in petrogenetic processes (since closure temperature, the temperature at which natural diffusion processes are frozen in, is dependent on E, log d₀, and cooling rate). I show that most diffusing species in feldspar have a closure-temperature close to the crossover or convergence temperature, implying that all species in feldspars can be expected to ‘freeze-in’ simultaneously at temperatures in the range 400–600°C (for cooling rates in the range 10¹–10⁵°C/myr). Closure temperatures of various species in olivine, on the other hand, span a much larger range (800°C) for a similar range in cooling rates, implying that different elements in olivine will record different time-temperature stages in petrogenetic processes.     

Dynamics of the stationary eddies in the lower stratospheric circulation in the wavenumber domain and monsoon activity

Meridional transports of momentum and sensible heat have been computed using the Fourier coefficients of the geopotential heights at 50 mb and 30 mb levels for each month during the years 1972 to 1979. Seasonal variations in these transports and in the energy conversionsC (K _E ,K _Z ) andC (A _z ,A _E ) in the contrasting years of monsoon activity have been discussed. The transport and the conversion terms undergo annual variations only with winter maxima and summer minima. Large northward transport of momentum and of sensible heat in the low latitude summer and in the high latitude preceeding winter suggests a linkage between monsoon activity and high latitude stratosphere. Seasonal variations in the energy conversion termsC (K _E ,K _Z ) andC (A _Z ,A _E ) conform with the changes in the system in the years of widely differing monsoon activity both in low and high latitudes. Large conversion of energy fromA _Z toA _E in low latitude summer indicates weakening of the existing meridional temperature gradient, in bad monsoon years.     

Community Oxygen and Nutrient Fluxes in Seagrass Beds of Florida Bay, USA

We used clear, acrylic chambers to measure in situ community oxygen and nutrient fluxes under day and night conditions in seagrass beds at five sites across Florida Bay five times between September 1997 and March 1999. Underlying sediments are biogenic carbonate with porosities of 0.7–0.9 and with low organic content (<1.6%). The seagrass communities always removed oxygen from the water column during the night and produced oxygen during daylight, and sampling date and site significantly affected both night and daytime oxygen fluxes. Net daily average fluxes of oxygen (?4.9 to 49 mmol m^?2 day^?1) ranged from net autotrophy to heterotrophy across the bay and during the 18-month sampling period. However, the Rabbit Key Basin site, located in the west-central bay and covered with a dense Thalassia testudinum bed, was always autotrophic with net average oxygen production ranging from 4.8 to 49 mmol m^?2 day^?1. In November 1998, three of the five sites were strongly heterotrophic and oxygen production was least at Rabbit, suggesting the possibility of hypoxic conditions in fall. Average ammonium (NH₄) concentrations in the water column varied widely across the bay, ranging from a mean of 6.9 μmol l^?1 at Calusa in the eastern bay to a mean of 0.6 μmol l^?1 at Rabbit Key for the period of study. However, average NH₄ fluxes by site and date (?240 to 110 μmol m^?2 h^?1) were not correlated with water column concentrations and did not vary in a consistent diel, seasonal, or spatial pattern. Concentrations of dissolved organic nitrogen (DON) in the water column, averaged by site (15–25 μmol l^?1), were greater than mean NH₄ concentrations, and the range of day and night DON fluxes (?920 to 1,300 μmol m^?2 h^?1), averaged by site and date, was greater than the range of mean NH₄ fluxes. Average DON fluxes did not vary consistently from day to night, seasonally or spatially. Mean silicate fluxes ranged from ?590 to 860 μmol m^?2 h^?1 across all sites and dates, but mean net daily fluxes were less variable and most of the time contributed small amounts of silicate to the water column. Mean concentrations of filterable reactive phosphorus (FRP) in the water column across the bay were very low (0.021–0.075 μmol l^?1); but site average concentrations of dissolved organic phosphorus (DOP) were higher (0.04–0.15 μmol l^?1) and showed a gradient of increasing concentration from east to west in the bay. A pronounced gradient in average surficial sediment total phosphorus (1.1–12 μmol g DW^?1) along an east-to-west gradient was not reflected in fluxes of phosphorus. FRP fluxes, averaged by site and date, were low (?5.2 to 52 μmol m^?2 h^?1), highly variable, and did not vary consistently from day to night or across season or location. Mean DOP fluxes varied over a smaller range (?8.7 to 7.4 μmol m^?2 h^?1), but also showed no consistent spatial or temporal patterns. These small DOP fluxes were in sharp contrast to the predominately organic phosphorus pool in surficial sediments (site means?=?0.66–7.4 μmol g DW^?1). Significant correlations of nutrient fluxes with parameters related to seagrass abundance suggest that the seagrass community may play a major role in nutrient recycling. Integrated means of net daily fluxes over the area of Florida Bay, though highly variable, suggest that seagrass communities might be a source of DOP and NH₄ to Florida Bay and might remove small amounts of FRP and potentially large amounts of DON from the waters of the bay.     

OSL ages and possible bioturbation signals at the Upper Paleolithic site of Lagoa do Bordoal,Algarve, Portugal

Three sediment samples were collected from a soil profile at the Lagoa do Bordoal site, Algarve, Portugal. Quartz extracted from soil horizons within the profile, was optically dated using the single-aliquot regenerative-dose (SAR) protocol outlined by Murray and Wintle (Radiation Measurements 5 (2000) 523). The optically stimulated luminescence (OSL) emitted by quartz within the 90–150 μm size range was measured using three aliquot sizes. The equivalent doses (D_E) that were obtained show an asymmetric distribution. As the numbers of grains in each aliquot are reduced, the distribution of doses is clearly shifted to lower D_E values including zero doses on single grain aliquots. This shift is accompanied by an increase in the asymmetry of the distribution. These patterns indicate that as the aliquot size decreases, the distributions are increasingly characterized by aliquots with lower D_E's. With respect to the present day modern surface, this shift is most evident in the sample collected from a depth of 37 cm, within an ancient B-horizon. It is least evident in the sample located only 10 cm below it, within a sand unit. An asymmetric distribution of D_E's can be a result of a large number of grains that were well bleached at burial being mixed with a small number of grains that were partially bleached at that time (Radiation Measurements 30 (1999) 207). However, the shift in D_E's that is seen in the Lagoa East samples is most likely due to the postburial downward movement of fully and partially bleached grains from the surface, with possible contributions from the downward movement of grains that received low doses while buried in overlying horizons. The simplest explanation for our results is that grains carrying zero or small D_E's have been moved downward during bioturbation events. These results suggest that downward bioturbation in ancient soil profiles can be identified based on the OSL characteristics of quartz grains. We are also able to provide a minimum age of 24.4±3.2 ka for the Upper Palaeolithic lithic assemblage at the site.     

An analysis of MONTBLEX data on heat and momentum flux at Jodhpur

Parameterization of sensible heat and momentum fluxes as inferred from an analysis of tower observations archived during MONTBLEX-90 at Jodhpur is proposed, both in terms of standard exchange coefficientsC _H andC _D respectively and also according to free convection scaling. Both coefficients increase rapidly at low winds (the latter more strongly) and with increasing instability. All the sensible heat flux data at Jodhpur (wind speed at 10 m Ū₁₀ < 8 ms⁻¹) also obey free convection scaling, with the flux proportional to the ‘4/3’ power of an appropriate temperature difference such as that between 1 and 30 m. Furthermore, for Ū₁₀ < 4 ms⁻¹ the momentum flux displays a linear dependence on wind speed.     

Solubility of Ca6[Al(OH)6]2(CrO4)3·26H2O,the chromate analog of ettringite; 5–75°C

Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O, the chromate analog of the sulfate mineral ettringite, was synthesized and characterized by X-ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetric analyses, energy dispersive X-ray spectrometry, and bulk chemical analyses. The solubility of the synthesized solid was measured in a series of dissolution and precipitation experiments conducted at 5–75°C and at initial pH values between 10.5 and 12.5. The ion activity product (IAP) for the reaction Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O⇌6Ca²⁺+2Al(OH)⁻₄+3CrO²⁻₄+4OH⁻+26H₂O varies with pH unless a CaCrO_4(aq) complex is included in the speciation model. The log K for the formation of this complex by the reaction Ca²⁺+CrO²⁻₄=CaCrO_4(aq) was obtained by minimizing the variance in the IAP for Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O. There is no significant trend in the formation constant with temperature and the average log K is 2.77±0.16 over the temperature range 5–75°C. The log solubility product (log K_SP) of Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O at 25°C is −41.46±0.30. The temperature dependence of the log K_SP is log K_SP=A−B/T+D log(T) where A=498.94±48.99, B=27,499±2257, and D=−181.11±16.74. The values of ΔG⁰_r,298 and ΔH⁰_r,298 for the dissolution reaction are 236.6±3.9 and 77.5±2.4 kJ mol⁻¹. the values of ΔC⁰_P,r,298 and ΔS⁰_r,298 are −1506±140 and −534±83 J mol⁻¹ K⁻¹. Using these values and published standard state partial molal quantities for constituent ions, ΔG⁰_f,298=−15,131±19 kJ mol⁻¹, ΔH⁰_f,298=−17,330±8.6 kJ mol⁻¹, ΔS⁰₂₉₈=2.19±0.10 kJ mol⁻¹ K⁻¹, and ΔC⁰_Pf,298=2.12±0.53 kJ mol⁻¹ K⁻¹, were calculated.     

Dynamics of carbon fluxes with responses to vegetation,meteorological and terrain factors in the south-eastern Tibetan Plateau

Tibetan Plateau (TP) is the highest and most extensive plateau in the world and has been known as the roof of the world, and it is sensitive to climate change. The researches of CO₂ fluxes (F _C) in the TP region play a significant role in understanding regional and global carbon balance and climate change. Eddy covariance flux measurements were conducted at three sites of south-eastern TP comprising Dali (DL, cropland ecosystem), LinZhi (LZ, alpine meadow ecosystem) and Wenjiang (WJ, cropland ecosystem); amongst those DL and LZ are located in plateau region, while WJ is in plain region. Dynamics of F _C and influences of vegetation, meteorological (air temperature, photosynthetically active radiation, soil temperature and soil water content) and terrain factors (altitude) were analysed on the basis of data taken during 2008. The results showed that, in the cool sub-season (March, April, October and December), carbon sink appeared even in December with fluxes of (?0.021 to ?0.05) mg CO₂ m^?2 s^?1 and carbon source only in October (0.03 ± 0.0048) mg CO₂ m^?2 s^?1 in DL and WJ site. In LZ site, carbon sink was observed in April: (?0.036 ± 0.0023) mg CO₂ m^?2 s^?1 and carbon sources in December and March (0.008–0.010 mg CO₂ m^?2 s^?1). In the hot sub-season (May–August), carbon source was observed only in May with (0.011 ± 0.0022), (0.104 ± 0.0029) and (0.036 ± 0.0017) fluxes in LZ, DL and WJ site, respectively, while carbon sinks with (?0.021 ± 0.0041), (?0.213 ± 0.0007) and (?0.110 ± 0.0015) mg CO₂ m^?2 s^?1 fluxes in LZ, DL, and WJ, respectively. Comparing with plain region (WJ), carbon sinks in plateau region (DL and LZ) lasted for a longer time, and the absorption sum was large and up to (–357.718 ± 0.0054) and (?371.111 ± 0.0039) g C m^?2 year^?1, respectively. The LZ site had the weakest carbon sink with (?178.547 ± 0.0070) g C m^?2 year^?1. Multivariate analysis of covariance showed that altitude (AL) as an independent factor explained 39.5 % of F _C (P < 0.026). F _C had a quadratic relationship with Normalized difference vegetation index (NDVI) (R ² ranges from 0.485 to 0.640 for three sites), an exponential relationship with soil temperature at 5-cm depth (ST ₅) at night time and a quadratic relationship with air temperature (T _a) at day time. Path analysis indicated that photosynthetically active radiation (PAR), sensible heat fluxes (H) and other factors all had direct or indirect effects on F _C in all of the three tested sites around the south-eastern TP.     

The interaction of magnesium with calcite during crystal growth at 25–90°C and one atmosphere

Calcite crystals were grown in a closed system by recrystallization of synthetic and natural aragonite crystals, in the presence of various CaCl2-MgCl2 solutions with and without NaCl.The distribution of Mg2+ between calcite and solution at the entire temperature range is heterogeneous, closely following the Doerner-Hoskins (Doerner and Hoskins, 1925) distribution law. λMg2+C is strongly dependent on temperature, being: 0·0573 ± 0·0017 at 25°C, 0·0681 ± 0·0019 at 35°C, 0·0778 ± 0.0022 at 50°C, 0·0973 ± 0·0021 at 70°C, and 0·1163 ±0 ·0034 at 90°C. λMg2+C is independent of the absolute concentration of Ca2+ in solution as well as of the presence of NaCl.Relatively high λMg2+C values are obtained during the initial reaction stages when too-highly reactive synthetic aragonites are recrystallized. SEM micrographs show that calcite crystals grown from such aragonites are imperfect and that their earlier formed Mg-rich cores redissolve later, resulting in apparently inconsistent λMg2+C values.Calculations applying the new λMg2+C value for 25°C and the solubility data for magnesian calcites (Chaveet al., 1962) demonstrate that although no calcite should be expected to precipate directly from open sea water, its direct precipitation (or recrystallization from aragonite) is possible in closed diagenetic systems which still contain marine solutions, provided a temporary increase in the dissolved calcium concentration takes place.The λMg2+C values obtained allow for a new insight into processes of calcite cementation of reefs and a variety of other carbonate sediments, and for a more precise definition of dedolomitization chemistry.     

Profile of the H<Subscript>2</Subscript>O supermaser emission: Structure of the ejector region in Orion KL

The structure of the ejector region in the active star-forming region Orion KL has been studied over a broad dynamic range with a high angular resolution of 0.1 milliarcsec, or 0.05 AU. The line profile of the H₂O supermaser emission has broad wings and can be represented as a superposition of two Gaussians with frequency widths Δf₁=31 kHz and Δf₂=163 kHz. The line intensities are I₁≈3×10⁵ Jy/beam and I₂≈400 Jy/beam, and the brightness temperatures, T_b1≈5×10¹⁶ K and T_b2≈6×10¹⁴ K. The broadband ejector emission is determined by a rotating bipolar outflow with a rotational period of 5 months. The ejector emission in the 31-kHz component at a velocity of 7.64 km/s is amplified by more than two orders of magnitude by the surrounding envelope. The maser amplification regime is partially saturated.     

Partitioning of Nb and Ta between rutile and felsic melt and the fractionation of Nb/Ta during partial melting of hydrous metabasalt

In order to fully assess the role of rutile in fractionation of Nb/Ta during partial melting of hydrous metabasalt, we have measured rutile - felsic melt partition coefficients (D values) for Nb and Ta with tonalitic to trondhjemitic compositions at 1.5-3.5 GPa, 900-1350 °C and ∼5.0-20 wt% H₂O. D_Nb, D_Ta and D_Nb/D_Ta range from 17 ± 1 to 246 ± 13, 34 ± 2 to 232 ± 25 and 0.51 ± 0.04 to 1.06 ± 0.13, respectively. For the compositions investigated, melt composition appears to have no observable effect on the partitioning; the effect of pressure is also slight; whereas temperature and H₂O have marked effects. D_Nb, D_Ta and D_Nb/D_Ta increase with decreasing temperature and H₂O content, showing a reversal of D_Nb/D_Ta from <1.0 to >1.0. Using the data that approached equilibrium and obeyed Henry’s law, expressions describing the dependences of D_Nb, D_Ta and D_Nb/D_Ta on temperature, pressure and melt H₂O content were obtained:

(1)     

A thermochemical study of vaterite

Vaterite is shown to be unstable with respect to calcite at 25°C by measurements of the enthalpies of solution in 0·1 N HCl under 0·97 atm CO₂ and the solubilities in water under 0·97 atm CO₂ of the two polymorphs. For a pure, synthetic vaterite ΔH (tr) = ?1036 ±16 cal mol^?1 and ΔG(tr) = ?790 ± 25 cal mol^?1 for the transition to calcite. For other vaterites aged longer during preparation ΔH(tr) is smaller and shows a linear relationship with the X-ray line broadening which extrapolates to ΔH(tr) = ?545 ± 30 cal mo^?1 for zero broadening. The use of X-ray line broadening as a measure of crystal imperfection and stability is discussed for various synthetic and natural vaterites.     

Crystal and molecular structure and spectroscopic behavior of isotypic synthetic analogs of the oxalate minerals stepanovite and zhemchuzhnikovite

The crystal structure of synthetic stepanovite, Na[Mg(H₂O)₆][Fe(C₂O₄)₃]·3H₂O, and zhemchuzhnikovite, Na[Mg(H₂O)₆][Al_0.55Fe_0.45(C₂O₄)₃]·3H₂O, has been determined by single-crystal X-ray diffraction methods. The compounds are isotypic to each other and to the previously reported Na[Mg(H₂O)₆][M(C₂O₄)₃]·3H₂O (M: Cr, Al). They crystallize in the trigonal P3c1 space group with Z = 6 molecules per unit cell and (hexagonal axes) a = 17.0483(4), c = 12.4218(4) Å for the iron compound, and a = 16.8852(5), c = 12.5368(5) Å for the Al/Fe solid solution. Comparison of our crystallographic results with previous X-ray diffraction and chemical data of type stepanovite and zhemchuzhnikovite minerals provides compelling evidence that these natural materials possess the same crystal and molecular structure as their synthetic counterparts. It is shown that the originally reported unit cell for stepanovite represents a pronounced sub-cell and that the correct unit cell and space group are based on weak superstructure reflections. The infrared and Raman spectra of both synthetic analogs were also recorded and are briefly discussed.     

Biogeochemical cycling in an organic-rich coastal marine basin. 6. Temporal and spatial variations in sulfate reduction rates

Rates of sulfate reduction were measured over a 3 year period in the anoxic nearshore sediments of Cape Lookout Bight, North Carolina, using both a tube incubation method and a ³⁵S-sulfate direct injection technique. The methods yielded similar depth-integrated rates over the upper 30 cm ranging from less than 10 mol SO⁼₄ · m⁻² · y⁻¹ in winter to greater than 50 mol SO⁼₄ · m⁻² · y⁻¹ in summer. There were also seasonal changes in the Arrhenius activation energies for the sulfate reduction rates indicating that the assumption that E_a is constant with temperature is not always valid. The time averaged annual turnover rate for all three years was 20.4 (±11.4) mol SO⁼₄ · m⁻² · y⁻¹. Surface rates ranged seasonally from less than 0.01 to over 3 mM SO⁼₄ · d⁻¹ between winter and summer, respectively. A subsurface rate maximum was observed to develop during the summer months which accounted for 28 percent of the annual depth integrated sulfate reduction rate. Subsurface rate maxima are the result of changes in the chemistry (substrate type and/or concentration) and the microbiology in the sediments. The possibility of the subsurface maximum being an artifact of the ³⁵S method is also discussed. However, the sulfate reduction rates compare well with previous measurements of the carbon sediment-water plus burial fluxes and with a depth integrated CO₂ production rate modelled from a ΣCO₂ concentration profile from the same site.     

Biogeochemical cycling in an organic rich coastal marine basin—II. Nutrient sediment-water exchange processes

The release of remineralized N and P from the organic-rich anoxic sediments of Cape Lookout Bight is controlled by processes occurring within the sediment column and at the sediment-water interface. The relatively rapid rates of temperature dependent microbial degradation of organic matter support seasonally varying nutrient fluxes ranging from 20 to 1200 μmol·m^?2·hr^?1 for dissolved ammonium and from ? 20 to 120 μmol·m^?2·hr^?1 for total dissolved phosphate (measured in situ over the period October, 1976 to October, 1978). Molecular diffusion along steep vertical pore water concentration gradients measured simultaneously cannot explain the high fluxes observed during warmer months. Gradients for ammonium and phosphate ranged from 0.33 to 1.10 and from 0 to 0.29 μmol·cm^?3_pw·cm^?1_s respectively. These high summertime fluxes appear to result from increased sediment-water transport associated with bubble tubes created and maintained by low-tide methane gas bubble ebullition. When these tubes are present, apparent bulk sediment diffusivities calculated from concurrent studies of methane and radon-222 sediment-water exchange are 1.0–3.1 times greater than molecular diffusivities. Nutrient fluxes calculated via Fick's first law taking into account this enhanced transport and the differential diffusive mobilities of dissolved ammonium, phosphate and phosphate ion pairs indicate that removal by aerobic adsorption and/or biological uptake at the sediment-water interface plays an important role in controlling nutrient exchange in these sediments.     

Hydrogen isotopic ratios of plant wax n-alkanes in a peat bog deposited in northeast China during the last 16 kyr

Based on paleoclimatic reconstructions using various proxies, the Holocene Climate Optimum (10.5–6 ka) has been characterized as a warmer and wetter period in most of East Asia. The summer monsoons associated with the East Asian Monsoon evidently intensified and extended further inland from the Pacific Ocean, a source region of moisture. A notable exception to this general pattern exists in northeast China, where less wet conditions are recorded. We determined molecular compositions of individual plant wax hydrocarbons and their hydrogen isotope compositions (δD values) in a radiocarbon-dated peat core recovered from the Hani marsh in Jilin Province (China) and confirmed that the temperature-dependent effective precipitation in northeast China decreased during the Holocene Climate Optimum. A combination of P_aq, an indicator of the relative contribution of aquatic to terrestrial plants, and the difference in δD between low (C₂₃, C₂₅ and C₂₇) and high molecular weight (C₃₁) n-alkanes in the Hani peat bog indicates a dramatic change in vegetation from the deglaciation to the Holocene. No significant differences were observed between the δD values of low and high molecular weight n-alkanes with relatively high δD values and low P_aq during the early Holocene, indicating that all n-alkanes were produced by evapotranspiration-sensitive terrestrial plants during that time. However, lower δD values of mid-chain n-alkanes (C₂₃, C₂₅ and C₂₇) relative to the long chain n-alkane (C₃₁), together with higher P_aq values during the deglaciation (14–11 ka), suggest an increase in the contribution of aquatic plants and a higher water level during the period. The study demonstrates that northeast China was under a markedly wetter climate condition during the late deglaciation. For the 16 kyr record in the Hani peat sequence, we infer that moisture delivery by the East Asian Monsoon was relatively invariable in northeast China, but increased evaporation during the warmer Holocene Climate Optimum reduced the effective precipitation, defined by the balance between precipitation and evaporation.     

Partitioning of transition elements between orthopyroxene and clinopyroxene in peridotitic and websteritic xenoliths: new empirical geothermometers

The partitioning of transition elements (Sc, Ti, V, Cr, Mn, Co, Ni) between orthopyroxene (opx) and clinopyroxene (cpx) in carefully selected garnet peridotite, spinel peridotite and garnet websterite xenoliths was determined by electron probe microanalyses (EPMA) and secondary ion mass spectrometry (SIMS). Xenoliths studied cover a wide compositional range and equilibrated under variable upper mantle conditions at temperatures between about 760 and 1370°C (two-pyroxene thermometer based on the enstatite-diopside solvus) and pressures between about 0.8 and 3.6 GPa (Al-in-opx and Ca-in-olivine barometers). We found that the partitioning of transition elements between opx and cpx (expressed as D_M = concentration of element M in opx [cations per formula unit]/concentration of M in cpx [cations per formula unit]) is mainly controlled by temperature and to a much lesser degree by pressure. Variations in major element compositions of pyroxenes (e.g., variable X_Mg, Al^IV or Na) have no influence on D_M. For Sc, V, Cr, Mn, and Co, our data result in good correlations between ln D_M and reciprocal absolute temperature, with correlation coefficients (r) between 0.950 and 0.981. It is therefore possible to use the partitioning of these elements between opx and cpx from peridotites and websterites as geothermometers. On the basis of our data, we suggest the following empirical thermometer equations: T_Sc = [(17.64 · P + 5663)/(3.25 − ln D_Sc)], T_V = [(18.06 · P + 3975)/(2.27 − ln D_V)], T_Cr = [(11.00 · P + 2829)/(1.56 − ln D_Cr)], T_Mn = [(−0.20 · P − 2229)/(−1.37 − ln D_Mn)], T_Co = [(−4.31 · P − 2358)/(−0.98 − ln D_Co)], where T is the absolute temperature in Kelvin and P the pressure in kilobars. For Ti and Ni observed correlations between ln D_M and 1/T are less well defined.     

Water diffusion in dacitic melt

H₂O diffusion in dacitic melt was investigated at 0.48-0.95 GPa and 786-893 K in a piston-cylinder apparatus. The diffusion couple design was used, in which a nominally dry dacitic glass makes one half and is juxtaposed with a hydrous dacitic glass containing up to ∼8 wt.% total water (H₂O_t). H₂O concentration profiles were measured on quenched glasses with infrared microspectroscopy. The H₂O diffusivity in dacite increases rapidly with water content under experimental conditions, similar to previous measurements at the same temperature but at pressure <0.15 GPa. However, compared with the low-pressure data, H₂O diffusion at high pressure is systematically slower. H₂O diffusion profiles in dacite can be modeled by assuming molecular H₂O (H₂O_m) is the diffusing species. Total H₂O diffusivity D_H2Ot within 786-1798 K, 0-1 GPa, and 0-8 wt.% H₂O_t can be expressed as: where D_H2Ot is in m²/s, T is temperature in K, P is pressure in GPa, K = exp(1.49 − 2634/T) is the equilibrium constant of speciation reaction (H₂O_m+O?2OH) in the melt, X = C/18.015/[C/18.015 + (100 − C)/33.82], C is wt.% of H₂O_t, and 18.015 and 33.82 g/mol correspond to the molar masses of H₂O and anhydrous dacite on a single oxygen basis. Compared to H₂O diffusion in rhyolite, diffusivity in dacite is lower at intermediate temperatures but higher at superliquidus temperatures. This general H₂O diffusivity expression can be applied to a broad range of geological conditions, including both magma chamber processes and volcanic eruption dynamics from conduit to the surface.     

Pressure and composition dependence of the electrical conductivity of iron-rich synthetic olivines to 200 kbar

The objectives of this study of olivines are, to calibrate the variation of electrical conductivity with pressure, up to 200 kbar in a diamond-anvil cell, and to determine how this is influenced by chemical composition. Experimentally, we have found that the variation of the electrical conductivity of three synthetic olivines containing 50, 75 and 100 mole percent of fayalite, is an exponential function of pressure P, closely represented at room temperature by:σ_xP=σ_x·exp ·(B _x·P) where x is the iron content of the olivine, σ _x the extrapolated value of conductivity at normal pressure and B _x the slope of the regression line in semi-logarithmic coordinates. It is thus possible to express the temperature dependence of conductivity through the Boltzmann relationship:σ_xPT= σ_αT· exp ·(-H*/RT)=σ_xT·exp ·[-(E*+PV _* ^x )/RT] where H* is the activation enthalpy, E* the activation energy and V _x ^* the activation volume. At constant temperature V _* ^x =B _x·RT and is approximately equal to 0,6 cm³/mole at 295 K. On the other hand, we have found that σ_xT is an exponential function of x and thus, B _x and of course V _x ^* are linear functions. The experimental procedure is described and the results discussed.     

Can sedimentary leaf waxes record D/H ratios of continental precipitation? Field, model, and experimental assessments

D/H ratios of leaf waxes (δD_wax) derived from terrestrial plants and preserved in lake sediments can provide important information on past continental hydrology. Ideally, δD_wax can be used to reconstruct precipitation D/H ratios (δD_P) which is a well-established paleoclimate proxy. However, many other factors, such as vegetation and relative humidity (RH), also affect δD_wax variation. How the combination of these factors affects sedimentary δD_wax is unclear. Here, we use a transect of 32 lake surface sediments across large gradients of precipitation, relative humidity, and vegetation composition in the southwestern United States to study the natural factors affecting sedimentary δD_wax. δD values of C₂₈n-alkanoic acids show significant correlation with δD_P values (R² = 0.76) with an apparent isotopic enrichment of ∼99 ± 8‰, indicating that sedimentary δD_wax values track overall δD_P variation along the entire transect. Leaf waxes produced by plants grown under controlled conditions (RH = 80%, 60%, 40%) show a small increase in D/H ratios as RH decreases, consistent with prediction from the Craig-Gordon model. However, the isotopic effect of RH on δD_wax along the natural transect is partially countered by the opposing influence of vegetation changes. The correlation between δD_wax and δD_P values is significantly higher (R² = 0.84) in the drier portions of the transect than in the wetter regions (R² = 0.64). This study suggests that D/H ratios of sedimentary leaf waxes can be used as a proxy for precipitation δD variations, with particularly high fidelity in dry regions, although more studies in other regions will be important to further test this proxy.