Soil n-alkane δD vs. altitude gradients along Mount Gongga, China

The altitude effect on the isotopic composition of precipitation and its application to paleoelevation reconstruction using authigenic or pedogenic minerals have been intensively studied. However, there are still no studies on variations in biomarker δD along altitude transects to investigate its potential as a paleoelevation indicator, although it has been observed that δD of higher plant lipid may record changes in precipitation δD (δD_p). Here, we present δD values of higher plant-derived C₂₇, C₂₉, and C₃₁n-alkanes from surface soil along the eastern slope of Mount Gongga, China with great changes in physical variables and vegetation over a range from 1000 to 4000 m above sea level. The weighted-mean δD values of these n-alkanes (δD_wax) show significant linear correlations with predicted δD_p values (R² = 0.76) with an apparent isotopic enrichment (ε_wax-p) of −137 ± 9‰, indicating that soil δD_wax values track overall δD_p variation along the entire altitudinal transect. Leaf δD_wax is also highly correlated with mountain altitude by a significant quadratic relationship (R² = 0.80). Evapotranspiration is found declining with altitude, potentially lowering δD_wax values at higher elevations. However, this evapotranspiration effect is believed to be largely compensated by the opposing effect of vegetation changes, resulting in less varied ε_wax-p values over the slope transect. This study therefore confirms the potential of using leaf δD_wax to infer paleoelevations, and more generally, to infer the δD of precipitation.     

Solid bitumen reflectance and Rock-Eval Tmax as maturation indices: an example from the “Nordegg Member”, Western Canada Sedimentary Basin

Marine, organic-rich rock units commonly contain little for vitrinite reflectance (VR₀) measurement, the most commoly used method of assessing thermal maturity. This is true of the Lower Jurassic “Nordegg Member”, a type I/II, sulphur-rich source rock from the Western Canada Sedimentary Basin. This study examines the advantages and pitfalls associated with the use of Rock-Eval T_max and solid bitumen reflectance (BR₀) to determined maturity in the “Nordegg”. Vitrinite reflectance data from Cretaceous coals and known coalification gradients in the study area are used to extrapolate VR₀ values for the “Nordegg”.T_max increases non-linearly with respect to both BR₀ and extrapolated VR₀ values. A sharp increase in the reflectaance of both solid bitumen and vitrinite occurs between T_max 440–450°C, and is coincident with a pronounced decrease in Hydrogen Index values and the loss of solid bitumen and telalginite fluorescence over the same narrow T_max interval. This T_max range is interpreted as the main zone of hydrocarbon generation in the “Nordegg”, and corresponds to extrapolated VR₀ values of 0.55–0.85%. The moderate to high sulphur contents in the kerogen played a significant role in determining the boundaries of the “Nordegg” oil window.A linear relationship between BR₀ and extrapolated VR₀, as proposed elsewhere, is not true for the “Nordegg”. BR₀ increases with respect to extrapolated VR₀ according to Jacob's (1985) formula (VR₀=0.618×(BR₀)+0.40) up to VR₀≈0.72% (BR₀≈0.52%). Beyond this point, BR₀ increases sharply relative to extrapolated VR₀, according to the relatioship VR₀ = 0.277 × (BR₀) + 0.57 (R² = 0.91). The break in the BR₀−VR₀ curve at 0.72%VR₀ is thought to signifiy the peak of hydrocarbon generation and represents a previously unrecognized coalification jump in the solid bitumen analogous to the first coalification jump of liptinites.     

The effect of different meteorological parameters on the temporal variations of reference evapotranspiration

Temporal changes of meteorological variables can affect reference evapotranspiration (ET₀). The goal of the present research is to analyze the changes of ET₀ and identify the impact of effective meteorological parameters to the changes of ET₀. For this purpose, daily meteorological data recorded in 30 synoptic stations of Iran during 1960–2014 were used. The annual and seasonal values of ET₀ were calculated by the recorded data. To calculate ET₀, FAO56 Penman–Monteith method (standard method) was used. The annual and seasonal trends of ET₀ and its eight effective parameters were analyzed. Then the contributions of effective parameters changes on ET₀ were determined. To analyze ET₀ trend at annual and seasonal scales, two common methods, Spearman’s Rho and Mann–Kendall tests, were used. The R ² = 0.99 showed that the results of the mentioned methods were similar and on the basis of T-statistic <0.057, their difference was not significant (95% confidence level). Therefore, only one method’s results (Spearman’s Rho) were reported. On the basis of Spearman’s Rho results, the annual and seasonal values of ET₀ had negative trend in most of arid and semi-arid stations while the trend of this parameter was positive in humid and very humid stations. At annual and seasonal scales, decreasing in wind speed (W), temperature (T), sunshine hours (n), minimum temperature (TN), dew point temperature (TD), maximum temperature (TX), saturation vapor pressure deficit (SVPD) and solar radiation (RS) was observed in 58, 54, 39, 43, 56, 65, 65 and 37% studied stations, respectively. In many scales, the results showed that TX and W were the most effective meteorological variables on ET₀ changes and then SVPD was located in second step in arid and semi-arid stations. In humid and very humid stations, W was the first effective parameter at all scales, except autumn.     

Effect of plant life form on relationship between δD values of leaf wax n-alkanes and altitude along Mount Taibai, China

We present δD_wax values from different forms of plants and soils, and δD_sw values from soil water along the northern slope of Mount Taibai, China. The results show a highly negative linear correlation of the δD_wax values for soils with altitude (R² 0.74) and we observed the same correlation for δD_sw values of soil water with altitude (R² 0.68). The δD_wax of living plants behaves like the soil, but does not exhibit a significant linear correlation with altitude (R² 0.11). The δD_wax values of woody plants and grasses also show a similar trend with respect to altitude with significant and no linear correlation, respectively (R² 0.50 for woody plants and 0.17 for grass), which suggest that the “altitude effect” can not be well documented for the δD_wax values of living plants, which may be due to differences in plant type and/or evapotranspiration controlled by the plant microclimate. The ε_wax-sw values of woody plants, grasses and soil show minor fluctuations with altitude. However, the ε_wax-sw and δD_wax values of woody plants are roughly 51‰ and 50‰ more positive, respectively, than those of grasses, suggesting that an “altitude effect” could be documented in the δD_wax of woody plants and grasses, with each responding independently to changes in precipitation along the altitude transect. Additionally, the ε_wax-sw values of soil are relatively constant with altitude, suggesting that the altitudinal change in the proportions between woody plant and grass input to soils will likely change the relationship between the δD_wax values of soil n-alkanes and altitude.     

Use of SWAT to determine the effects of climate and land use changes on streamflow and sediment concentration in the Purna River basin,India

A semi-distributed, physically based, basin-scale Soil and Water Assessment Tool (SWAT) model was developed to determine the key factors that influence streamflow and sediment concentration in Purna river basin in India and to determine the potential impacts of future climate and land use changes on these factors. A SWAT domain with a Geographical Information System (GIS) was utilized for simulating and determining monthly streamflow and sediment concentration for the period 1980–2005 with a calibration period of 1980–1994 and validation period of 1995 to 2005. Additionally, a sequential uncertainty fitting (SUFI-2) method within SWAT-CUP was used for calibration and validation purpose. The overall performance of the SWAT model was assessed using the coefficient of determination (R²) and Nash–Sutcliffe efficiency parameter (E_NS) for both calibration and validation. For the calibration period, the R² and E_NS values were determined to be 0.91 and 0.91, respectively. For the validation period, the R² and E_NS were determined to be 0.83 and 0.82, respectively. The model performed equally well with observed sediment data in the basin, with the R² and E_NS determined to be 0.80 and 0.75 for the calibration period and 0.75 and 0.65 for the validation, respectively. The projected precipitation and temperature show an increasing trend compared to the baseline condition. The study indicates that SWAT is capable of simulating long-term hydrological processes in the Purna river basin.     

Experimental tests of the effects of Al substitution on the goethite-water D/H fractionation factor

Twelve goethite samples with different degrees of substitution of Al for Fe were synthesized at 22-48 °C and pH values of 1.5-14 under closed system conditions and used to study the effects of Al substitution on the hydrogen isotopic fractionation between goethite and its ambient water. The syntheses followed two pathways: (1) Fe³⁺ hydrolysis in high pH aqueous solutions; (2) oxidation of Fe²⁺ to Fe³⁺ in mid to low pH solutions. XRD and SEM analyses indicated that, irrespective of temperature and pH, goethite was the predominant product of the syntheses in all of the experiments (with degrees of Al substitution as high as ∼13 mol %). “High temperature nonstoichiometric” (HTN) water is present in all of the samples and rapidly exchanges D/H with ambient vapor at room temperature. Uncertainties in the value of the apparent D/H fractionation factor (α_e-v) between HTN water and ambient exchange water at 22 °C lead to significant uncertainties in determinations of the δD values of structural hydrogen (δD_s) in goethites which contain high proportions of HTN water. As determined for the samples of this study, α_e-v has a nominal value of 0.942 (±0.02). δD_s values determined using an α_e-v value of 0.942 indicate that Al substitution increases the δD value of structural hydrogen in goethite by about 1.4 (±0.4)‰ for each increase in Al of 1 mol %. This dependence on Al is of the same sign as, but somewhat larger in magnitude than, the effect of Al predicted by a published model (∼0.7‰ per mol % Al). The overall uncertainties in the current results suggest that an increase of ∼1‰ per mol % Al, as adopted by previous studies, may be a reasonable estimate with which to adjust δ D_s values of natural goethites to those of the pure FeOOH endmember and could be valid for degrees of Al substitution of up to at least 15 mol %. These synthesis experiments also yield a hydrogen isotopic fractionation factor (^Dα_G-W) between pure goethite (α-FeOOH) and liquid water of 0.900 (±0.006), which is analytically indistinguishable from the published value of 0.905 (±0.004). Thus, use of an ^Dα_G-W value of 0.905 in applications to the FeOOH component of natural goethites is supported by the current study.     

Intercalibration of the Hb3gr Ar/Ar dating standard

The ⁴⁰Ar/³⁹Ar dating technique is based on the knowledge of the age of neutron fluence monitors (standards). Recent investigations have improved the accuracy and precision of the ages of most of the Phanerozoic-aged standards (e.g. Fish Canyon Tuff sanidine (FCs), Alder Creek sanidine, GA1550 biotite and LP-6 biotite); however, no specific study has been undertaken on the older standards (i.e. Hb3gr hornblende and NL-25 hornblende) generally used to date Precambrian, high Ca/K, and/or meteoritic rocks.In this study, we show that Hb3gr hornblende is relatively homogenous in age, composition (Ca/K) and atmospheric contamination at the single grain level. The mean standard deviation of the ⁴⁰Ar^?/³⁹Ar_K (F-value) derived from this study is 0.49%, comparable to the most homogeneous standards. The intercalibration factor (which allows direct comparison between standards) between Hb3gr and FCs is R_FCs^Hb3gr = 51.945 ± 0.167. Using an age of 28.02 Ma for FCs, the age of Hb3gr derived from the R-value is 1073.6 ± 5.3 Ma (1σ; internal error only) and ± 8.8 Ma (including all sources of error). This age is indistinguishable within uncertainty from the K/Ar age previously reported at 1072 ± 11 Ma [Turner G., Huneke, J.C., Podosek, F.A., Wasserburg, G.J., 1971. ⁴⁰Ar-³⁹Ar ages and cosmic ray exposure ages of Apollo 14 samples. Earth Planet. Sci. Lett. 12, 19-35].The R-value determined in this study can also be used to intercalibrate FCs if we consider the K/Ar date of 1072 Ma as a reference age for Hb3gr. We derive an age of 27.95 ± 0.19 Ma (1σ; internal error only) for FCs which is in agreement with the previous determinations. Altogether, this shows that Hb3gr is a suitable standard for ⁴⁰Ar/³⁹Ar geochronology.     

Dissociation constants of calcite and CaHC03+ from 0 to 50°C

From conductance measurements, the negative logarithm of the dissociation constant of the CaHCO₃₊ ion pair, pK(CaHCO₃⁺), is 0.7, 1.0 and 1.35 within ±0.05 units at 0, 25 and 60°C, respectively. A revaluation of published and unpublished data yields pK(CaCO₃⁰) ≈ 3.2 at 25°C. Use of these pK's to compute the dissociation constant of calcite (Kc) from published calcite solubility measurements in pure water gives pKc values which increase markedly with ionic strength. However, if the ion pairs are ignored, computed pKc values are nearly constant with ionic strength. All reasonable attempts to eliminate the trend in pKc by adjusting ion activity coefficients, and/or values of K(CaCO₃⁰) failed, so the dilemma remains. Kc values computed from the most reliable published calcite solubility data are in good agreement with such values based on solubility data measured in this study at 5, 15, 35 and 50°C. Study results ignoring ion pairs are accurately represented by the equation log Kc = 13.870 — (3059/T) ?0.04035T, and correspond to ?8.35, ?8.42, and ?8.635 at 0, 25 and 50°C, respectively. The logarithmic expression leads to ΔH_r^o = ?2420 ± 300 cal/mol, ΔCp = ?110 ± 2 cal/deg mol, and ΔS_r^o = ?46.6 ± 1.0 cal/deg mol for the calcite dissociation reaction at 25°C. The dependence of Kc on temperature when CaCO₃⁰ and CaHCO₃⁺ are assumed, is described by log Kc = 13.543 ? (3000/T) ? 0.0401T which yields ?8.39, ?8.47, and -8.70 at 0, 25 and 50°C. This gives ΔH_r^o = ?2585 ± 300 cal/mol, ΔCp = ?109 ± 2 cal/deg mol, and ΔS_r⁰ = ?47.4 ± 1.0 cal/deg mol at 25°C.     

过硫酸钠氧化-流动注射化学发光法在地下水腐植酸含量测定中的应用

在碱性条件下过硫酸钠能氧化腐植酸发生化学发光反应。本研究以过硫酸钠-腐植酸化学发光体系为基础,建立了腐植酸的过硫酸钠氧化-流动注射化学发光测定方法,同时对测定方法的负高压及增益、泵速、过硫酸钠浓度、氢氧化钠浓度等影响因素进行了优化实验。方法的线性范围为0.1～500 mg/L(相关系数为0.9985),检出限为0.076 mg/L,对浓度为0.5 mg/L的腐植酸进行11次平行测定,相对标准偏差(RSD)为3.47%。利用该方法对5种不同地区地下水中的腐植酸进行测定,样品的加标回收率在98.33%～107.50%之间。该方法无需分离,简单易行,对实际样品测定结果满意。     

Pressure derivatives of shear and bulk moduli from the thermal Grüneisen parameter and volume-pressure data

Grüneisen’s parameters are central to studies of Earth’s interior because these link elastic data to thermodynamic properties through the equation of state and can be measured using either microscopic or macroscopic techniques. The original derivation requires that the mode Grüneisen parameter (γ_i) of the longitudinal acoustic (LA) mode equals the thermodynamic parameter (γ_th) for monatomic solids. The success of the Debye model indicates that γ_LA = γ_th is generally true. Available elasticity data for crystalline solids contain 30 reliable measurements, covering 10 structures, of the pressure derivatives of the bulk (K_S) and the shear (G) moduli. For these phases, the measured values of γ_th and γ_LA agree well. Other solids in the database have disparate γ_LA values, suggesting large experimental uncertainties within which γ_LA = γ_th. This relationship allows inference of the pressure (P) derivative of the shear modulus (∂G/∂P = G′) from widely available measurements of γ_th, the isothermal bulk modulus (K_T), ∂K_T/∂P, and G. We predict G′ as 1.55 for stishovite, 1.6 to 2.15 for MgSiO₃ ilmenite, 1.0 for γ-Mg_1.2Fe_0.8SiO₄, and 0 for FeS (troilite). Similarly, G′ measured for MgSiO₃ perovskite suggests that K_S′ = 4, corroborating volume-pressure data. For many materials, pairs of G′ and K_S′ = ∂K_S/∂P from independent elasticity studies of a given phase define a nearly linear trend, suggesting systematic errors. Non-hydrostatic conditions and/or pressure calibration likely cause the observed variance in K_S′ and G′. The best values for pressure derivatives can be ascertained because the trend defined by measured pairs of G′ with K_S′ intersects the relationship of G′ to K′ defined by γ_LA = γ_th at a steep angle. Our results for isostructural series show linear correlations of K_S′ with K_S and of G′ with G. Values of K_S′ are nearly 4 for high-pressure phases, which is consistent with the harmonic oscillator model, whereas G′ has a wide range of −1 to 3. Hence, inference of a detailed mineralogy inside the Earth is best constrained by comparing seismic determinations of shear moduli to laboratory measurements.     

The star-formation efficiency and density of the disks of spiral galaxies

The four well studied spiral galaxies M33, M81, M100, and M101 are used to analyze the dependences of the star-formation rate (SFR) and star-formation efficiency (SFE = SFR/M _gas ) on galactocentric distance R and the photometric and some kinematic parameters of galactic disks. The dependences SFR(R) were estimated based on UV and far-infrared data using published extinction-corrected UV brightness profiles of the galaxies. The local SFE values are most closely related to the surface brightness (density) of the galactic disk at a given R, with this dependence being the same for all four galaxies (except for their central regions). In order to explain the observed disk densities in terms of a simple conservative model (“toy model”) for the evolution of the gas density, the local value of the parameter N in the Schmidt law for the disk (SFR ～ σ _gas ^N ) must not exceed unity. In this case, the observed dependences σ _gas (R) and SFE(R) can be matched assuming that accretion is occuring in the central regions of the disks.     

Non-biological fractionation of stable Ca isotopes in soils of the Atacama Desert, Chile

We measured Ca stable isotope ratios (δ^44/40Ca) in an ancient (2 My), hyperarid soil where the primary source of mobile Ca is atmospheric deposition. Most of the Ca in the upper meter of this soil (3.5 kmol m⁻²) is present as sulfates (2.5 kmol m⁻²), and to a lesser extent carbonates (0.4 kmol m⁻²). In aqueous extracts of variably hydrated calcium sulfate minerals, δ^44/40Ca_E values (vs. bulk Earth) increase with depth (1.4 m) from a minimum of −1.91‰ to a maximum of +0.59‰. The trend in carbonate-δ^44/40Ca in the top six horizons resembles that of sulfate-δ^44/40Ca, but with values 0.1-0.6‰ higher. The range of observed Ca isotope values in this soil is about half that of δ^44/40Ca values observed on Earth. Linear correlation among δ^44/40Ca, δ³⁴S and δ¹⁸O values indicates either (a) a simultaneous change in atmospheric input values for all three elements over time, or (b) isotopic fractionation of all three elements during downward transport. We present evidence that the latter is the primary cause of the isotopic variation that we observe. Sulfate-δ³⁴S values are positively correlated with sulfate-δ¹⁸O values (R² = 0.78) and negatively correlated with sulfate δ^44/40Ca_E values (R² = 0.70). If constant fractionation and conservation of mass with downward transport are assumed, these relationships indicate a δ^44/40Ca fractionation factor of −0.4‰ in CaSO₄. The overall depth trend in Ca isotopes is reproduced by a model of isotopic fractionation during downward Ca transport that considers small and infrequent but regularly recurring rainfall events. Near surface low Ca isotope values are reproduced by a Rayleigh model derived from measured Ca concentrations and the Ca fractionation factor predicted by the relationship with S isotopes. This indicates that the primary mechanism of stable isotope fractionation in CaSO₄ is incremental and effectively irreversible removal of an isotopically enriched dissolved phase by downward transport during small rainfall events.     

Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solutions

A surface reaction kinetic model is developed for predicting Ca isotope fractionation and metal/Ca ratios of calcite as a function of rate of precipitation from aqueous solution. The model is based on the requirements for dynamic equilibrium; i.e. proximity to equilibrium conditions is determined by the ratio of the net precipitation rate (R_p) to the gross forward precipitation rate (R_f), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of R_p has been experimentally measured under varying conditions, but the magnitude of R_f is not generally known, and may depend on several factors. It is posited that, for systems with no trace constituents that alter the surface chemistry, R_f can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (R_b or k_b), since at equilibrium R_f = R_b, and R_p = 0. Hence it can be inferred that R_f ≈ R_p + R_b. The dissolution rate of pure calcite is measureable and is known to be a function of temperature and pH. At given temperature and pH, equilibrium precipitation is approached when R_p (=R_f − R_b) ? R_b. For precipitation rates high enough that R_p ? R_b, both isotopic and trace element partitioning are controlled by the kinetics of ion attachment to the mineral surface, which tend to favor more rapid incorporation of the light isotopes of Ca and discriminate weakly between trace metals and Ca. With varying precipitation rate, a transition region between equilibrium and kinetic control occurs near R_p ≈ R_b for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate R_f for calcite precipitation. Mechanistic models for calcite precipitation indicate that the molecular exchange rate is not constant at constant T and pH, but rather is dependent also on solution saturation state and hence R_p. Allowing R_b to vary as , consistent with available precipitation rate studies, produces a better fit to some trace element and isotopic data than a model where R_b is constant. This model can account for most of the experimental data in the literature on the dependence of ⁴⁴Ca/⁴⁰Ca and metal/Ca fractionation in calcite as a function of precipitation rate and temperature, and also accounts for ¹⁸O/¹⁶O variations with some assumptions. The apparent temperature dependence of Ca isotope fractionation in calcite may stem from the dependence of R_b on temperature; there should be analogous pH dependence at pH < 6. The proposed model may be valuable for predicting the behavior of isotopic and trace element fractionation for a range of elements of interest in low-temperature aqueous geochemistry. The theory presented is based on measureable thermo-kinetic parameters in contrast to models that require hyper-fast diffusivity in near-surface layers of the solid.     

Semi-empirical proton binding constants for natural organic matter

Average proton binding constants (K_H,i) for structure models of humic (HA) and fulvic (FA) acids were estimated semi-empirically by breaking down the macromolecules into reactive structural units (RSUs), and calculating K_H,i values of the RSUs using linear free energy relationships (LFER) of Hammett. Predicted log K_H,COOH and log K_H,Ph-OH are 3.73 ± 0.13 and 9.83 ± 0.23 for HA, and 3.80 ± 0.20 and 9.87 ± 0.31 for FA. The predicted constants for phenolic-type sites (Ph-OH) are generally higher than those derived from potentiometric titrations, but the difference may not be significant in view of the considerable uncertainty of the acidity constants determined from acid-base measurements at high pH. The predicted constants for carboxylic-type sites agree well with titration data analyzed with Model VI (4.10 ± 0.16 for HA, 3.20 ± 0.13 for FA; Tipping, 1998), the Impermeable Sphere model (3.50-4.50 for HA; Avena et al., 1999), and the Stockholm Humic Model (4.10 ± 0.20 for HA, 3.50 ± 0.40 for FA; Gustafsson, 2001), but differ by about one log unit from those obtained by Milne et al. (2001) with the NICA-Donnan model (3.09 ± 0.51 for HA, 2.65 ± 0.43 for FA), and used to derive recommended generic values. To clarify this ambiguity, 10 high-quality titration data from Milne et al. (2001) were re-analyzed with the new predicted equilibrium constants. The data are described equally well with the previous and new sets of values (R² ? 0.98), not necessarily because the NICA-Donnan model is overparametrized, but because titration lacks the sensitivity needed to quantify the full binding properties of humic substances. Correlations between NICA-Donnan parameters are discussed, but general progress is impeded by the unknown number of independent parameters that can be varied during regression of a model fit to titration data. The high consistency between predicted and experimental K_H,COOH values, excluding those of Milne et al. (2001), gives faith in the proposed semi-empirical structural approach, and its usefulness to assess the plausibility of proton stability constants derived from simulations of titration data.     

Microspectrofluorescence measurements of coals and petroleum source rocks

Good, reproducible microspectrofluorescence data, similar to published fluorescence trends, are obtainable from samples of coals and petroleum source rocks (shales). These data are reproducible when measured by different operators, different instruments, or at different times (for example, the remeasurement of samples several months apart). These fluorescence data are used to predict maturity or rank to within about 0.10% R₀ (mean vitrinite reflectance, oil immersion). Commercially available computerized fluorescence equipment, with customized software and specific hardware mod modifications, makes the acquisition of fluorescence data feasible. Fluorescence can be used for measuring low-maturity samples, in which the measurement of vitrinite reflectance is difficult. Source rocks from oil-rich basins frequently do not contain enough particles of vitrinite for a reflectance determination, but they may contain fluorescing particles which can be measured. Although the results from only two different kinds of fluorescence equipment (Zeiss Zonax and Vickers Gamma-Scientific) are discussed, any instrument with equivalent stability and sensitivity can be used to attain reproducible and accurate fluorescence data.We propose the use of the term “R_F” to report fluorescence data in equivalent vitrinite reflectance values. Although the principles and techniques of measuring fluorescence were introduced several years ago, much work remains to establish standardized methods of maesuring as well as data evaluation. The current method of reporting fluorescence data in terms of spectral characteristics (such as the wavelength of maximum intensity or wavelength ratios) is awkward to use and difficult to compare results from various laboratories. R_F values convey rank or maturation meaning and can be easily compared among laboratories.Data from fluorescing grains in both coal and petroleum source rock samples are given in this study. Polished samples of coal, this sections, and kerogen strewn slides of source rocks are measured. Spectral data are evaluated by four parameters: the wavelength of maximum intensity (Peak), the red/green ratio (Q), the coordinates of a metric color system (CIE), and the relative intensity at 490 nm. The measurement of intensity, reported in units of radiance, is possible with the Vickers Gamma-Scientific instrument. Measuring both fluorescent colors (R_F) and intensities may help explain some of the relationships among organic particles, maturation, and hydrocarbon generation.     

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.     

Effect of precipitation regime on δD values of soil n-alkanes from elevation gradients - Implications for the study of paleo-elevation

We measured δD values of long chain n-alkanes isolated from 30 surface soil samples along two elevation transects on the Tibetan Plateau differing in precipitation regime and water source. The East Asian Monsoon precipitation dominates the wetter regime on the eastern slope (from 1230 to 4300 m) of Gongga Shan on the eastern Tibetan Plateau. Precipitation from the Polar Westerlies dominates the drier region on the slope from 1900 to 5000 m in the West Kunlun Shan on the northwestern Tibetan Plateau. The decrease in δD value with elevation in the wetter region greatly exceeded that in drier region by, −1.9 ± 0.1‰/100 m and −1.4 ± 1.0‰/100 m respectively. The apparent fractionation between leaf wax and precipitation ε_wax-p values in the wetter region (ca. −164‰) were more negative than those in drier region (ca. −125‰ above 3200 m).We also measured δD values in leaves of six common living trees (values from −287‰ to −193‰) from Gongga Shan, ranging from about 2900-4200 m. The abundance-weighted average values of the n-alkanes (δD_wax) show a strong reverse correlation with sample source elevation (R² 0.78 for soils from Gongga Shan; R² 0.85 for soils from West Kunlun Shan above 3200 m), suggesting that n-alkane δD_wax faithfully records the precipitation δD and that the isotopic altitude effect of precipitation controls δD_wax altitudinal gradients in the mountains. The data show a fairly strong monotonic dependency of n-alkane δD values on elevation for the eastern Plateau, but a complex relationship between n-alkane δD values and elevation for the northwestern Plateau. The δD_wax values at sites below 3200 m from the Kunlun Shan area exhibit an unexpected positive correlation with elevation. The study confirms the potential for using sediment δD_wax values to reconstruct paleo-elevation in wetter regions, but suggests caution in applying the approach to dry regions. Our results also show it is essential to consider the intricacy of the pattern of atmospheric circulation and water sources and their influence on the lapse rate of δD values with elevation.     

Marine reservoir correction for the Pacific coast of central Japan using C ages of marine mollusks uplifted during historical earthquakes

In this study we utilize marine shell samples from two levels of historically uplifted sessile mollusk assemblages and raised wave-cut benches to evaluate the marine reservoir correction (ΔR) for the Pacific coast of central Japan. Elevation measurements of the uplifted marine shells indicate that the lower assemblage emerged during the 1923 Taisho Kanto earthquake (M7.9), whereas uplift of the upper assemblage is most likely but less confidently ascribed to the 1703 Genroku Kanto earthquake (M8.2). Radiocarbon dating of carefully selected samples from the upper and lower assemblages yielded very similar ΔR values of 82 ± 33 and 77 ± 32 yr, respectively. We regard the former ΔR value as a representative and more reliable value given the uncertainty in correlation of the upper assemblage with the 1703 earthquake. This result is consistent with previously reported ΔR values for the Pacific coast of south-central Japan and areas around the Sea of Japan that are influenced by warm ocean currents. Radiocarbon dating of coseismically uplifted shells can aid in estimating marine reservoir ages in the tectonically active Japan Islands.     

Sorption of inorganic 14C on to calcite,montmorillonite and soil

Although ¹⁴C occurs naturally, it is also a waste product of the nuclear industry, and can be important because of its long half-life, high mobility as an anion, and ready incorporation into biota. Some aqueous inorganic species are anionic with migration minimally retarded by most geological and soil materials. Substantial retardation is expected when calcite is present, but there are few data to quantify this effect. The present study measured partition coefficient values, R_d (concentration on solids divided by concentration in liquids), of 8–85 l kg⁻¹ for a series of calcite materials and for a carbonated soil. In contrast, R_d was zero for montmorillonite. The series of calcite materials varied in particle size. In order to investigate the effects of particle size, dissolution and degassing of ¹⁴C and ¹²C were monitored as pH was slowly decreased. The change in pH with addition of acid was strongly affected by particle size, as expected, but there was no systematic effect of particle size on the relative dissolution rates of ¹⁴C vs ¹²C, or on R_d. Apparently, surface area was not a limiting factor in the interaction of ¹⁴C with these materials. The ¹⁴C in soil behaved most like the very fine calcite, indicating that the specific surface of the soil carbonate was similar to that of the very fine calcite.     

Stable isotopic compositions of waters in the karst environments of China: Climatic implications

A total of 117 water samples, including cave water, ground water, spring water and river water, collected from the monsoonal area of China have been analyzed for their H- and O-isotope composition. Overall, a δ¹⁸O–δD correlation is observed of δD = −4.45 + 6.6δ¹⁸O (R² = 0.90) and a significant evaporation effect observed for the southern sites. Average δ¹⁸O and δD site values generally correspond to those of precipitation in nearby cities, with correlations of δD = 2.18 + 7.23δ¹⁸O (R² = 0.95) for the sample sites and δD = 11.05 + 7.95δ¹⁸O (R² = 0.95) for the cities. The effects of rainfall amount and temperature on precipitation δ¹⁸O were calculated using a simplified theoretical model derived from the Rayleigh distillation equation, which demonstrated that the sign of δ¹⁸O_pvs. T correlation is dependent on precipitation intensity. The mean δ¹⁸O value of cave waters exhibit decreasing trends with increasing latitude and reveal a spatial pattern of positive correlation with annual mean temperature and precipitation, mainly reflecting isotopic fractionations in the moisture source traveling from the ocean side to the inland continent. This spatial pattern implies that the δ¹⁸O values recorded in the proxy climate records derived from speleothems might be influenced by shifts in monsoon boundary during the past, especially between glacial and interglacial intervals.