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Agricultural grasses cover a major part of the land surface in temperate agro-ecosystems and contribute significantly to the formation of soil organic matter. Crop-derived lipids are assumed to be responsible for fast carbon turnover in soils. Differences in lipid distribution patterns between crops following C3 and C4 photosynthesis pathways have rarely been described, but could be useful for source apportionment of crop-derived input into soils or sediments. The distribution of long chain n-carboxylic acids (C22, C24, C26) reveals significant differences between crop plants following either the C3 or the C4 photosynthetic carbon fixation pathway. The plant compartments leaves, stems and roots of C4 plants contain relatively large proportions (> 40%) of n-C24 carboxylic acid when compared to C3 plants. These reveal larger relative proportions of n-C22 and n-C26 acids, whose relative abundance is subject to change between different plant compartments and during the growing season. The carboxylic acid ratio [CAR = n-C24/(n-C22 + n-C26) carboxylic acids] provides distinct ratios for C4 (> 0.67) and C3 crops (< 0.67) and can thus be used as a molecular marker for the differentiation of crop plant biomass. In combination with the bulk stable carbon isotopic composition (δ13C) the CAR can be used as a tool for the estimation of the C4 derived carbon proportion in soils or sediments. 相似文献
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John W. Washington Robert C. Thomas Katherine L. Schroer 《Geochimica et cosmochimica acta》2006,70(14):3533-3548
Excess N from agriculture induces eutrophication in major river systems and hypoxia in coastal waters throughout the world. Much of this N is from headwaters far up the watersheds. In turn, much of the N in these headwaters is from ground-water discharge. Consequently, the concentrations and forms of N in groundwater are important factors affecting major aquatic ecosystems; despite this, few data exist for several species of N in groundwater and controls on speciation are ill-defined. Herein, we report N speciation for a spring and well that were selected to reflect agricultural impacts, and a spring and well that show little to no agricultural-N impact. Samples were characterized for NO3−, NO2−, N2O, NH4+, urea, particulate organic N(), and dissolved organic N(). These analytes were monitored in the agricultural spring for up to two years along with other analytes that we reported upon previously. For all samples, when oxidized N was present, the dominant species was NO3− (88-98% of total fixed N pool) followed by (<4-12%) and only trace fractions of the other N analytes. In the non-agriculturally impacted well sample, which had no quantifiable NO3− or dissolved O2, comprised the dominant fraction (68%) followed by NH4+ (32%), with only a trace balance comprised of other N analytes. Water drawn from the well, spring and a wetland situated in the agricultural watershed also were analyzed for dissolved N2 and found to have a fugacity in excess of that of the atmosphere. H2O2 was analyzed in the agricultural spring to evaluate the O2/H2O2 redox potential and compare it to other calculated potentials. The potential of the O2/H2O2 couple was close in value to the NO3−/NO2− couple suggesting the important role of H2O2 as an O2-reduction intermediate product and that O2 and NO3− are reduced concomitantly. The O2/H2O2 and NO3−/NO2− couples also were close in value to a cluster of other inorganic N and Fe couples indicating near partial equilibrium among these species. Urea mineralization to NO2− was found to approach equilibrium with the reduction of O2 to H2O2. By modeling as amide functional groups, as justified by recent analytical work, similar thermodynamic calculations support that mineralization to NO2− proceeds nearly to equilibrium with the reduction of O2 to H2O2 as well. This near equilibration of redox couples for urea- and -oxidation with O2-reduction places these two couples within the oxidized redox cluster that is shared among several other couples we have reported previously. In the monitored agricultural spring, [NO3−] was lower in the summer than at other times, whereas [N2O] was higher in the summer than at other times, perhaps reflecting a seasonal variation in the degree of denitrification reaction progress. No other N analytes were observed to vary seasonally in our study. In the well having no agricultural-N impact, Corg/Norg = 5.5, close to the typical value for natural aqueous systems of about 6.6. In the agricultural watershed Corg/Norg varied widely, from ∼1.2 to ?9. 相似文献
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E. Davesne K. Dideriksen B.C. Christiansen K.B. Ayala-Luis H.C.B. Hansen 《Geochimica et cosmochimica acta》2010,74(22):6451-6467
In a recent study, sulphate-bearing green rust (GRSO4) was shown to incorporate Na+ in its structure (NaFeII6FeIII3(OH)18(SO4)2(s); GRNa,SO4). The compound was synthesised by aerial oxidation of Fe(OH)2(s) in the presence of NaOH. This paper reports on its free energy of formation .Freshly synthesised GRNa,SO4 was titrated with 0.5 M H2SO4 in an inert atmosphere at 25 °C, producing dissolved Fe2+ and magnetite or goethite. Solution concentrations, PHREEQC and the MINTEQ database were used to calculate reaction constants for the reactions:
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We investigated relationships between sedimentary solvent-extractable long-chain alkenone (LCA) concentration and composition and environmental factors in a suite of endorheic lakes from inland Spain. LCAs were found in 14 of the 54 lakes examined, with concentrations comparable with those from previously published lacustrine settings. The composition of LCAs in our sites, however, contrast from the majority of those previously reported from lake environments; in our study the tri-unsaturated component is the most abundant component at most sites where LCAs are detected, and C38:3 is the most abundant LCA in the majority of sites. LCA occurrence appears to be restricted to brackish-hypersaline sites and C37 LCAs are absent above a salinity of ∼40 g L−1 suggesting a salinity control on LCA-producing organisms in these sites. Low concentrations of C37 LCA components means and temperature indices are generally not applicable. Instead we find good relationships between C38 components and (in particular mean autumn) temperature and the strongest LCA-temperature relationships are found when using a combination of all C37 and C38 compounds. We propose a new alkenone temperature index for lakes with elevated salinity and where the C38 components dominate the LCA distributions. This is expressed as (r2 = 0.80, n = 13). In this paper, we provide the first account of sedimentary LCA distributions from lakes in inland Spain, extending the range of environments within which these compounds have been found and highlighting their significance as indicators of both salinity and temperature in saline, endorheic lake environments. This has important implications for extending the potential role of LCAs as palaeoclimatic indicators in lacustrine environments. 相似文献
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Andrei V. Sharygin Robert H. Wood Victor N. Balashov 《Geochimica et cosmochimica acta》2006,70(20):5169-5182
The electrical conductivities of aqueous solutions of Li2SO4 and K2SO4 have been measured at 523-673 K at 20-29 MPa in dilute solutions for molalities up to 2 × 10−2 mol kg−1. These conductivities have been fitted to the conductance equation of Turq, Blum, Bernard, and Kunz with a consensus mixing rule and mean spherical approximation activity coefficients. In the temperature interval 523-653 K, where the dielectric constant, ε, is greater than 14, the electrical conductance data can be fitted by a solution model which includes ion association to form , , and , where M is Li or K. The adjustable parameters of this model are the first and second dissociation constants of the M2SO4. For the 673 K and 300 kg m−3 state point where the Coulomb interactions are the strongest (dielectric constant, ε = 5), models with more extensive association give good fits to the data. In the case of the Li2SO4 model, including the multi-ion associate, , gave an extremely good fit to the conductance data. 相似文献
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Jun Li 《Geochimica et cosmochimica acta》2011,75(15):4351-4376
A thermodynamic model is developed for the calculation of both phase and speciation equilibrium in the H2O-CO2-NaCl-CaCO3-CaSO4 system from 0 to 250 °C, and from 1 to 1000 bar with NaCl concentrations up to the saturation of halite. The vapor-liquid-solid (calcite, gypsum, anhydrite and halite) equilibrium together with the chemical equilibrium of H+,Na+,Ca2+, , , and CaSO4(aq) in the aqueous liquid phase as a function of temperature, pressure and salt concentrations can be calculated with accuracy close to the experimental results.Based on this model validated from experimental data, it can be seen that temperature, pressure and salinity all have significant effects on pH, alkalinity and speciations of aqueous solutions and on the solubility of calcite, halite, anhydrite and gypsum. The solubility of anhydrite and gypsum will decrease as temperature increases (e.g. the solubility will decrease by 90% from 360 K to 460 K). The increase of pressure may increase the solubility of sulphate minerals (e.g. gypsum solubility increases by about 20-40% from vapor pressure to 600 bar). Addition of NaCl to the solution may increase mineral solubility up to about 3 molality of NaCl, adding more NaCl beyond that may slightly decrease its solubility. Dissolved CO2 in solution may decrease the solubility of minerals. The influence of dissolved calcite on the solubility of gypsum and anhydrite can be ignored, but dissolved gypsum or anhydrite has a big influence on the calcite solubility. Online calculation is made available on www.geochem-model.org/model. 相似文献
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Longitudinal acoustic velocities were measured at 1 bar in 10 Na2O-TiO2-SiO2 (NTS) liquids for which previous density and thermal expansion data are reported in the literature. Data were collected with a frequency-sweep acoustic interferometer at centered frequencies of 4.5, 5, and 6 MHz between 1233 and 1896 K; in all cases, the sound speeds decrease with increasing temperature. Six of the liquids have a similar TiO2 concentration (∼25 mol %), so that the effect of varying Na/Si ratio on the partial molar compressibility of the TiO2 component can be evaluated. Theoretically based models for βT and (∂V/∂P)T as a function of composition and temperature are presented. As found previously for the partial molar volume of TiO2 in sodium silicate melts, values of (13.7-18.8 × 10−2/GPa) vary systematically with the Na/Si and Na/(Si + Ti) ratio in the liquid. In contrast values of for the SiO2 and Na2O components (6.6 and 8.0 × 10−2/GPa, respectively, at 1573 K) are independent of composition. Na2O is the only component that contributes to the temperature dependence of the compressibility of NTS liquids (1.13 ± 0.04 × 10−4/GPa K). The results further indicate that the TiO2 component is twice as compressible as the Na2O and SiO2 components. The enhanced compressibility of TiO2 appears to be related to the abundance of five-coordinated Ti ([5]Ti) in these liquids, but not with a change in Ti coordination. Instead, it is proposed that the asymmetric geometry of [5]Ti in a square pyramidal site promotes different topological rearrangements in alkali titanosilicate liquids, which lead to the enhanced compressibility of TiO2. 相似文献
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Dawsonite synthesis and reevaluation of its thermodynamic properties from solubility measurements: Implications for mineral trapping of CO2 总被引：1，自引：0，他引：1
Pascale Bénézeth Donald A. Palmer Juske Horita 《Geochimica et cosmochimica acta》2007,71(18):4438-4455
Over the last decade, a significant research effort has focused on determining the feasibility of sequestering large amounts of CO2 in deep, permeable geologic formations to reduce carbon dioxide emissions to the atmosphere. Most models indicate that injection of CO2 into deep sedimentary formations will lead to the formation of various carbonate minerals, including the common phases calcite (CaCO3), dolomite (CaMg(CO3)2), magnesite (MgCO3), siderite (FeCO3), as well as the far less common mineral, dawsonite (NaAlCO3(OH)2). Nevertheless, the equilibrium and kinetics that control the precipitation of stable carbonate minerals are poorly understood and few experiments have been performed to validate computer codes that model CO2 sequestration.In order to reduce this uncertainty we measured the solubility of synthetic dawsonite according to the equilibrium: , from under- and oversaturated solutions at 50-200 °C in basic media at 1.0 mol · kg−1 NaCl. The solubility products (Qs) obtained were extrapolated to infinite dilution to obtain the solubility constants (. Combining the fit of these values and fixing at 25 °C, which was derived from the calorimetric data of Ferrante et al. [Ferrante, M.J., Stuve, J.M., and Richardson, D.W., 1976. Thermodynamic data for synthetic dawsonite. U.S. Bureau of Mines Report Investigation, 8129, Washington, D.C., 13p.], the following thermodynamic parameters for the dissolution of dawsonite were calculated at 25 °C: , and . Subsequently, we were able to derive values for the Gibbs energy of formation (, enthalpy of formation ( and entropy ( of dawsonite. These results are within the combined experimental uncertainties of the values reported by Ferrante et al. (1976). Predominance diagrams are presented for the dawsonite/boehmite and dawsonite/bayerite equilibria at 100 °C in the presence of a saline solution with and without silica-containing minerals. 相似文献
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James D. Prikryl 《Geochimica et cosmochimica acta》2008,72(18):4508-4520
The dissolution and growth of uranophane [Ca(UO2)2(SiO3OH)2·5H2O] have been examined in Ca- and Si-rich test solutions at low temperatures (20.5 ± 2.0 °C) and near-neutral pH (∼6.0). Uranium-bearing experimental solutions undersaturated and supersaturated with uranophane were prepared in matrices of ∼10−2 M CaCl2 and ∼10−3 M SiO2(aq). The experimental solutions were reacted with synthetic uranophane and analyzed periodically over 10 weeks. Interpretation of the aqueous solution data permitted extraction of a solubility constant for the uranophane dissolution reaction and standard state Gibbs free energy of formation for uranophane ( kJ mol−1). 相似文献
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Climatic and environmental controls on the occurrence and distributions of long chain alkenones in lakes of the interior United States 总被引：1，自引：0，他引：1
Jaime L. Toney Yongsong Huang Sherilyn C. Fritz Eric Grimm 《Geochimica et cosmochimica acta》2010,74(5):1563-7565
Long chain alkenones (LCA) are temperature-sensitive lipids with great potential for quantitative reconstruction of past continental climate. We conducted the first survey for alkenone biomarkers from 55 different lakes in the Northern Great Plains and Nebraska Sand Hills of the United States. Among those surveyed, we found 13 lakes that contain LCAs in the surface sediments. The highest concentrations of alkenones in sediments are found in cold (mean annual air temperature ∼11 °C versus 17 °C in our warmest sites), brackish to mesosaline (salinity = 8.5-9.7 g/L), and alkaline (pH = 8.4-9.0) lakes with high concentrations of sodium and sulfate. The dynamics of stratification and nutrient availability also appear to play a role in LCA abundance, as early spring mixing promotes a bloom of alkenone-producing haptophytes. Four of the alkenone-containing sites contain the C37:4 alkenone; however, we discovered an unprecedented lacustrine alkenone distribution in a cluster of lakes, with a total absence of C37:4 alkenone. We attribute this unusual composition to a different haptophyte species and show that the sulfate:carbonate ratio may control the occurrence of these two distinct populations. We created a new in-situ temperature calibration for lacustrine sites that contain C37:4 using a water-column calibration from Lake George, ND and show that is linearly correlated to lake water temperature (R2 = 0.74), but is not. A number of lakes contain an unidentified compound series that elutes close to the LCAs, highlighting the importance of routine GC-MS examination prior to using lacustrine LCAs for paleotemperature reconstructions. 相似文献
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The rates of Sb(III) oxidation by O2 and H2O2 were determined in homogeneous aqueous solutions. Above pH 10, the oxidation reaction of Sb(III) with O2 was first order with respect to the Sb(III) concentration and inversely proportional to the H+ concentrations at a constant O2 content of 0.22 × 10−3 M. Pseudo-first-order rate coefficients, kobs, ranged from 3.5 × 10−8 s−1 to 2.5 × 10−6 s−1 at pH values between 10.9 and 12.9. The relationship between kobs and pH was:
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The solubility of KFe(CrO4)2·2H2O, a precipitate recently identified in a Cr(VI)-contaminated soil, was studied in dissolution and precipitation experiments. Ten dissolution experiments were conducted at 4–75°C and initial pH values between 0.8 and 1.2 using synthetic KFe(CrO4)2·2H2O. Four precipitation experiments were conducted at 25°C with final pH values between 0.16 and 1.39. The log KSP for the reaction
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Alkenone unsaturation ratios of sedimentary lipids are used as a geochemical proxy for sea surface temperatures, and interest is growing in their potential as indicators of different water masses and possibly of salinity. We analyzed the abundance of unsaturated C37 to C38 ketones in lipid extracts of 57 surface sediment (0-1 cm) samples along a salinity gradient from 8 to 33 psu in the transition from the Skagerrak to the Baltic Sea (NW Europe). In addition to surface sediments, we analyzed alkenones in suspended particulate matter at 13 stations—over a gradient in salinity from 25 to 33 psu—during a bloom of the coccolithophore Emiliania huxleyi. Alkenones were detected in all samples (suspended matter and sediment) with variable contributions of the tetra-unsaturated C37 alkenone compound (%C37:4; range from 2 to 10% of total C37 alkenone content). Comparing the alkenone unsaturation index (U37K′) and %C37:4 data to climatological sea surface temperature and sea surface salinity data sets revealed that SST estimated from U37K′ of saline end members (samples from the Skagerrak) is in the general range of modern SST during bloom periods of haptophytes. At salinities below ∼30 psu %C37:4 increases to above 5% and the unsaturation ratios cease to be related to climatological annual or seasonal sea surface temperatures. On the other hand, the %C37:4 appears to be inversely and significantly correlated to salinity: Highest C37:4 proportions in the inner Baltic Sea are caused by an unidentified organism, but in the transition area at salinities down to 10 psu, the producer apparently is E. huxleyi. The suspended matter data together with those from the water column support the hypothesis of changing biosynthesis of alkenones under salt stress by the coccolithophore E. huxleyi, but constrain the maximum of %C37:4 attributable to salt stress to 10% of all C37 alkenones. 相似文献
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Sunita R. Shah Gesine Mollenhauer Timothy I. Eglinton 《Geochimica et cosmochimica acta》2008,72(18):4577-4594
Understanding the supply and preservation of glycerol dibiphytanyl glycerol tetraethers (GDGTs) in marine sediments helps inform their use in paleoceanography. Compound-specific radiocarbon measurements of sedimentary alkenones from multiple environments have been used to gain insight into processes that affect paleotemperature reconstructions. Similar analyses are warranted to investigate how analogous processes affecting GDGTs impact TEX86 paleotemperatures. Here we present radiocarbon measurements on individual GDGTs from Bermuda Rise and Santa Monica Basin sediments and discuss the results in the context of previous studies of co-depositional alkenones and foraminifera. The 14C contents of GDGTs and planktonic foraminifera in Bermuda Rise are very similar, suggesting a local source; and TEX86-derived temperatures agree more closely with foraminiferal temperatures than do temperatures. In contrast, GDGTs in Santa Monica Basin are depleted in 14C relative to both alkenones and foraminifera, and TEX86 temperatures agree poorly with known surface water values. We propose three possible factors that could explain these results: (i) GDGTs may be labile relative to alkenones during advective transport through oxic waters; (ii) archaeal production deep in the water column may contribute 14C-depleted GDGTs to sediments; and (iii) some GDGTs also may derive from sedimentary archaeal communities. Each of these three processes is likely to occur with varying relative importance depending on geographic location. The latter two may help to explain why TEX86 temperature reconstructions from Santa Monica Basin do not appear to reflect actual sea surface temperatures. Terrigenous GDGTs are unlikely to be major contributors to Bermuda Rise or Santa Monica Basin sediments, based on values of the BIT index. The results also indicate that the crenarchaeol regioisomer is governed by processes different from other GDGTs. Individual measurements of the crenarchaeol regioisomer are significantly depleted in 14C relative to co-occurring GDGTs, indicating an alternative origin for this compound that presently remains unknown. Re-examination of the contribution of crenarchaeol regioisomer to the TEX86 index shows that it is a significant influence on the sensitivity of temperature reconstructions. 相似文献