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1.
A study was undertaken in order to understand the kinetics and mechanism of the chemical oxidation of N,N-diethyl-m-toluamide, an insect repellent, by sulfate radical. In this experiment, sulfate radical was generated using peroxymonosulfate with iron(II) and cobalt(II) as activator. The second-order rate constant for the reaction of the sulfate radical with N,N-diethyl-m-toluamide was found to be (1.9 ± 0.1) × 109 M?1 s?1 at pH 7 and a temperature of 25 °C. Experiments for the chemical oxidation of N,N-diethyl-m-toluamide in river water and secondary wastewater revealed that the percentage of the removal of N,N-diethyl-m-toluamide was slightly influenced by the water matrices. However, the selected oxidation systems are not effective for the removal of N,N-diethyl-m-toluamide in seawater. Transformation by-products of N,N-diethyl-m-toluamide generated using peroxymonosulfate/iron(II) sulfate, peroxymonosulfate/iron(II) chloride, peroxymonosulfate/cobalt(II) sulfate and peroxymonosulfate/cobalt(II) chloride systems were identified. The results indicated that there are slight differences in the distributions of the transformation by-products detected depending on the activator. The common transformation by-products detected in all selected oxidation systems are N,N-diethylbenzamide, N-ethyl-m-toluamide, N,N-dimethyl-m-toluamide, N-ethyl-N-acetyl-m-toluamide, 2-(diethylamino)-1-m-tolylethanone, monohydroxylated N-ethyl-m-toluamide, and dihydroxylated N,N-diethyl-m-toluamide. Monohydroxylated N,N-diethyl-m-toluamide were detected only when the peroxymonosulfate/iron(II) system was applied. For the peroxymonosulfate/cobalt(II) systems, additional isomers of monohydroxylated N-ethyl-m-toluamide were detected. Peroxymonosulfate/cobalt(II) also transformed 2-(diethylamino)-1-m-tolylethanone into N-ethyl-N-(2-oxo-2-m-tolylethyl)acetamide and monohydroxylated 2-(ethyl(vinyl)amino)-1-m-tolylethanone as transformation by-products.  相似文献   

2.
Four new types of paramagnetic centers — NH+ 3, N2?, Al-O?, E 1 — have been detected in microcline perthites from pegmatites in the Ukrainian Shield. Values are tabulated for their g and A tensors and limits of thermal stability determined. The NH+ 3 center substitutes the K+ ion. It occurs naturally in potash feldspars but is intensified by gamma or X-ray irradiation. It is regarded as a radiational development of the more general NH+ 4 ? K+ isomorphism. It disappears after heating to temperatures higher than 470 K. The N2? center is an uncommon example of isomorphous substitution of a bridging oxygen, being located on a O D(m) site between T 2(o) and T 1(m) silicon sites. It is stable to 820 K. The hole center, Al-O?, has been detected on an O A(l) oxygen shared by T 1(o) and T 1(m) tetrahedra. It is stable to 590 K. The E 1 center in these alkali feldspars is similar to the E 1 center in quartz, being an electron trapped in an oxygen vacancy in the O B (o) position. It is stable to 420 K. The NH+ 3, Al-O? and E 1 centers can be restored from temperatures above their stability limits by gamma radiation. Concentration of centers varies from sample to sample depending on conditions of formation and subsequent history of the minerals.  相似文献   

3.
The solubility of all possible Zn and Pb species in aqueous chloride fluids was evaluated by means of thermodynamic simulations in systems ZnO(PbO)-aqueous solution of NaCl (KCl, NaCl + HCl) within broad ranges of temperature (600–900°C), pressure (0.7–5 kbar), and chloride concentrations, under parameters corresponding to the crystallization and degassing of granitoid magmas in the Earth’s crust. Our simulation results demonstrate that the addition of Cl to the fluid phase in the form of Na(K)Cl and HCl significantly increases the concentrations of Cl-bearing Zn and Pb complexes and the total concentration of the metals in the solutions in equilibrium with the solid oxides. In Zn-bearing fluids, the Zn(OH) 2 0 , ZnOH+, and Zn(OH) 3 ? —hydroxyl complexes and the ZnCl 2 0 , and ZnCl+ chlorocomplexes, which are predominant at low Cl concentrations (CCl < 0.05–0.1 m) give way to ZnCl 4 2? with increasing CCl, which becomes the predominant Zn species of the fluid at CCl > 0.1–0.5 m throughout the whole temperature range in question and pressures higher than 1 kbar. For Pb-bearing fluids, the T-P-X region dominated by the Pb(OH) 2 0 , and Pb(OH) 3 ? hydroxyl complexes is remarkably wider than the analogous region for Zn, particularly at elevated temperatures (≥700°C) in alkaline solutions. An increase in CCl is associated with an increase in the concentration and changes in the speciation of Pb chlorocomplexes: PbCl 2 0 → PbCl 3 ? → PbCl 4 2? . The concentrations of Zn and Pb chlorocomplexes increase with increasing pressure, decreasing temperature, and decrease pH with the addition of HCl to the system. It is demonstrated that the solubility of ZnO at any given T-P-X in alkaline solutions with low chloride concentrations are lower than the solubility of PbO. The Zn concentration increases more significantly than with the Pb concentration with increasing CCl and decreasing pH, so that the Zn concentration in acidic solutions is higher than the Pb concentration over broad ranges of temperature, pressure, and Cl concentration. Chloride complexes of Zn (ZnCl 2 0 , and ZnCl 4 2? ) and Pb (PbCl 2 0 , and PbCl 3 ? are proved to be predominant within broad T-P-X-pH ranges corresponding to the parameters under which magmatic fluid are generated. Our simulation results confirm the hypothesis that chlorocomplexes play a leading role in Zn and Pb distribution between aqueous chloride fluids and granitic melts. These simulation results are consistent with experimental data on the Zn and Pb distribution coefficients (D(Zn)f/m and D(Pb)f/m, respectively) between aqueous chloride fluids and granitic melts that demonstrated that (1) D(Zn)f/m and D(Pb)f/m increase with increasing Na and K chloride concentrations in the aqueous fluid, (2) both D(Zn)f/m and D(Pb)f/m drastically increase when HCl is added to the fluid, and (3) (D(Zn)f/m is higher than D(Pb)f/m at any given T-P-X parameters. The experimentally established decrease in D(Zn)f/m and D(Pb)f/m with increasing pressure (at unchanging temperature and Cl concentration) is likely explained by an increase in the alkalinity of the aqueous chloride fluid in equilibrium with granite melt and, correspondingly, a decrease in the Zn and Pb solubility in this fluid.  相似文献   

4.
Weathering indices typified by the Miura index (Wom) that are the ratios of geochemically mobile to relatively immobile elements can be shown to be logarithmically related to the free energy of the weathering reaction. This can be demonstrated for silicate minerals; other extensive properties such as the moduli of elasticity and rigidity are similarly correlated. The mass strength envelope implied by the corresponding o-log W plot concurs well with plotted values for rocks, suggesting that the correlation is valid for intact rocks as well.By a combination of the Miura index and an index believed to show not only the state of weathering but also the susceptibility to further weathering (the Parker index Wop), it is possible to obtain estimates of the activation energy for the incongruent aqueous dissolution of minerals, which compare favourably with experimental determinations. Although the engineering behaviour of rocks is generally governed by physical parameters, and thus by short-term mechanical or physico-chemical forces, there are some instances where failure has been attributed to the chemistry of the rock itself. For these rocks a good correlation is obtained between a chemical weatherability index (log Wom/Wop) and rock durability, as measured by the Los Angeles abrasion test.  相似文献   

5.
The authors report the results of X-ray diffraction (XRD) and geochemical studies on bastnaesites (lanthanum cerium fluoro-carbonate) hosted in alkali Kanigiri Granite of the Prakasam district in Andhra Pradesh, India. The XRD pattern of the investigated bastnaesite displays sharply-defined reflections. The observed d-spacings of the bastnaesite are in very close agreement with those published for bastnaesite standard in International Centre for Diffraction Data (ICDD) Card No. 11–340. The calculated unit cell parameters (a o ; c o ) and unit cell volume (V) of the studied bastnaesite (a o 7.1301–7.1413 Å, c o 9.7643–9.7902Å and V 429.8940–432.3875 Å3) are almost equal to values published for bastnaesite standard (c o 7.1290 Å, c o 9.7744 Å and V 430.19 Å3) in the relevant data card. Geochemical data of bastnaesite reveals high content of Ce (mean 27.22%) followed by La (mean 16.82%), Nd (mean 6.12%) and Pr (mean 1.91%). Compared to light REE (LREE) content (mean 437165 ppm), heavy REE (HREE) content (mean 5867 ppm) is drastically low, with unusually high LREE/HREE ratio (mean 80). The chondrite-normalised plot also exhibits drastic enrichment of LREE relative to HREE with pronounced negative Euanomaly (mean Eu/Eu* = 0.15). High (LREE) N / (HREE) N , (La/Lu) N , (La/Yb) N and (Ce/Yb) N ratios reveal higher fractionation of LREE relative to HREE. The rare earth element (REE) contents of the studied bastnaesite are very close to REE contents of bastnaesite hosted in alkali syenite from Madagascar. The presence of bastnaesite in Kanigiri Granite and soils derived from it enhances the scope of further exploration for bastnaesite in several bodies of alkaline rocks and alkali granitoids present along the eastern margins of the Cuddapah basin, Andhra Pradesh.  相似文献   

6.
This study investigates the performance of empirical and semiempirical models to predict soil moisture from the data of RADARSAT II synthetic aperture radar (SAR) for the Yarmouk basin in Jordan. Data of SAR were obtained for May and June 2010 and were processed to obtain backscatter (σ o ) data for the study area. Results showed significant correlations between soil moisture content (m v ) and horizontally polarized σ o , with coefficient of determination (R 2) of 0.64. The root mean square error for the SAR volumetric soil moisture content was 0.09 and 0.06 m3/m3 for the empirical and semiempirical regression models, respectively. Both models had different clustering patterns in the soil moisture maps in the study area. The spatial agreement between maps of soil moisture was in the range of 55 to 65 % when the maps were reclassified based on intervals of 5 % m v for both models. In terms of soil moisture interval, both models showed that most of soil moisture changes between the two images (dates) were in the range of ±5 %. Some high differences in ?m v were observed between the two models. These were mainly attributed to the non-inverted pixels in the soil moisture maps produced by the semiempirical model. Therefore, this model may be applied for a limited range of soil moisture prediction. The use of regression model could predict a wider range for soil moisture when compared with the semiempirical model. However, more work might be needed to improve the empirical model before scaling it up to the whole study area.  相似文献   

7.
The photometric behavior of the hot, young Herbig Be starMWC 297 on various time scales is studied using published data, as well as new observations. The series of photometric observations covers about 25 years. Over this time, the star showed low-amplitude (ΔV ≈ 0.3 m ) irregular variabilitymodulated by large-scale cyclic variabilitywith an amplitude close to 0.2 m and a period (or quasi-period) of 5.4±0.1 yr. A detailed seasonal analysis of the data shows that the light curve of MWC 297 displays two types of photometric features: low-amplitude Algol-like fading with an amplitude close to 0.2 m and low-amplitude flares resembling the flares of UV Ceti stars, but being more powerful and having longer durations. The variations of the stellar brightness are accompanied by variations of the B-V and V -R colors: when the brightness decreases, B-V decreases, while V -R increases (the star reddens). The reddening law is close to the standard interstellar reddening law. Although the character of the brightness variability ofMWC 297 resembles the photometric activity of UX Ori type stars, which is due to variations of their circumstellar extinction, its scale is very far from the scales observed for UX Ori stars. It is difficult to reconcile the level of photometric activity with the idea that MWC 297 is observed through its own gas-dust disk viewed almost edge-on, as has been suggested in several studies.  相似文献   

8.
Vanadium adsorption by soils representing different soil types from Germany has been studied. For 30 soils ‘Freundlich’ type sorption isotherms have been deduced from laboratory vanadium(V) adsorption experiments. The native adsorbed vanadium quantity of a soil (S0) and the Freundlich parameters m and log k have been determined by non linear regression of the experimental data to the Freundlich model. Pronounced differences in vanadium adsorption of different soils exist and could be quantified. The vanadium adsorption data could be generalized by grouping the soils into four classes according to their vanadium adsorption properties. For each class (sandy soils, top soils, sub soils with pH < 5.5, and sub soils with pH > 5.5) mean Freundlich parameters m and log k have been calculated to be 0.59, 0.72, 0.52, 0.57 and 2.55, 2.89, 4.29, 3.41, respectively. These parameters can be used to estimate vanadium sorption properties of soils for which no vanadium sorption experiments are available. Aqua regia soluble vanadium contents of the studied soils (range 1.7–143 mg/kg; median 32 mg/kg) and leached vanadium concentrations from experiments without vanadium addition (range 0.08–37 µg/l; median 2.1 µg/l) are also given.  相似文献   

9.
Annual acetylene reduction rates associated with interidal communities in a chronically oil polluted Virginia salt marsh were compared to rates measured in an undisturbed marsh. Chronic oil treatment resulted in visible damage to the higher plants of theSpartina alterniflora zones; however, vegetation-associated acetylene, reduction was not different from the untreated control. Sediment rates generally were affected little by oil application, except during the summer when rates in the median tidal elevation zones were considerably higher than those of the control. Acetylene reduction occurred in all transects, each of which extended from upper mudflat to theSpartina patens zone. Intertidal sediment acetylene reduction was patchy, both spatially and seasonally. Estimated rates were greatest near the surface; free-living bacterial N2 fixation activity averaged 2.23 mg N per m2 per d (range=undetectable to 365 mg N per m2 per d) in the untreated and 3.17 mg N per m2 per d (range=undetectable to 564 mg N per m2 per d) in the oil-treated marsh during the year. Vegetation-associated N2 fixation activity yielded highest overall mean rates (156 mg N per m2 per d). The seasonal pattern of sediment and vegetation-associated fixation may be controlled by temperature and availability of oxidizable substrates.  相似文献   

10.
The flushing time of the Providence River was estimated using three different data sets and three different methodologies. Dye concentrations were measured following instantaneous dye releases during wet weather experiments performed by the Narragansett Bay Project between October 1988 and June 1989. These data were analyzed to obtain flushing time estimates. Salinity measurements collected during the Sinbadd (Sampling In Narragansett Bay All During the Day) cruises, Spray (Sampling the Providence River All Year) cruises and wet weather experiments were used with the fraction of fresh water method and box model to calculate flushing time. The Sinbadd cruises performed 4 seasonal surveys at 22 stations in Narragansett Bay during 1986 to obtain a view of the whole Narragansett Bay with respect to the concentrations of nutrients and trace metals. The Spray cruises collected data in the Providence River at 10 stations to determine the relationship of nutrients and trace metals concentrations in the Seekonk and Providence rivers as a function of point source inputs. Based on the flushing time estimates, an exponential relationship between freshwater inflow and flushing time was developed (correlation coefficient of 0.826). The flushing time ranged from 0.8 d at high (90 m3 m?1) freshwater inflows to 4.4 d at low (20 m3 s?1) freshwater inflows. The average flushing time of the Providence River was estimated as 2.5 d for the mean freshwater inflow of 42.3 m3 s?1.  相似文献   

11.
The relationships between free radical concentration (Ng) and vitrinite reflectance (%Ro) of coal were tested through 36 laboratory anhydrous pyrolysis experiments. The experiments were carried out at isothermal reactor with pyrolysis temperatures ranging from 300 to 550 °C over 30–480 min. The effects of temperature and retention time on the Ng were investigated. The concentrations of free radicals in pyrolysis coal samples increase with increasing time and temperature of experiments and reach a maximum value at about 1.75 %Ro, and then decrease with further maturation. The Temperature Time Index (TTI) integral equation was applied to establish the relationship between the TTI and Ng in this paper. As the free radical concentration in organic matter is strongly maturity dependent, it may prove to be a valuable geothermometer for paleogeotemperature study in sedimentary basins.  相似文献   

12.
Solubilities of methane in multisalt solutions at 550 psia and 25°C can be predicted from single-salt salting coefficients. The ionic strength contribution of the ith salt, Ii, is multiplied by its molal salting coefficient, kmi, in the following summation over all salts:
logMoMs = ∑i kmiIi
where mo and ms are molal methane solubilities in distilled water and the salt solution, respectively, at the T, P and methane fugacity of interest.This equation predicts methane solubility in multisalt brines containing Na+, K+, Mg+2, Ca+2, Cl?, SO4?2 and CO3?2 ions. kmi values reported by Stoessell and Byrne (1982b) can be used in solubility predictions in brines at earth surface conditions. Prediction in reservoir brines would require determination of kmi, for the different salts at reservoir temperatures and pressures.  相似文献   

13.
Rates of CO2 emission from bare salt-marsh sediments in areas of short and tall formSpartina alterniflora were measured monthly for 1 yr. Maximum emission rates, as high as 325 ml CO2m?2h?1, were observed during summer months, while minimum rates, 10.2 ml CO2 m?2h?1, were observed during the winter. An exponential function of inverse soil temperature explained most of the seasonal variability, but other factors are involved in regulating CO2 emissions as demonstrated by rates that were higher in spring than in late summer at equivalent temperatures. Annual CO2 emissions from bare sediments were 27.3 and 18.6 mol C m?2 yr?1 in communities of short and tallS. alterniflora, respectively. It was estimated that losses of dissolved inorganic carbon from the turnover of pore water, up to 14.6 mol C m?2 yr?1 at the creek bank (tall,S. alterniflora) site, and diffusion of CO2 from the root system ofS. alterniflora through the culms, 12.3 to 16.2 mol C m?2 yr?1, could also be important pathways of carbon loss from marsh sediments. If the internal flux of CO2 from the root system through the culm is refixed within the leaves, then the observed rate of 9.8 μI CO2 min?1 cm?2 of culm cross sectional area appears to make a small but significant contribution to total photosynthesis.  相似文献   

14.
In order to better understand the spatiotemporal variations and interrelationships of greenhouse gases (GHG), monthly surface fluxes and profile concentrations of GHG (CO2, N2O and CH4) in karst areas in the Guizhou Province, southwest China, were measured from June 2006 to May 2007. GHG fluxes showed high variability, with a range of 460.9?C1,281.2?mg?m?2?h?1 for CO2, ?25.4 to 81.5???g?m?2?h?1 for N2O and ?28.7 to ?274.9???g?m?2?h?1 for CH4, but no obvious seasonal change trends of the fluxes existed. Profile concentrations of CO2, N2O and CH4 varied between 0.5 and 31.5?mL?L?1, 0.273 and 0.734, and 0.1 and 3.5???L?L?1, respectively. In general, concentrations of CO2 and N2O increased with depth, while CH4 had an inverse trend. However, in October, November and January, the reversal of depth patterns of GHG concentrations took place below 15?cm, close to the soil?Crock interface. The spatiotemporal distribution of CO2 in soil profile was significantly positively correlated with that of N2O (p?<?0.05?C0.01) and negatively correlated with that of CH4 (p?<?0.01). The correlation analysis showed that soil temperature and moisture may be responsible for GHG dynamics in the soils, rather than the exchange of GHG between land and atmosphere.  相似文献   

15.
The Fe-rich Li-bearing magnesionigerite-6N6S occurs in the Xianghualing tin-polymetallic ore field, Linwu County, Hunan Province, Peoples Republic of China. It was found near the outer contact zone of the Laizhiling granite body and in the Middle-Upper Devonian carbonate rocks of Qiziqiao Formation. The mineral formed during the skarn stage. Its empirical formula is Sn1.81Li0.67(Fe1.43Zn1.19 Mn0.41)Σ3.03(Al14.89Mg1.46 Ti0.11Si0.01)Σ16.47O30(OH)2. The structure for magnesionigerite-6N6S was solved and refined in space group R-3?m, with a?=?5.7144(8), c?=?55.446(11) Å, V?=?1568.0(4) Å3, to R1?=?0.0528. Based on the structural refinement of single crystal diffraction data the formula of magnesionigerite-6N6S is Sn1.80Li0.97(Fe1.89Zn0.91) Σ2.80 (Al14.60Mg1.63 Ti0.20)Σ16.43O30(OH)2 with Z?=?3. Fe-rich Li-bearing magnesionigerite-6N6S contains 0.74 wt.% Li2O. The idealized charge-balanced composition of magnesionigerite-6N6S may be expressed by bivalent and trivalent cations: (Mg2+)4(Al3+)18O30(OH)2. The simplified general formula for the 6N6S polysomes in the nigerite and högbomite groups can be given as A x B18-x O30(OH)2, x?=?~4, where A?=?Mg2+, Fe2+, Zn2+; B?=?Al3+, Sn4+, Ti4+, Li+, □.  相似文献   

16.
The two most abundant network-modifying cations in magmatic liquids are Ca2+ and Mg2+. To evaluate the influence of melt structure on exchange of Ca2+ and Mg2+ with other geochemically important divalent cations (m-cations) between coexisting minerals and melts, high-temperature (1470-1650 °C), ambient-pressure (0.1 MPa) forsterite/melt partitioning experiments were carried out in the system Mg2SiO4-CaMgSi2O6-SiO2 with ?1 wt% m-cations (Mn2+, Co2+, and Ni2+) substituting for Ca2+ and Mg2+. The bulk melt NBO/Si-range (NBO/Si: nonbridging oxygen per silicon) of melt in equilibrium with forsterite was between 1.89 and 2.74. In this NBO/Si-range, the NBO/Si(Ca) (fraction of nonbridging oxygens, NBO, that form bonds with Ca2+, Ca2+-NBO) is linearly related to NBO/Si, whereas fraction of Mg2+-NBO bonds is essentially independent of NBO/Si. For individual m-cations, rate of change of KD(m−Mg) with NBO/Si(Ca) for the exchange equilibrium, mmelt + Mgolivine ? molivine + Mgmelt, is linear. KD(m−Mg) decreases as an exponential function of increasing ionic potential, Z/r2 (Z: formal electrical charge, r: ionic radius—here calculated with oxygen in sixfold coordination around the divalent cations) of the m-cation. The enthalpy change of the exchange equilibrium, ΔH, decreases linearly with increasing Z/r2 [ΔH = 261(9)-81(3)·Z/r2 (Å−2)]. From existing information on (Ca,Mg)O-SiO2 melt structure at ambient pressure, these relationships are understood by considering the exchange of divalent cations that form bonds with nonbridging oxygen in individual Qn-species in the melts. The negative ∂KD(m−Mg)/∂(Z/r2) and ∂(ΔH)/∂(Z/r2) is because increasing Z/r2 is because the cations forming bonds with nonbridging oxygen in increasingly depolymerized Qn-species where steric hindrance is decreasingly important. In other words, principles of ionic size/site mismatch commonly observed for trace and minor elements in crystals, also govern their solubility behavior in silicate melts.  相似文献   

17.
A laser-heated diamond-anvil cell that is capable of operating up to a pressure of 63 GPa, with X-ray diffraction facilities using a synchrotron radiation source at the SPring-8, has been developed to observe the compressibility of a hexagonal aluminous phase, [K0.15Na1.66Ca0.11Mg1.29Fe2+ 0.86Al3.13Ti0.09Si1.98] Σ9.27O12. The hexagonal aluminous phase is a potassium host mineral from the subducted oceanic crust in the Earth's lower mantle. A sample was heated using a YAG laser at each pressure increment to relax the deviatoric stress in the sample. X-ray diffraction measurements were carried out at 300 K using an angle-dispersive technique. Pressure was measured using an internal platinum pressure calibrant. The observed unit-cell volumes were used to obtain a third-order Birch–Murnaghan equation of state: unit-cell volume V o=185.94(±16) Å3, density ρ o=4.145 g/cm3, and bulk modulus K o=198(±3) GPa when the first pressure is derivative of the bulk modulus K ′ o is fixed to 4. The density of hexagonal aluminous phase is lower than that of coexisting Mg-perovskite in the subducted oceanic crust.  相似文献   

18.
Based on potentiometric data and gypsum solubility in mixed salt solutions, respectively, the activity coefficients of MgCOo3 and CaSOo4 ion pairs decrease with ionic strength (I) at 25°C. Computed γ's for the ion pairs fit the empirical equation log γi = ? BI. B coefficients of 0.63 ±0.10 for MgCOo3 and 0.45 ± 0.15 for CaSOo4 are obtained from linear regression of log γi values vs I between 0.04 and 0.6 molal. Assumptions that the activity coefficients of these neutral ion pairs equal unity or are approximated by the Setchenow expression (log γi = kI) are therefore invalid at moderate ionic strengths. Log γi = ? BI is the same general form as the equation of Kirkwood (Chem. Rev.24, 233–251, 1939) for neutral dipoles.  相似文献   

19.
Complexes formed by the addition of vanadyl salts to a peat humic acid have been studied by EPR spectroscopy. The spectra show that the vanadium is in an environment with approximately axial symmetry. The g-values and 51V hyperfine coupling constants indicate that the vanadium remains in the vanadyl state and is complexed possibly either by oxygen donor groups or by mixed oxygennitrogen donor groups in the humic acid. Identical spectra were obtained when the vanadium was added to the humic acid as the metavanadate ion, thus showing that reduction of vanadium from oxidation state (V) to (IV) occurs.  相似文献   

20.
《China Geology》2020,3(4):545-557
The composition of gas released under vacuum by crushing from the gas shale of Longmaxi Formation in Upper Yangtze Plate, Southern China was systematically investigated in this study. The effect of residual gas release on pore structures was checked using low-pressure nitrogen adsorption techniques. The influence of particle size on the determination of pore structure characteristics was considered. Using the Frenkel-Halsey-Hill method from low-pressure nitrogen adsorption data, the fractal dimensions were identified at relative pressures of 0−0.5 and 0.5−1 as D1 and D2, respectively, and the evolution of fractal features related to gas release was also discussed. The results showed that a variety component of residual gas was released from all shale samples, containing hydrocarbon gas of CH4 (29.58% −92.53%), C2H6 (0.97% −2.89%), C3H8 (0.01% −0.65%), and also some non-hydrocarbon gas such as CO2 (3.54% − 67.09%) and N2 (1.88%−8.07%). The total yield of residual gas was in a range from 6.1 μL/g to 17.0 μL/g related to rock weight. The geochemical and mineralogical analysis suggested that the residual gas yield was positively correlated with quartz (R2=0.5480) content. The residual gas released shale sample has a higher surface area of 17.20−25.03 m2/g and the nitrogen adsorption capacity in a range of 27.32−40.86 ml/g that is relatively higher than the original samples (with 9.22−16.30 m2/g and 10.84−17.55 ml/g). Clearer hysteresis loop was observed for the original shale sample in nitrogen adsorption-desorption isotherms than residual gas released sample. Pore structure analysis showed that the proportions of micro-, meso- and macropores were changed as micropores decreased while meso- and macropores increased. The fractal dimensions D1 were in range from 2.5466 to 2.6117 and D2 from 2.6998 to 2.7119 for the residual gas released shale, which is smaller than the original shale. This factor may indicate that the pore in residual gas released shale was more homogeneous than the original shale. The results indicated that both residual gas and their pore space have few contributions to shale gas production and effective reservoir evaluation. The larger fragments samples of granular rather than powdery smaller than 60 mesh fraction of shale seem to be better for performing effective pore structure analysis to the Longmaxi shale.  相似文献   

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