共查询到20条相似文献，搜索用时 31 毫秒
1.
2.
Chemical and mineralogical analyses of a well-controlled suite of ferromanganese encrustations from the Line Islands Archipelago (Central Pacific) suggest that they represent purely hydrogenous deposits—i.e. they have formed through the slow accumulation of trace metal-enriched oxides directly from the water-column. Mineralogically they consist predominantly of δMnO2 and amorphous FeOOHxH2O. Compositionally, they are similar to δMnO2 nodules from adjoining basinal areas but are enriched in both Mn (mean = 20.4%, max = 29.3%) and Co (mean = 0.55%, max = 1.57%). δMnO2 is the most important trace metal bearing phase; strong associations are noted between it and Co, Mo, Ni, Zn, and Cd, whilst only Be is associated specifically with FeOOH. V, Sr and Pb are partitioned between the authigenic oxide phases, whilst Ti most probably occurs as TiO2xH2O. Cu is contained in both aluminosilicate contaminant phases and Fe oxide phases. These relations are considered to reflect the differing scavenging behaviour of Mn and Fe oxides in the water column.Crusts from ~1–2 km are enriched in Mn and the Mn-related elements and exhibit higher ratios than deeper crusts, which are compositionally constant. The higher ratios may result from a supply of Mn from continental borderland sediments at these depths, which is transported horizontally by advective-diffusive processes. Since manganophile elements are enriched relative to Mn in the 1–2 km crusts, it is considered that the supply of Mn is scavenged by existing oxides, is oxidised and effectively occludes them. A higher proportion of oxide particles thus exhibit Mn oxide scavenging properties in the 1–2 km depth zone. The increased vertical flux of Mn resulting from the supply at ~1–2 km is not reflected by higher ratios in deeper crusts, so that the vertical flux of oxides is not simply related to the standing crop. The ratios of the crusts thus reflect the composition of suspended oxides at similar depths. 相似文献
3.
Microbial Mn(II) oxidation kinetics in response to oxygen concentration were assessed in suboxic zone water at six sites throughout the Black Sea. Mn(II) oxidation rates increased asymptotically with increasing oxygen concentration, consistent with Michaelis-Menten enzyme kinetics. The environmental half-saturation constant, KE, of Mn(II) removal (oxidation) varied from 0.30 to 10.5 μM dissolved oxygen while the maximal environmental rate, VE−max, ranged from 4 to 50 nM h−1. These parameters varied spatially and temporally, consistent with a diverse population of enzymes catalyzing Mn oxide production in the Black Sea. Coastally-influenced sites produced lower KE and higher VE−max constants relative to the Western and Eastern Gyre sites. In the Bosporus Region, the Mn(II) residence time calculated using our KE and VE−max values with 0.1 μM oxygen was 4 days, 25-fold less than previous estimates. Our results (i) indicate that rapid Mn(II) oxidation to solid phase Mn oxides in the Black Sea’s suboxic zone is stimulated by oxygen concentrations well below the 3-5 μM concentration reliably detected by current oceanographic methods, (ii) suggest the existence of multiple, diverse Mn(II)-oxidizing enzymes, (iii) are consistent with shorter residence times than previously calculated for Mn(II) in the suboxic zone and (iv) cast further doubt on the existence of proposed reactions coupling solid phase Mn oxide production to electron acceptors other than oxygen. 相似文献
4.
Dissolved humic material from three locations on the Ogeechee River Estuary near Savannah, GA, was ultrafiltered into three size fractions and used for kinetic experiments with Cu(II). A Cu(II)-humic mixture was reacted with a colorimetric reagent for Cu(II) and absorbance observed from 50 msec to at least 1835 sec corresponding to rate constants from 0.001–40 sec?1. The apparent dissociation rate constants were distributed over a wide range, with most bound Cu(II) having k > 1 sec?1 (). Nearly all the variation seen in the kinetic distribution was among size fractions; as size fraction decreased, the distribution of bound Cu(II) shifted to larger rate constants. Location of sampling stations on the estuary had little effect on results. 相似文献
5.
Frank J Millero 《Geochimica et cosmochimica acta》1985,49(2):547-553
The effect of ionic interactions of the major components of natural waters on the oxidation of Cu(I) and Fe(II) has been examined. The various ion pairs of these metals have been shown to have different rates of oxidation. For Fe(II), the chloride and sulfate ion pairs are not easily oxidized. The measured decrease in the rate constant at a fixed pH in chloride and sulfate solutions agrees very well with the values predicted. The effect of pH (6 to 8) on the oxidation of Fe(II) in water and seawater have been shown to follow the rate equation where k1 and k2 are the pseudo first order rate constants, β1 and β2 are the hydrolysis constants for Fe(OH)+ and Fe(OH)0. The value of αFE is the fraction of free Fe2+. The value of k1 (2.0 ±0.5 min?1) in water and seawater are similar within experimental error. The value of k2 (1.2 × 105 min?1) in seawater is 28% of its value in water in reasonable agreement with predictions using an ion pairing model.For the oxidation of Cu(I) a rate equation of the form was found where k0 (14.1 sec?1) and k1 (3.9 sec?1) are the pseudo first order rate constants for the oxidation of Cu+ and CuCl0, β1 is the formation constant for CuCl0 and αCu is the fraction of free Cu+. Thus, unlike the results for Fe(II), Cu(I) chloride complexes have measurable rates of oxidation. 相似文献
6.
Micaceous kimberlites from South Africa and Canada contain two types of groundmass mica less than 1 mm across. Very rare Type I micas are relatively iron-rich with , TiO2 3–6 wt%, Al2O3 14–16wt%, no Fe3+ required in tetrahedral sites, low NiO (~0.02 wt%), and relatively high na [Na2O/(Na2O + K2O)] 0.02–0.03. The much more abundant Type II micas are variable in composition, but relative to Type I micas are more magnesium (mg 0.80-0.93), lower in TiO2 (0.7–4.0 wt%) and Al2O3 (6.8–14.2 wt%), have substantial Fe3+ in tetrahedral sites, and have relatively low na. Both types may have rims with compositions indicative of mica-‘serpentine’ mixtures resulting from reaction with a highly aqueous fluid. The petrographically-determined ‘serpentine’ is chemically of two types: Fe-rich serpentine and Fe-rich talc. Associated phases in the ground-mass vary from one kimberlite to another: calcite, dolomite, diopside, chromite, Mg-ilmenite, perovskite, barite, pyrite, pentlandite, millerite?, heazlewoodite?, quartz.Inter-grain variations in composition of Type II micas may result from establishment of local reservoirs on a mm scale, consequent upon mechanical mixing and competition of other phases for minor elements (e.g. chromite for Cr, serpentine for Ni).Type I micas may result from an intrusive precursor (carbonatitic?) to kimberlite, perhaps genetically related, which was incorporated into a later pulse of kimberlite from which the Type II micas crystallized. 相似文献
7.
Calorimetric and potentiometric titrations have been used to evaluate direct and indirect methods of analysis for the carboxyl content of aquatic humic substances. The effects of cation binding, base strength, and removal of humic reaction products on carboxyl content values have been examined. The results suggest that the most appropriate analytical method for determination of an operationally defined carboxyl content would utilize a weak base that does not contain a polyvalent cation in an indirect titration on a reaction mixture from which all humic reaction products have been removed prior to titration. Titration data have been analyzed in terms of a formation function (δnOH) and in terms of operationally defined ‘mass action quotients’ (). The dependence of on pH is more readily and realistically described if no artificial differentiation of carboxyl groups into two or more sub-groups is imposed upon the data. 相似文献
8.
Sorption of metals on humic acid 总被引：1，自引：0，他引：1
The sorption on humic acid (HA) of metals from an aqueous solution containing Hg(II). Fe(III), Pb, Cu, Al, Ni, Cr(III), Cd, Zn, Co and Mn, was investigated with special emphasis on effects of pH, metal concentration and HA concentration. The sorption efficiency tended to increase with rise in pH, decrease in metal concentration and increase in HA concentration of the equilibrating solution. At pH 2.4. the order of sorption was: Hg? Fe? Pb? CuAl ? Ni ? CrZnCdCoMn. At pH 3.7. the order was: Hg and Fe were always most readily removed, while Co and Mn were sorbed least readily. There were indications of competition for active sites (CO2H and phenolic OH groups) on the HA between the different metals. We were unable to find correlations between the affinities of the eleven metals to sorb on HA and their atomic weights, atomic numbers, valencies, and crystal and hydrated ionic radii. The sorption of the eleven metals on the HA could be described by the equation , where Y = % metal removed by HA; X = mgHA; and A and B are empirical constants. 相似文献
9.
F Wlotzka H Palme B Spettel H Wänke K Fredriksson A.F Noonan 《Geochimica et cosmochimica acta》1983,47(4):743-757
The LL-group chondrites Krähenberg (Krbg) and Bhola are heterogeneous agglomerates containing a variety of lithic fragments and chondrules as well as crystal fragments. The + Mg content of most olivine grains is uniform (Fa28), although a few with distinctly lower Fe contents were found (Fa19). Both meteorites contain large, cm-sized, fragments with high enrichments of K (~12×), Rb (~45×) and Cs (~70×) relative to LL-chondrites, while the REE concentrations are normal (except for a negative Eu anomaly); Na and Sr are depleted (~0.5×) and the weight ratio is 0.33 compared to 11 in the host. However, there is no difference in the sum of Na + K atoms. Also, the major elements, Si, Al, Mg, Ca and Fe, are nearly the same in fragments as in the host material. The K-rich igneous lithic fragments have a microporphyritic texture of euhedral to skeletal olivines in a partly devitrified glass with ~4% K2O. The main pans of both Krbg and Bhola contain mesostasis glasses in porphyritic chondrules and lithic fragments with varying K content (0.1–8.6% K2O) and ratios (0.2–100). Crystalline plagioclase is depleted in K with an average ratio of 22, i.e. higher than that for ordinary chondritic plagioclase, 8.4. Olivines in the large, K-rich fragments and in the host meteorites have the same iron content (Fa28), indicating that both formed under the same oxygen fugacity and probably on the same parent body.Conceivable mechanisms for the formation of the K-rich rocks from normal LL-chondrite parent material are: 1, magmatic differentiation: 2. Na-K exchange via a vapor phase; 3. silicate liquid immiscibility; 4. volatilization and condensation in impact events. Process 2 appears most feasible for forming a rock enriched only in K and heavier alkalies and depleted in Na without noticeably changing other elements including the REE. 相似文献
10.
Calculations based on approximately 350 new measurements (CaT-PCO2) of the solubilities of calcite, aragonite and vaterite in CO2-H2O solutions between 0 and 90°C indicate the following values for the log of the equilibrium constants KC, KA, and KV respectively, for the reaction CaCO3(s) = Ca2+ + CO2?3: where T is in oK. At 25°C the logarithms of the equilibrium constants are ?8.480 ± 0.020, ?8.336 ± 0.020 and ?7.913 ± 0.020 for calcite, aragonite and vaterite, respectively.The equilibrium constants are internally consistent with an aqueous model that includes the CaHCO+3 and CaCO03 ion pairs, revised analytical expressions for CO2-H2O equilibria, and extended Debye-Hückel individual ion activity coefficients. Using this aqueous model, the equilibrium constant of aragonite shows no PCO2-dependence if the CaHCO+3 association constant is between 0 and 90°C, corresponding to the value logKCahco+3 = 1.11 ± 0.07 at 25°C. The CaCO03 association constant was measured potentiometrically to be between 5 and 80°C, yielding logKCaCO03 = 3.22 ± 0.14 at 25°C.The CO2-H2O equilibria have been critically evaluated and new empirical expressions for the temperature dependence of KH, K1 and K2 are , and logK2 = ?107.8871 ? 0.03252849T + 5151.79/T + 38.92561 logT ? 563713.9/T2 which may be used to at least 250°C. These expressions hold for 1 atm. total pressure between 0 and 100°C and follow the vapor pressure curve of water at higher temperatures.Extensive measurements of the pH of Ca-HCO3 solutions at 25°C and 0.956 atm PCO2 using different compositions of the reference electrode filling solution show that measured differences in pH are closely approximated by differences in liquid-junction potential as calculated by the Henderson equation. Liquid-junction corrected pH measurements agree with the calculated pH within 0.003-0.011 pH.Earlier arguments suggesting that the CaHCO+3 ion pair should not be included in the CaCO3-CO2-H2O aqueous model were based on less accurate calcite solubility data. The CaHCO+3 ion pair must be included in the aqueous model to account for the observed PCO2-dependence of aragonite solubility between 317 ppm CO2 and 100% CO2.Previous literature on the solubility of CaCO3 polymorphs have been critically evaluated using the aqueous model and the results are compared. 相似文献
11.
Stability constants of hydroxocomplexes of Al(III):Al(OH)2+ and A1(OH)4? have been measured in the 20–70°C temperature range by reactions involving only dissolved species. The stability constant of the first complex ion is studied by measuring pH of solutions of aluminium salts at several concentrations. of aluminate ion is deduced from equilibrium constants of the reaction between the trioxalato aluminium (III) complex ion and Al3+ in acid medium, and between the same complex ion and A1(OH)4? in alkaline medium. The K values and the associated ΔH are and ΔH1 = 11.8 Kcal; and ΔH4 = 42.45 Kcal. These last results are not in agreement with the values of recent tables for and of Al3+ and Al(OH)4?. We suggest a consistent set of data for dissolved and solid Al species and for some aluminosilicates. 相似文献
12.
James W Murray Laurie S Balistrieri Barbara Paul 《Geochimica et cosmochimica acta》1984,48(6):1237-1247
Marine sediments and ferromanganese nodules from the Pacific Ocean have been analyzed for the ratio of solid manganese. We tested six chemical methods and concluded that the iodometric and oxalate methods were equivalent and were the best choice in terms of accuracy and precision on natural samples. We choose the iodometric method for most of our analyses because the oxalate procedure is a method of differences.The ferromanganese nodules that we analyzed were all from MANOP site H and had ratios that ranged from 5.6 to 70. These nodules were invariably highly oxidized with values ranging from 1.90 to 2.00. Our most precise analyses suggest that less than 1% of the total manganese is present as Mn(II).We also analyzed red clay and hemipelagic sediments from the eastern tropical Pacific (Baja borderland and MANOP site H) and carbonate ooze samples from the equatorial Pacific. These sediments are also highly oxidized () except when Mn(II) appears in the interstitial water. As dissolved Mn(II) increases the value of the ratio in the solid phase decreases. The ratio decreases to values as low as 1.40. This decrease appears to be due to a decrease in oxidized manganese by reduction, however, an increase in reduced manganese in the solid sediments by adsorption or MnCO3 formation can not be ruled out in all cases. 相似文献
13.
Frank J Millero 《Geochimica et cosmochimica acta》1979,43(10):1651-1661
The apparent constants (K'i) for the ionization of carbonic acid in seawater at various salinities (S,%.) have been fit to equations of the form ln whereKi is the thermodynamic ionization constant in water, Ai, and Bi are adjustable parameters. The temperature dependence (TK) of Ki, Ai and Bi were of the form, a0 + a1/T + a3 ln T. Equations of similar forms have been used to analyze the ionization constants for water and boric acid and the solubility product of calcite in seawater. The effect of pressure on the apparent constants () have been fit to equations of the form ln where the volume (ΔV) and compressibility (ΔK) changes are polynomial functions of temperature. The equations generated for various açids in seawater have been used to examine the carbonate system in seawater. Equations relating the NBS and Tris pH scales have been derived as well as equations of pH as a function of temperature and pressure. The equations from Hansson (1972, Ph.D. Thesis, University of Göteborg, Sweden) and Mehrbachet al. (1973, Limnol. Oceanogr.18, 897–907) have been used to examine the components of the carbonate system. At a fixed total alkalinity and total carbon dioxide, differences of ±0.01 m-equiv kg?1 in HCO?3 and CO2?3 were found; however, the [CO2] and Pco2 are nearly the same. The contribution of borate ion, B(OH)?4 determined from the equations of Hansson (1972, Ph.D. Thesis, University of Göteborg, Sweden) and Lyman (1957, Ph.D. Thesis, University of California, Los Angeles) differ by ±0.01 m-equiv kg?1 for waters with the same salinity and temperature. 相似文献
14.
15.
Mass absorption coefficients (A2) for a series of standard rocks, have been calculated in the wavelength region 0.492–3.03 . Plots of these data against the intensity of the Compton scattered peak [(I) Compton] give an excellent correlation for the wavelengths 0.429 to the Fe-absorption edge (1.74 ); the data confirm the observations of Reynolds. Hence, routine measurement of one peak will give the mass absorption coefficient of a sample in an analytically important region (Sn/1bKα to Ni/1bKα). A2 has also been directly measured on three of the samples and systematic differences between calculated and measured are attributed to the measuring technique. At wavelengths longer than the Fe-absorption edge, (up to 3.03 ) A2 can be estimated using a combination of (I) Compton and Fe/1bKα c.p.s. This technique enables meaningful matrix corrections to be carried out on the elements Co, Mn, Cr, V, Ti, Sc (K spectra) and Ba (L spectra). Cr and Ba results are presented for some standard rocks. 相似文献
16.
The relative reactivities of pulverized samples (100–200 mesh) of 3 marcasite and 7 pyrite specimens from various sources were determined at 25°C and pH 2.0 in ferric chloride solutions with initial ferric iron concentrations of 10?3 molal. The rate of the reaction: was determined by calculating the rate of reduction of aqueous ferric ion from measured oxidation-reduction potentials. The reaction follows the rate law: where mFe3+ is the molal concentration of uncomplexed ferric iron, k is the rate constant and is the surface area of reacting solid to mass of solution ratio. The measured rate constants, k, range from 1.0 × 10?4 to 2.7 × 10?4 sec?1 ± 5%, with lower-temperature/early diagenetic pyrite having the smallest rate constants, marcasite intermediate, and pyrite of higher-temperature hydrothermal and metamorphic origin having the greatest rate constants. Geologically, these small relative differences between the rate constants are not significant, so the fundamental reactivities of marcasite and pyrite are not appreciably different.The activation energy of the reaction for a hydrothermal pyrite in the temperature interval of 25 to 50°C is 92 kJ mol?1. This relatively high activation energy indicates that a surface reaction controls the rate over this temperature range. The BET-measured specific surface area for lower-temperature/early diagenetic pyrite is an order of magnitude greater than that for pyrite of higher-temperature origin. Consequently, since the lower-temperature types have a much greater ratio, they appear to be more reactive per unit mass than the higher temperature types. 相似文献
17.
Frank J Millero 《Geochimica et cosmochimica acta》1981,45(11):2085-2089
The stoichiometric, , and apparent, K'HA, constants for the ionization of a number of weak acids (NH4+, HSO4?, HF, H2O, B(OH)3, H2CO3, HCO3?, H3PO4, H2PO4?, HPO42, H3AsO4 H2AsO4? and HAsO42?) in seawater at 25°C diluted with water have been fitted to equations of the form (Millero, 1979). In where In KHA is the thermodynamic constant in water, S is the salinity, A and B are adjustable parameters. The validity of this equation in estuarine waters has been examined by using an ion pairing model (Millero and Schreiber, 1981). The calculated values of and K'HA at S = 35%. are in good agreement with the measured values for all the systems examined. The equation used to extrapolate the measured values to pure water KHA predicted values that agreed with those determined by using the ion pairing model. The exception was the ionization of HPO42? due to the strong interactions of Ca2+ and Mg2+ with PO43?. The differences in the predicted values of in seawater diluted with pure water and average river water were very small for all the acids except HPO42? (the maximum ΔpK = 0.96 in average river water). The larger difference in the for HPO42? in river waters is due to the strong interactions of Ca2+ and PO43?. 相似文献
18.
Dewey M. McLean 《Cretaceous Research》1985,6(3):235-259
Mantle degassing continually releases gases onto the earth's surface. Over geologically long time intervals, a general equilibrium probably exists between mantle CO2 release and uptake by surficial sinks. However, during periods of rapid plate movement, or continental flood basalt volcanism, the increased rate of mantle CO2 release may exceed that of uptake, leading to CO2 accumulation in the atmosphere and the marine mixed layer (top 50–100 m). This in turn triggers chemical changes in the mixed layer, climatic warming, and bioevolutionary turnover. The Cretaceous/Tertiary () transition at 65 Ma seems to have been a time of major mantle degassing which induced a perturbation of the carbon cycle. During the transition, Deccan Traps volcanism, perhaps the greatest episode of continental flood basalt volcanism in the Phanerozoic, flooded an estimated 2.6 × 106 km2 of India with basaltic lavas, releasing 5 × 1017 moles of CO2 into the earth's atmosphere over a duration 0.53–1.36 Ma at the rate of 3.9 × 1011 to 9.6 × 1011 moles CO2 per year. The modern mean annual rate of mantle CO2 release from all sources is 4.1 × 1012 moles CO2 per year; assuming a comparable rate of release prior to the Deccan Traps volcanism, the Deccan Traps addition would have elevated the rate of mantle CO2 release by 10–25%. Sluggish marine circulation and warm, deep, oceans (14–15°C) would have exacerbated CO2 buildup in the atmosphere, accounting for the Cretaceous to Tertiary drop in oxygen-18 via climatic warming, and, in the marine mixed layer (top 50–100 m), explaining the selective nature of the terminal Cretaceous marine extinctions via a pH change. The extinctions were most severe amongst the calcareous microplankton of the mixed layer; calcareous microplankton (planktonic foraminifera and coccolithophorids) begin to have pH problems at 7.8 and 7.5, respectively. Failure of the coccolithophorids would have disrupted the Williams-Riley pump (algal productivity-gravity pump of CO2 from the atmosphere and mixed layer into the deep oceans) producing dead ocean conditions (severely reduced photosynthesis and CaCO3 production). Failure of the Williams-Riley pump is reflected in the extinctions themselves, and in the loss of biogenic CaCO3 to the sea floor, causing the boundary hiatus and (or) the boundary clay. Failure of the pump today would elevate atmospheric pCO2 severalfold; the failure would have responded comparably. Dead ocean conditions would, in themselves, have produced a major CO2 buildup. Early Tertiary “Strangelove” conditions in the mixed layer, characterized by a dominance of the thoracosphaerids, braarudosphaerids and small planktonic foraminifera, were coeval with the main pulse of Deccan Traps volcanism. Overall, the record is one of gradual bioevolutionary turnover during a period of disequilibrium between the rate of mantle CO2 degassing and uptake by sinks. Mantle degassing during the Deccan Traps volcanism unifies the biological and physicochemical records. 相似文献
19.
Frank J Millero 《Geochimica et cosmochimica acta》1982,46(1):11-22
The effect of presure on the solubility of minerals in water and seawater can be estimated from In where the volume (ΔV) and compressibility (ΔK) changes at atmospheric pressure (P = 0) are given by Values of the partial molal volume () and compressibilty () in water and seawater have been tabulated for some ions from 0 to 50°C. The compressibility change is quite large (~10 × 10?3 cm3 bar?1 mol?1) for the solubility of most minerals. This large compressibility change accounts for the large differences observed between values of ΔV obtained from linear plots of In Ksp versus P and molal volume data (Macdonald and North, 1974; North, 1974). Calculated values of for the solubility of CaCO3, SrSO4 and CaF2 in water were found to be in good agreement with direct measurements (Macdonald and North, 1974). Similar calculations for the solubility of minerals in seawater are also in good agreement with direct measurements (Ingle, 1975) providing that the surface of the solid phase is not appreciably altered. 相似文献
20.
James W Murray John G Dillard Rudolf Giovanoli Harald Moers Werner Stumm 《Geochimica et cosmochimica acta》1985,49(2):463-470
The initial solid phase oxidation products formed during the oxidation of aqueous Mn(II) at 25°C were studied as a function of time. The analyses included morphology (TEM), mineralogy (x-ray diffraction), ratio (iodometric method), oxidation state of manganese (XPS), and dissolved manganese. The initial solid formed under our conditions was Mn3O4 (hausmannite) which converted completely to γMnOOH (manganite) after eight months. βMnOOH (feitknechtite) appeared to be an intermediate in this transformation. The ratio was initially 1.37 and increased to 1.49 over the same time span. Throughout the course of this study the XPS analyses showed that the surface of the solids (<50 Å) was dominated by Mn(III). The solution pH and dissolved manganese concentrations were consistent with disproportionation and oxidation reactions that favor the transformation of Mn3O4 to γMnOOH but not to γMnO2. 相似文献