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1.
Tetraethylenepentamine-modified sugarcane bagasse (SCB) was prepared to improve its adsorption capacity and selectivity toward Cu2+. Adsorption performances of the modified sorbent for Cu2+ were studied in batch system. Separation of Cu2+ from Pb2+ by the modified sorbent fixed-bed column were studied under dynamic system with initial molar concentration ratio \(\left( {C_{0}^{\text{Cu}} /C_{0}^{\text{Pb}} } \right)\) ranging from 1:1 to 1:100. The amount of Cu2+ and Pb2+ adsorbed on the saturated column was calculated by the elution curve. Batch experimental results showed that the adsorption capacity of the sorbent for Cu2+ increased from 0.12 to 0.21 mmol g?1 after modification. Dynamic adsorption results showed that the modified SCB had higher adsorption affinity toward Cu2+ than Pb2+. 0.07 mmol g?1 of adsorbed Pb2+ was pushed off by Cu2+ during the competitive adsorption process at \(C_{0}^{\text{Cu}} /C_{0}^{\text{Pb}} = {\text{1:1}}.\) The breakthrough curves and adsorption kinetics of Cu2+ in the column could be fitted well by the Yoon–Nelson and modified Yoon–Nelson model, respectively. According to the elution curve, the amount of Cu2+ adsorbed on the fixed-bed column were 0.16, 0.16 and 0.15 mmol g?1, while that of Pb2+ were 0.0016, 0.0051 and 0.0094 mmol g?1 when \(C_{0}^{\text{Cu}} /C_{0}^{\text{Pb}}\) increased from 1:1 to 1:10 and 1:100. Cu2+ could be selectively adsorbed and separated from Pb2+ by using the modified sorbent fixed-bed column.  相似文献   

2.
A model is developed for the calculation of coupled phase and aqueous species equilibrium in the H2O-CO2-NaCl-CaCO3 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite. The vapor-liquid-solid (calcite, halite) equilibrium together with the chemical equilibrium of H+, Na+, Ca2+, , Ca(OH)+, OH−, Cl−, , , CO2(aq) and CaCO3(aq) in the aqueous liquid phase as a function of temperature, pressure, NaCl concentrations, CO2(aq) concentrations can be calculated, with accuracy close to those of experiments in the stated T-P-m range, hence calcite solubility, CO2 gas solubility, alkalinity and pH values can be accurately calculated. The merit and advantage of this model is its predictability, the model was generally not constructed by fitting experimental data.One of the focuses of this study is to predict calcite solubility, with accuracy consistent with the works in previous experimental studies. The resulted model reproduces the following: (1) as temperature increases, the calcite solubility decreases. For example, when temperature increases from 273 to 373 K, calcite solubility decreases by about 50%; (2) with the increase of pressure, calcite solubility increases. For example, at 373 K changing pressure from 10 to 500 bar may increase calcite solubility by as much as 30%; (3) dissolved CO2 can increase calcite solubility substantially; (4) increasing concentration of NaCl up to 2 m will increase calcite solubility, but further increasing NaCl solubility beyond 2 m will decrease its solubility.The functionality of pH value, alkalinity, CO2 gas solubility, and the concentrations of many aqueous species with temperature, pressure and NaCl(aq) concentrations can be found from the application of this model. Online calculation is made available on www.geochem-model.org/models/h2o_co2_nacl_caco3/calc.php.  相似文献   

3.
A suite of vanadian magnesiochromites from the Sludyanka metamorphic complex (South Lake Baikal, Russia) were investigated by means of X-ray single-crystal structural refinements and microprobe analyses. Various morphological types of Cr–V-bearing Mg spinels are located in calc–silicate metamorphic rocks, in an assemblage that also contains other Cr–V minerals such as escolaite–karelianite, uvarovite–goldmanite, Cr–V-bearing clinopyroxene, tourmaline, amphibole, mica, etc. Along the suite there is widespread V–Cr substitution (0.14 V3+ 0.95 afu, 1.02 Cr3+ 1.80 afu), and minor, variable Al contents. The Mg content of slightly lesser than 1 afu, is almost constant. Cell parameters and octahedral bond distances increase with V3+. Unexpectedly, the Mg–O tetrahedral bond distance also increases slowly with V3+. This weak dragging effect contributes towards maintaining distortion of the oxygen array with respect to the ideal CCP, thus providing a shielding effect, which reduces V3+–V3+ repulsion. This leads to the energetic stabilization of the structure, in spite of the increase of bond strain with increasing V3+ contents.  相似文献   

4.
The relatively low-variance mineral assemblage of a talc-kyanite eclogite from Dabie Shan enabled application of both conventional geothermobarometers (garnet-clinopyroxene geothermometer and the garnet-omphacite-phengite geobarometer) and a multi-equilibrium method to determine peak P-T conditions (THERMOCALC, average PT). The results were highly discrepant: 840 °C / 31.1 kbar vs. 590 °C / 29.8 kbar. Mössbauer spectroscopy showed that Fe3+/Fetotal in omphacite was significantly higher than the value obtained from standard formula recalculation. When the activities were corrected for Fe endmembers, geothermobarometry gave consistent results (606 °C / 31.3 kbar vs. 585 °C / 30.8 kbar). These are close to those obtained earlier by average PT, confirming the robustness of the multi-equilibrium approach. The high Fe3+ concentration in omphacite is best explained using a Ca-eskola endmember Ca0.5[]0.5AlSi2O6 and allowing corresponding vacancies in the omphacite structure.Editorial responsibility: W. Schreyer  相似文献   

5.
Extended X-ray absorption fine-structure (EXAFS) spectroscopy is used to characterize the local coordination of selected rare-earth elements (Nd3+, Sm3+, Dy3+, Yb3+) coprecipitated with calcite in minor concentrations from room-temperature aqueous solutions. Fitting results confirm substitution in the Ca site, but first-shell Nd-O and Sm-O distances are longer than the Ca-O distance in calcite and longer than what is consistent with ionic radii sums for sixfold coordination in the octahedral Ca site. In contrast, first-shell Dy-O and Yb-O distances are shorter than the Ca-O distance and are consistent with ionic radii sums for sixfold coordination. Comparison of Nd-O and Sm-O bond lengths with those in lanthanide sesquioxides and with ionic radii trends across the lanthanide series suggests that Nd3+ and Sm3+ have sevenfold coordination in a modified Ca site in calcite. This would require some disruption of the local structure, with an expected decrease in stability, and possibly a different charge compensation mechanism between Nd and Sm vs. Yb and Dy. A possible explanation for the increased coordination for the larger rare-earth elements involves bidentate ligation from a CO3 group. Because trivalent actinides such as Am3+ and Cm3+ have ionic radii similar to Nd3+, their incorporation in calcite may result in a similar defect structure.  相似文献   

6.
Kanonaite, with compositions plotting on the join Mn3+AlSiO5–Fe3+AlSiO5, was discovered in a late quartz vein of the Le Coreux metamorphic manganese deposit. A typical structural formula is (Mn3+3.69Fe3+0.36)Al3.95Si4.00O20, representing maximum solid solution within the system Al2SiO5–Mn2SiO5–Fe2SiO5. Refractive indices are =1.777; =1.855. The end-member compositions form the outermost, latest products in zoned crystals ranging to less manganiferous kanonaite. A crystal structure determination of a Mn-rich kanonaite confirms that about 96% of all the Mn3+ present is located in the strongly Jahn-Teller-distorted octahedron of the andalusite-type structure. Combining all relevant mineral-chemical and petrological data available on the deposit, a speculative model is presented in which kanonaite crystals with successively higher Mn3+ contents form during decreasing temperatures in the course of the anticlockwise PTt path of extensional metamorphism. Kaolinite occurring in zones within composite kanonaite porphyroblasts of adjacent phyllites is regarded here as by-product of a continuous retrograde breakdown reaction of less manganiferous kanonaite. In places, kanonaite was peripherally replaced by muscovite and Mn- and Fe-oxides.Editorial responsibility: J. HoefsDedicated to the late Dr. H.S. Yoder, Jr.  相似文献   

7.
Initial Nd isotope ratios are determined for components of 1.9-1.7 Ga age continental crust in the Ketilidian terrain of South Greenland. The Ketilidian has well-documented ages of migmatization/metamorphism (1.80 Ga) and post-tectonic granitoid intrusion (1.76-1.74 Ga) from U-Pb zircon studies. The Nd results show that: (1) metatholeiites with chondritic 147Sm/144Nd have Nd=+4 to +5 at 1.8 Ga; (2) migmatites, paragneisses and an early granitoid have Nd close to zero; (3) post-tectonic norites have Nd +1.5, while spatially associated more-abundant granitoids have Nd=0 to +1. The metatholeiites show that a normal depleted mantle (Nd=+4 to +5) was present beneath this 1.9-1.7 Ga orogenic zone, as is the case in such environments today. However, metatholeiites are an insignificant part of the Ketilidian crust, and the bulk initial ratio of the whole terrain lies close to Nd=0. Rather than invoking depleted and undepleted mantle sources whose products did not mix, we infer the Nd=0 value to be caused by mixing of a component derived from depleted mantle (Nd=+ 4 to +5) with Archean crustal material (Nd=-9 to -13). As there are no proven relics of Archean crust beyond the border zone of the Ketilidian, and the Nd= 0 value appears to be a wellhomogenized feature, we propose that the Archean material was added in the form of sediments transported to the orogenic zone on oceanic crust. The Archean component comprised between 5 and 17% of the Ketilidian, and the most reasonable estimate is 10%. Thus this 1.9-1.7 Ga terrain consisted of 90% new mantle-derived crust.  相似文献   

8.
Oxygen isotope ratios have been measured by ion microprobe and millimeter-scale dental drill along detailed sampling traverses across the boundary between periclase-bearing (δ18O = 11.8‰) and periclase-free (δ18O = 17.2‰) marble layers in the periclase (Per) zone of the Alta Stock aureole, Utah. These data define a steep, coherent gradient in δ18O that is displaced a short distance (~4 cm) into the periclase-free (Cal + Fo) layer. SEM and ion microprobe analyses show two isotopically and texturally distinct types of calcite at the grain scale. Clear (well polished) calcite grains are isotopically homogeneous (within analytical uncertainty; ±0.27‰, 2SD). More poorly polished (pitted), texturally retrograde ‘turbid’-looking calcite has lower and more variable δ18O values, and replaces clear calcite along fractures, cleavage traces or grain boundaries. Despite significant lowering of the δ18O values in calcite throughout both layers during prograde metamorphism, ion microprobe analyses indicate that individual clear calcite grains are now isotopically homogeneous across the entire gradient in δ18O. Diffusion calculations indicate that conservative time scales required for isotopic homogenization of calcite grains by volume diffusion, 30,000–62,000 years at 575–600°C, exceed significantly the timescale (~1,250 years) estimated for the prograde development of the δ18O gradient at the boundary between these two marble layers. The ion microprobe data and these diffusion calculations suggest instead that surface reaction mechanisms accompanying recrystallization are responsible for the observed oxygen isotope homogeneity of these calcite grains. Thus, the ion microprobe data are consistent with the formation of calcite in oxygen isotope exchange equilibrium with infiltrating fluid during prograde reaction and recrystallization. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

9.
Presence of young groundwater (post-1950) in the Goose River basin is demonstrated with 3H and 85Kr analyses. A total of 96 wells and four springs were sampled quarterly from 1999 to 2001 to determine the extent of any recent recharge and to what depth hydraulic continuity existed in the groundwatershed (33.3 km2). Recharge groundwater is less than 50 years in about 31% (3H) to 37% (85Kr) of sampled wells and 75% of sampled springs. Young groundwater ages are recorded in wells up to 320 m in depth within fractured- and arsenic-bearing crystalline bedrock. Total arsenic 10 g L–1 occurs significantly in drinking water with young groundwater flowing through the pumping well intervals. Astotal occurs in 89% (85Kr) to 93% (3H) of all wells with post-1950 groundwater ages. Young groundwater recharge and elevated geogenic arsenic were discovered only in the anatectic granitoids and migmatized country rock of the southwestern part of the Goose River basin.  相似文献   

10.
The adsorption of phosphate onto calcite was studied in a series of batch experiments. To avoid the precipitation of phosphate-containing minerals the experiments were conducted using a short reaction time (3 h) and low concentrations of phosphate (?50 μM). Sorption of phosphate on calcite was studied in 11 different calcite-equilibrated solutions that varied in pH, PCO2, ionic strength and activity of Ca2+, and . Our results show strong sorption of phosphate onto calcite. The kinetics of phosphate sorption onto calcite are fast; adsorption is complete within 2-3 h while desorption is complete in less than 0.5 h. The reversibility of the sorption process indicates that phosphate is not incorporated into the calcite crystal lattice under our experimental conditions. Precipitation of phosphate-containing phases does not seem to take place in systems with ?50 μM total phosphate, in spite of a high degree of super-saturation with respect to hydroxyapatite (SIHAP ? 7.83). The amount of phosphate adsorbed varied with the solution composition, in particular, adsorption increases as the activity decreases (at constant pH) and as pH increases (at constant activity). The primary effect of ionic strength on phosphate sorption onto calcite is its influence on the activity of the different aqueous phosphate species. The experimental results were modeled satisfactorily using the constant capacitance model with >CaPO4Ca0 and either >CaHPO4Ca+ or > as the adsorbed surface species. Generally the model captures the variation in phosphate adsorption onto calcite as a function of solution composition, though it was necessary to include two types of sorption sites (strong and weak) in the model to reproduce the convex shape of the sorption isotherms.  相似文献   

11.
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   

12.
The Fe3+/Fetot of all Fe-bearing minerals has been analysed by Mössbauer spectroscopy in a suite of biotite-rich to biotite-free graphitic metapelite xenoliths, proxies of an amphibolite-granulite transition through progressive biotite melting. Biotite contains 9 to 16% Fe3+/Fetot, whereas garnet, cordierite and ilmenite are virtually Fe3+ -free (0–1% Fe3+/Fetot) in all samples, regardless of biotite presence. Under relatively reducing conditions (graphite-bearing assemblages), biotite is the only carrier of Fe3+ during high-temperature metamorphism; therefore, its disappearance by melting represents an important event of iron reduction during granulite formation, because haplogranitic melts usually incorporate small amounts of ferric iron. Iron reduction is accompanied by the oxidation of carbon and the production of CO2, according to the redox reaction:
Depending on the nature of the peritectic Fe-Mg mineral produced (garnet, cordierite, orthopyroxene), the CO2 can either be present as a free fluid component, or be completely stored within melt and cordierite. The oxidation of graphite by iron reduction can account for the in situ generation of CO2, implying a consequential rather than causal role of CO2 in some granulites and migmatites. This genetic model is relevant to graphitic rocks more generally and may explain why CO2 is present in some granulites although it is not required for their formation.  相似文献   

13.
Zinclipscombite, a new mineral species, has been found together with apophyllite, quartz, barite, jarosite, plumbojarosite, turquoise, and calcite at the Silver Coin mine, Edna Mountains, Valmy, Humboldt County, Nevada, United States. The new mineral forms spheroidal, fibrous segregations; the thickness of the fibers, which extend along the c axis, reaches 20 μm, and the diameter of spherulites is up to 2.5 mm. The color is dark green to brown with a light green to beige streak and a vitreous luster. The mineral is translucent. The Mohs hardness is 5. Zinclipscombite is brittle; cleavage is not observed; fracture is uneven. The density is 3.65(4) g/cm3 measured by hydrostatic weighing and 3.727 g/cm3 calculated from X-ray powder data. The frequencies of absorption bands in the infrared spectrum of zinclipscombite are (cm?1; the frequencies of the strongest bands are underlined; sh, shoulder; w, weak band) 3535, 3330sh, 3260, 1625w, 1530w, 1068, 1047, 1022, 970sh, 768w, 684w, 609, 502, and 460. The Mössbauer spectrum of zinclipscombite contains only a doublet corresponding to Fe3+ with sixfold coordination and a quadrupole splitting of 0.562 mm/s; Fe2+ is absent. The mineral is optically uniaxial and positive, ω = 1.755(5), ? = 1.795(5). Zinclipscombite is pleochroic, from bright green to blue-green on X and light greenish brown on Z (X > Z). Chemical composition (electron microprobe, average of five point analyses, wt %): CaO 0.30, ZnO 15.90, Al2O3 4.77, Fe2O3 35.14, P2O5 33.86, As2O5 4.05, H2O (determined by the Penfield method) 4.94, total 98.96. The empirical formula calculated on the basis of (PO4,AsO4)2 is (Zn0.76Ca0.02)Σ0.78(Fe 1.72 3+ Al0.36)Σ2.08[(PO4)1.86(AsO4)0.14]Σ2.00(OH)1. 80 · 0.17H2O. The simplified formula is ZnFe 2 3+ (PO4)2(OH)2. Zinclipscombite is tetragonal, space group P43212 or P41212; a = 7.242(2) Å, c = 13.125(5) Å, V = 688.4(5) Å3, Z = 4. The strongest reflections in the X-ray powder diffraction pattern (d, (I, %) ((hkl)) are 4.79(80)(111), 3.32(100)(113), 3.21(60)(210), 2.602(45)(213), 2.299(40)(214), 2.049(40)(106), 1.663(45)(226), 1.605(50)(421, 108). Zinclipscombite is an analogue of lipscombite, Fe2+Fe 2 3+ (PO4)2(OH)2 (tetragonal), with Zn instead of Fe2+. The mineral is named for its chemical composition, the Zn-dominant analogue of lipscombite. The type material of zinclipscombite is deposited in the Mineralogical Collection of the Technische Universität Bergakademie Freiberg, Germany.  相似文献   

14.
Piemontite- and thulite-bearing assemblages from highly oxidized metapelitic and metacalcareous schists associated with braunite quartzites at Vitali, Andros island, Greece, were chemically investigated. The Mn-rich metasediments are intercalated in a series of metapelitic quartzose schists, marbles, and basic metavolcanites which were affected by a regional metamorphism of the highP/T type (T=400–500° C,P>9 kb) and a later Barrovian-type greenschist metamorphism (T=400–500° C,P～-5–6 kb). Texturally and chemically two generations of piemontite (I and II) can be distinguished which may show complex compositional zoning. Piemontite I coexisted at highP/T conditions with braunite, manganian phengite (alurgite), Mn3+-Mn2+-bearing Na-pyroxene (violan), carbonate, quartz, hollandite, and hematite. Zoned grains generally exhibit a decreasing Mn3+ and an increasing Fe3+ and Al content towards the rim. Chemical compositions of piemontite I range from 2.0 to 32.1 mole % Mn3+, 0 to 25.6 mole % Fe3+, and 60.2 to 81.2 mole % Al. Up to 12.5 mole % Ca on the A(2) site can be substituted by Sr. Piemontites formed in contact or close to braunite (±hematite) attained maximum (Mn3++Fe3+)Al?1 substitution corrresponding to about 33 mole % Mn3++Fe3+ in lowiron compositions and up to about 39 mole % Mn3++ Fe3+ at intermediate Fe3+/(Fe3++Mn3+) ratios. Piemontite II which discontinuously overgrows piemontite I or occurs as separate grains may have been formed by greenschist facies decomposition of manganian Na-pyroxenes according to the reaction: (1) $$\begin{gathered} {\text{Mn}}^{{\text{3 + }}} - Mn^{2 + } - bearing omphacite/chloromelanite \hfill \\ + CO_2 + H_2 O + HCl \pm hermatite \hfill \\ = piemontite + tremolite + albite + chlorite \hfill \\ + calcite + quartz + NaCl \pm O_2 . \hfill \\ \end{gathered} $$ Thulites crystallized in coexistence with Al-rich piemontite II. All thulites analysed are low-Fe3+ manganian orthozoisites with Mntot～-Mn3+ substituting for Al on the M(3) site. Their compositions range from 2.9 to 7.2 mole % Mn3+, 0 to 1.2 mole % Fe3+, and 91.8 to 96.7 mole % Al. Piemontites II in thulite-bearing assemblages range from 5.8 to 15.9 mole % Mn3+, 0 to 3.7 mole % Fe3+, and 83.7 to 93.6 mole % Al. By contrast, piemontites II in thulite-free assemblages are similarly enriched in Mn3+ + Fe3+ — and partially in Sr2+ — as core compositions of piemontite I (21.1 to 29.6 mole % Mn3+, 2.0 to 16.5 mole % Fe3+, 60.6 to 68.4 mole % Al, 0 to 29.4 mole % Sr in the A(2) site). The analytical data presented in this paper document for the first time a continuous low-Fe3+ piemontite solid solution series from 5.8 to 32.1 mole % Mn3+. Aluminous piemontite II is enriched by about 3 mole % Mn3++Fe3+ relative to coexisting thulite in Fe3+-poor samples and by about 6 mole % Mn3++Fe3+ in more Fe3+-rich samples. Mineral pairs from different samples form a continuous compositional loop. Compositional shift of mineral pairs is attributed to the effect of a variable fluid composition at constantP fluid andT on the continuous reaction: (2) $$\begin{gathered} piemontite + CO_2 \hfill \\ = thulite + calcite + quartz \hfill \\ + Mn^{2 + } Ca_{ - 1} [calcite] + H{_2} O + O{_2} \hfill \\ \end{gathered} $$ Further evidence for a variable \(x_{H_2 O} \) and/or \(f_{O_2 } \) possibly resulting from fluid infiltration and local buffering during the greenschist metamorphism is derived from the local decomposition of piemontite, braunite, and rutile to form spessartine, calcite, titanite, and hematite by the reactions: (3) $$\begin{gathered} piemontite + braunite + CO_2 \hfill \\ = sperssartine + calcite + quartz \pm hermatite \hfill \\ + H{_2} O + O{_2} \hfill \\ \end{gathered} $$ and more rarely: (4) $$\begin{gathered} piemontite + quartz + rutile + braunite \hfill \\ = spessartine + titanite + hematite + H{_2} O + O{_2} . \hfill \\ \end{gathered} $$   相似文献   

15.
The segregation of ten isovalent impurities (Al3+ Cr3+, Eu3+, Gd3+, Ho3+, La3+, Lu3+, Nd3+, Tb3+, Y3+) to the and the (0001) surfaces of haematite (-Fe2O3) have been studied using atomistic simulation where the forces between the atoms are modelled using the Born model of solids. Segregation is found to be energetically favoured in virtually every case. The results for the surface show that the most favourable impurity surface concentration is 33.33%. The (0001) surface has two possible terminations, one terminated by iron atoms and the other by oxygen. No minimum is calculated for the Fe termination of the (0001) surface at low temperatures, but when the effect of raising the temperature is considered, an energy minimum is found, also at 33.33% impurity coverage. In contrast, the O terminated (0001) surface has a minimum in the segregation energy for between 16.67 and 33.33% depending on the cation being considered.  相似文献   

16.
Homogenized samples of raw clays resulting from two (2) different lots of natural clays from Maghnia (Algeria) have been assessed for their potential use in the removal of Pb2+ and Zn2+ ions from industrial liquid wastes (LW). Raw and acid-activated samples have been characterized by powder X-ray diffraction, FT-IR spectroscopy, electron microscopy (SEM), and X-ray fluorescence (XRF) and used as adsorbents for the removal of Pb2+ and Zn2+ ions from aqueous system using adsorption method under different conditions. The effect of factors including contact time, pH, and dosage on the adsorption properties of Pb2+ and Zn2+ ions onto clays was investigated at 25 °C. The obtained results revealed that the removal percentages of Pb2+ and Zn2+ ions, from both aqueous solution (AS) and LW, were varying between 90 and 98% for 40 min and optimal pH values ranged from 5 to 6 for Pb2+ and Zn2+ ions, respectively. The kinetics of both Pb2+ and Zn2+ ion adsorption fitted well with the pseudo-second-order model. Langmuir, Freundlich, and Temkin adsorption isotherms were used, and their constants were evaluated. The values of thermodynamic parameters, ΔH°, ΔS°, and ΔG° indicated that the adsorption of Pb2+ and Zn2+ ions was spontaneous and exothermic process in nature. The adsorption and desorption isotherms indicated that Pb2+ and Zn2+ adsorption to raw clays was reversible. The experimental results obtained showed that the raw clays from Maghnia (Algeria) had a great potential for removing Pb2+ and Zn2+ ions from industrial liquid wastes using adsorption method.  相似文献   

17.
Adsorption and Desorption of Phosphate on Calcite and Aragonite in Seawater   总被引：3，自引：0，他引：3  
The adsorption and desorption of phosphate on calcite and aragonite were investigated as a function of temperature (5–45 °C)and salinity (0–40) in seawater pre-equilibrated with CaCO3. An increase in temperature increased the equilibrium adsorption; whereas an increase in salinity decreased the adsorption. Adsorption measurements made in NaCl were lower than the results in seawater. The higher values in seawater were due to the presence of Mg2+ and Ca2+ ions. The increase was 5 times greater for Ca2+ than Mg2+. The effects ofCa2+ and Mg2+ are diminished with the addition of SO4 2- apparently due to the formation of MgSO4 and CaSO4 complexes in solution and/or SO4 2- adsorption on the surface of CaCO3. The adsorbed Ca2+ and Mg2+ on CaCO3 (at carbonate sites) may act as bridges to PO4 3- ions. The bridging effect of Ca2+is greater than Mg2+ apparently due to the stronger interactions of Ca2+ with PO4 3-.The apparent effect of salinity on the adsorption of PO4 was largely due to changes in the concentration of HCO3 - in the solutions. An increase in the concentration of HCO3 - caused the adsorption of phosphate to decrease, especially at low salinities. The adsorption at the same level of HCO3 - (2 mM) was nearly independent of salinity. All of the adsorption measurements were modeled empirically using a Langmuir-type adsorption isotherm[ [PO4]ad = KmCm[PO4]T/(1 +Km [PO4]T) , ]where [PO4]ad and [PO4]T are the adsorbed and total dissolved phosphate concentrations, respectively. The values of Cm (the maximum monolayer adsorption capacity, (mol/g) and Km (the adsorption equilibrium constant, g/(mol) over the entire temperature (t, °C) and salinity (S) range were fitted to[ Cm = 17.067 + 0.1707t - 0.4693S + 0.0082S2 ( = 0.7) ][ ln Km = - 2.412 + 0.0165t - 0.0004St - 0.0008S2 ( = 0.1) ]These empirical equations reproduce all of our measurements of[PO4]ad up to 14 mol/g and within ±0.7 mol/g.The kinetic data showed that the phosphate uptake on carbonate minerals appears to be a multi-step process. Both the adsorption and desorption were quite fast in the first stage (less than 30 min) followed by a much slower process (lasting more than 1 week). Our results indicate that within 24 hours aragonite has a higher sorption capacity than calcite. The differences between calcite and aragonite become smaller with time. Consequently, the mineral composition of the sediments may affect the short-term phosphate adsorption and desorption on calcium carbonate. Up to 80 % of the adsorbed phosphate is released from calcium carbonate over one day. The amount of PO4 left on the CaCO3 is close to the equilibrium adsorption. The release of PO4 from calcite is faster than from aragonite. Measurements with Florida Bay sediments produced results between those for calcite and aragonite. Our results indicate that the calcium carbonate can be both a sink and source of phosphate in natural waters.  相似文献   

18.
Initial Nd isotopic ratios are reported for 23 samples representing magmatic crustal components in the Svecokarelian terrain of South Finland. U-Pb zircon ages are determined for all geologic units, involving 21 separate upper concordia intercept ages based on more than 100 UP-b analyses. The ages range for all the rocks from 1.90 Ga for primitve plutonic rocks to 1.79 Ga for post-tectonic intrusions. The well-known gabbro-diorite-tonalite-trondhjemite association of the Kalanti district appears to consist of components with different ages: trondhjemites are probably 1.90 Ga or older, diorites/tonalites belong to the main Svecokarelian plutonic eposide at 1.89-1.87 Ga, and at least some gabbro has a post-tectonic age of 1.80 Ga. Nd (T) values range between +2 to +3 for meta-andesites, large gabbros and primitive granitoids to –0.5 for more evolved granitoids. A magma source with Nd of at least +2 to +3 was available during 1.90 to 1.87 Ga, but evolved granitoids have Nd close to zero. The preferred interpretation is that depleted mantle with Nd=+4 to +5 was present beneath the Svecokarelian crust forming during 1.9-1.8 Ga, and that all rocks have been affected more or less by addition of an Archean crustal component with Nd=–9 to –13. The primitive rocks with Nd=+2 to + 3 were only slightly affected, while granitoids with Nd close to zero include a 10% Archean component. The widespread nature of the Archean addition and the distance of up to 500 km to actual exposed Archean crust make it most realistic that the Archean component was added to the form of sediments delivered by subducting Proterozoic ocean crust. The plutonic rocks of the Finnish Svecokarelian crust in areas away from Archean cratons consist of 90% newly mantle-derived material.  相似文献   

19.
The major-ion (Mg2+, Ca2+, Na+, K+, , and Cl−) chemistry of Cretaceous seawater was determined from analyses of seawater-derived brines preserved as fluid inclusions in marine halites. Fluid inclusions in primary halite from three evaporite deposits were analyzed by the environmental scanning electron microscopy (ESEM) X-ray energy dispersive spectrometry (EDS) technique: the Early Cretaceous (Aptian, 121.0-112.2 Ma) of the Sergipe basin, Brazil and the Congo basin, Republic of the Congo, and the Early to Late Cretaceous (Albian to Cenomanian, 112.2-93.5 Ma) of the Khorat Plateau, Laos, and Thailand. The fluid inclusions in halite indicate that Cretaceous seawater was enriched several fold in Ca2+, depleted in , Na+, and Mg2+, and had lower Na+/Cl−, Mg2+/Ca2+, and Mg2+/K+ ratios compared to modern seawater. Elevated Ca2+ concentrations, with Ca2+ >  at the point of gypsum saturation, allowed Cretaceous seawater to evolve into Mg2+-Ca2+-Na+-K+-Cl− brines lacking measurable .The major-ion composition of Cretaceous seawater was modeled from fluid inclusion chemistries for the Aptian and the Albian-Cenomanian. Aptian seawater was extreme in its Ca2+ enrichment, more than three times higher than present day seawater, with a Mg2+/Ca2+ ratio of 1.1-1.3. Younger, Albian-Cenomanian seawater had lower Ca2+ concentrations, and a higher Mg2+/Ca2+ ratio of 1.2-1.7. Cretaceous (Aptian) seawater has the lowest Mg2+/Ca2+ ratios so far documented in Phanerozoic seawater from fluid inclusions in halite, and within the range chemically favorable for precipitation of low-Mg calcite ooids and cements. Results from halite fluid inclusions, together with Mg2+/Ca2+ ratios measured from echinoderm and rudist calcite, all indicate that Early Cretaceous seawater (Hauterivian, Barremian, Aptian, and Albian) had lower Mg2+/Ca2+ ratios than Late Cretaceous seawater (Coniacian, Santonian, and Campanian). Low Aptian-Albian Mg2+/Ca2+ seawater ratios coincide with negative excursions of 87Sr/86Sr ratios and δ34SSO4, and peak Cretaceous ocean crust production rates, all of which suggests a link between seawater chemistry and midocean ridge hydrothermal brine flux.  相似文献   

20.
Interdiffusion coefficients have been determined for H2O-CO2 mixtures by quantifying the flux of CO2 between two fluid-filled chambers in a specially designed piston-cylinder cell. The two chambers, which are maintained at 1.0 GPa and at temperatures differing by ∼100°C, each contain the XCO2-buffering assemblage calcite + quartz + wollastonite, in H2O. The positive dependence of XCO2 on temperature results in a down-temperature, steady-state flux of CO2 through a capillary tube that connects the two chambers. This flux drives the wollastonite = calcite + quartz equilibrium to the right in the cooler chamber, producing a measurable amount of calcite that is directly related to CO2-H2O interdiffusion rates. Diffusivities calculated from seven experiments range from 1.0 × 10−8 to 6.1 × 10−8 m2/s for mean capillary temperatures between ∼490 and 690°C. The data set can be approximated by an Arrhenius-type relation:
  相似文献   

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