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1.
An Inceptisol A-horizon from Hawaii was subjected to a series of reduction-oxidation cycles—14 d cycle length over a 56 d duration—across the “soil-Fe” [Fe(OH)3.Fe2+(aq), log Ko = 15.74] equilibrium in triplicate redox-stat reactors. Each reducing event simulated the flush of organic C and diminished O2 that accompanies a rainfall-induced leaching of bioavailable reductants from the forest floor into mineral soil. The soil contained considerable amounts of short-range ordered (SRO) minerals (e.g., nano-goethite and allophane) and organic matter (11% org-C). Room temperature and cryogenic 57Fe Mössbauer spectroscopy showed that the iron-bearing minerals were dominated by nano- to micro-scale goethite, and that ferrihydrite was not present. Over the four full cycles, fluctuations in Eh (from 200 to 700 mV) and pFe2+ (from 2.5 to 5.5) were inversely correlated with those of pH (5.5 to 4). Here, we focus on the solubility dynamics of the framework elements (Si, Fe, Ti, and Al) that constitute 35% of the oxygen-free soil dry mass. Intra-cycle oscillations in dissolved (<3 kDa) metals peaked during the reduction half-cycles. Similar intra-cycle oscillations were observed in the HCl and acid ammonium oxalate (AAO) extractable pools. The cumulative response of soil solids during multiple redox oscillations included: (1) a decrease in most HCl and AAO extractable metals and (2) a transformation of SRO Fe (as nano-goethite) to micro-crystalline goethite and micro-crystalline hematite. This may be the first direct demonstration that Fe oxide crystallinity increases during redox oscillations—an a priori unexpected result. 相似文献
2.
《Applied Geochemistry》2001,16(11-12):1413-1418
In order to understand the relationship between forms of Al in soils and the uptake of Al from soil into tea plants, tea leaves and soils were collected from 13 tea gardens in the east of China. The Al concentration measured in the tea leaves was found to be best predicted by ‘available’ Al extracted by 0.02 M CaCl2. The relationship appears to be linear, with a correlation coefficient of 0.77 (P=0.01). The Al content of tea leaves increases with a decrease of soil pH. This relationship is non-linear with a marked increase in leaf Al for soils with pH <5.0. The amounts of Al in soils extracted with 0.02 M CaCl2 was much less than other forms of Al in soils. The amount of Al measured in the tea leaves was directly related to both the ‘available’ form of Al in the soils and soil pH. Soil pH was identified as a major factor that controls the uptake of Al from soil into the tea leaves. 相似文献
3.
Fe and Al oxides distribution in some ultisols and inceptisols of southeastern Nigeria in relation to soil total phosphorus 总被引：3，自引：1，他引：2
Ten highly weathered soils in southeastern Nigeria were sampled from their typical A and B horizons for analyses. The objectives
were to determine the different forms of Fe and Al oxides in the soils and relating their occurrence to phosphate availability
and retention in the soils. The soils are deep and often physically degraded but are well drained and coarse in the particle
size distribution. They are mostly dominated by kaolinite in their mineralogy with very high values of SiO2. The soils are acidic with low soil organic carbon (SOC) contents. The elements in the exchange complex are also low thus
reflecting in the low CEC of the soil. Available phosphorus (P) in the soils are generally low while total P ranged from 157
to 982 mg kg−1 with an overall average of 422 mg kg−1. Total Fe in the soil is highest and their order represented as follows: Fet > Fed > Feox ≥ Fep. The pyrophosphate extractable Fe was always higher in the top soil than in the subsoil and was attributed to the fact that
these forms of Fe are associated with organic matter which is more abundant in topsoil than in subsoil. Like in Fe forms,
the order of Al occurrence could generally be presented as; Alt > Ald > Alox > Alp. More Fe and Al oxides in the soils are strongly crystalline while a small quantity is poorly crystalline Fe forms. The amorphous
forms of both Fe and Al are very low in the soils when compared with the crystalline forms. The oxides that show very strong
affinity to total P are Fed–Feox, Fed, Ald, Fet, Feox and Alox/Ald. To overcome this problem of P retention in the soil, we recommend constant liming of these soils to neutralize them, application
of organic matter and of high dosage of phosphate fertilizer to the soils. 相似文献
4.
The influence of ferrous and ferric iron on the low-temperature heat capacity and vibrational entropy of silicate glasses has been determined by adiabatic calorimetry. Two pairs of samples based on sodium disilicate and calcium Tschermak molecule compositions have been studied. Along with previous data for another Fe-bearing glass, these results have been used to complement the available set of composition independent partial molar relative entropies of oxides in silicate glasses with S298 − S0 values of 56.7 and 116 J/mol for FeO and Fe2O3, respectively. The calorimetric data indicate that the fraction of fivefold coordinated Al is significant in the CaO-“FeO”-Al2O3-SiO2 system and that association of Ca2+ and Na+ with Fe3+ in tetrahedral coordination for charge compensation does not entail significant changes in coordination for these two cations. At very low temperatures, however, the heat capacity is no longer an additive function of composition because of unexpectedly high positive deviations from Debye laws. These anomalies are stronger for the reduced than the oxidized glasses and considerably larger than for iron-free glasses, but their origin cannot be established from the present measurements. 相似文献
5.
We present δDwax values from different forms of plants and soils, and δDsw values from soil water along the northern slope of Mount Taibai, China. The results show a highly negative linear correlation of the δDwax values for soils with altitude (R2 0.74) and we observed the same correlation for δDsw values of soil water with altitude (R2 0.68). The δDwax of living plants behaves like the soil, but does not exhibit a significant linear correlation with altitude (R2 0.11). The δDwax values of woody plants and grasses also show a similar trend with respect to altitude with significant and no linear correlation, respectively (R2 0.50 for woody plants and 0.17 for grass), which suggest that the “altitude effect” can not be well documented for the δDwax values of living plants, which may be due to differences in plant type and/or evapotranspiration controlled by the plant microclimate. The εwax-sw values of woody plants, grasses and soil show minor fluctuations with altitude. However, the εwax-sw and δDwax values of woody plants are roughly 51‰ and 50‰ more positive, respectively, than those of grasses, suggesting that an “altitude effect” could be documented in the δDwax of woody plants and grasses, with each responding independently to changes in precipitation along the altitude transect. Additionally, the εwax-sw values of soil are relatively constant with altitude, suggesting that the altitudinal change in the proportions between woody plant and grass input to soils will likely change the relationship between the δDwax values of soil n-alkanes and altitude. 相似文献
6.
Revealing the atomic structure and disorder in oxide glasses, including sodium silicates and aluminosilicates, with varying degrees of polymerization, is a challenging problem in high-temperature geochemistry as well as glass science. Here, we report 17O MAS and 3QMAS NMR spectra for binary sodium silicate and ternary sodium aluminosilicate glasses with varying degrees of polymerization (Na2O/SiO2 ratio and Na2O/Al2O3 ratio), revealing in detail the extent of disorder (network connectivity and topological disorder) and variations of NMR parameters with the glass composition. In binary sodium silicate glasses [Na2O-k(SiO2)], the fraction of non-bridging oxygens (NBOs, Na-O-Si) increases with the Na2O/SiO2 ratio (k), as predicted from the composition. The 17O isotropic chemical shifts (17O δiso) for both bridging oxygen (BO) and NBO increase by about 10-15 ppm with the SiO2 content (for k = 1-3). The quadrupolar coupling products of BOs and NBOs also increase with the SiO2 content. These trends suggest that both NBOs and BOs strongly interact with Na; therefore, the Na distributions around BOs and NBOs are likely to be relatively homogenous for the glass compositions studied here, placing some qualitative limits on the extent of segregation of alkali channels from silica-enriched regions as suggested by modified random-network models. The peak width (in the isotropic dimension) and thus bond angle and length distributions of Si-O-Si and Na-O-Si increase with the SiO2 content, indicating an increase in the topological disorder with the degree of polymerization. In the ternary aluminosilicate glasses [Na2O]x[Al2O3]1−xSiO2, the NBO fraction decreases while the Al-O-Si and Al-O-Al fractions apparently increase with increasing Al2O3 content. The variation of oxygen cluster populations suggests that deviation from “Al avoidance” is more apparent near the charge-balanced join (Na/Al = 1). The Si-O-Si fraction, which is closely related to the activity coefficient of silica, would decrease with increasing Al2O3 content at a constant mole fraction of SiO2. Therefore, the activity of silica may decrease from depolymerized binary silicates to fully polymerized sodium aluminosilicate glasses at a constant mole fraction of SiO2. 相似文献
7.
The 26Al-26Mg isotope systematics in 33 petrographically and mineralogically characterized plagioclase-rich chondrules (PRCs) from 13 carbonaceous chondrites (CCs) - one ungrouped (Acfer 094), six CR, five CV, and one CO - reveal large variations in the initial 26Al/27Al ratio, (26Al/27Al)0. Well-resolved 26Mg excesses (δ26Mg) from the in situ decay of the short-lived nuclide 26Al (t1/2 ∼ 0.72 Ma) were found in nine chondrules, two from Acfer 094, five from the CV chondrites, Allende and Efremovka, and one each from the paired CR chondrites, EET 92147 and EET 92042, with (26Al/27Al)0 values ranging from ∼3 × 10−6 to ∼1.5 × 10−5. Data for seven additional chondrules from three CV and two CR chondrites show evidence suggestive of the presence of 26Al but do not yield well defined values for (26Al/27Al)0, while the remaining chondrules do not contain excess radiogenic 26Mg and yield corresponding upper limits of (11-2) × 10−6 for (26Al/27Al)0. The observed range of (26Al/27Al)0 in PRCs from CCs is similar to the range seen in chondrules from unequilibrated ordinary chondrites (UOCs) of low metamorphic grade (3.0-3.4). However, unlike the UOC chondrules, there is no clear trend between the (26Al/27Al)0 values in PRCs from CCs and the degree of thermal metamorphism experienced by the host meteorites. High and low values of (26Al/27Al)0 are found equally in PRCs from both CCs lacking evidence for thermal metamorphism (e.g., CRs) and CCs where such evidence is abundant (e.g., CVs). The lower (26Al/27Al)0 values in PRCs from CCs, relative to most CAIs, are consistent with a model in which 26Al was distributed uniformly in the nebula when chondrule formation began, approximately a million years after the formation of the majority of CAIs. The observed range of (26Al/27Al)0 values in PRCs from CCs is most plausibly explained in terms of an extended duration of ∼2-3 Ma for the formation of CC chondrules. This interval is in sharp contrast to most CAIs from CCs, whose formation appears to be restricted to a narrow time interval of less than 105 years. The active solar nebula appears to have persisted for a period approaching 4 Ma, encompassing the formation of both CAIs and chondrules present in CCs, and raising important issues related to the storage, assimilation and mixing of chondrules and CAIs in the early solar system. 相似文献
8.
Stabilisation of soil organic matter by interactions with minerals as revealed by mineral dissolution and oxidative degradation 总被引：4，自引：0，他引：4
Karin Eusterhues Cornelia Rumpel Markus Kleber Ingrid Kgel-Knabner 《Organic Geochemistry》2003,34(12):1591-1600
Soil organic matter is known to contain a stable fraction with an old radiocarbon age. Size and stabilisation processes leading to the formation of this old soil carbon pool are still unclear. Our study aims to differentiate old organic matter from young and labile carbon compounds in two acid forest soils (dystric cambisol, haplic podzol). To identify such fractions soil samples were exposed to oxidation with Na2S2O8 and to dissolution by hydrofluoric acid (HF). A negative correlation between 14C activity and carbon release after dissolution of the mineral matrix by HF indicates a strong association of stabilised carbon compounds with the mineral phase. A negative correlation between the 14C activity and the relative proportion of carbon resistant to oxidation by Na2S2O8 shows that young carbon is removed preferentially by this treatment. The fraction remaining after oxidation represents a certain stabilised, long residence time carbon pool. This old fraction comprises between 1 and 30% of the total soil organic carbon in the surface horizons, but reaches up to 80% in the sub-surface horizons. Old OC is mainly stabilised by organo-mineral associations with clay minerals and/or iron oxides, whereas intercalation in clay minerals was not found to be important. 相似文献
9.
Previous electron paramagnetic resonance (EPR) spectroscopic study of gamma-ray-irradiated stishovite at 77 K detected an
Al hole center, which was proposed to be an [O2
3−–Al3+] defect. First-principles quantum-mechanical calculations show that the unpaired spin is 85% localized on one of the six
oxygen atoms at an AlO6 octahedron, while the calculated 27Al hyperfine constants are similar to those determined by EPR experiments. Theoretical results allow us to propose the Al
center to represent an [AlO6]0 defect, and hole hoping among equivalent oxygen atoms is responsible for its detection only at cryogenic temperatures. Theoretical
calculations also show that the diamagnetic precursors [AlO6/H+]0, [AlO6/Li+]0, and [AlO6/Na+]0 are stable in stishovite. The calculated OH bond distance and orientation are in excellent agreement with those inferred
from FTIR spectra and previous theoretical calculations. The calculated [AlO6/Li+]0 and [AlO6/Na+]0 defects suggest that the monovalent cations such as Li+ and Na+ are potentially important in accommodating Al in stishovite in the lower mantle. 相似文献
10.
11.
Scott G. Johnston Edward D. Burton Richard T. Bush Annabelle F. Keene Leigh A. Sullivan Douglas Smith Angus E. McElnea Col R. Ahern Bernard Powell 《Applied Geochemistry》2010
Tidal inundation was restored to a severely degraded tropical acid sulfate soil landscape and subsequent changes in the abundance and fractionation of Al, Fe and selected trace metals were investigated. After 5 a of regular tidal inundation there were large decreases in water-soluble and exchangeable Al fractions within former sulfuric horizons. This was strongly associated with decreased soil acidity and increases in pH, suggesting pH-dependent immobilisation of Al via precipitation as poorly soluble phases. The water-soluble fractions of Fe, Zn, Ni and Mn also decreased. However, there was substantial enrichment (2–5×) of the reactive Fe fraction (FeR; 1 M HCl extractable) near the soil surface, plus a closely corresponding enrichment of 1 M HCl extractable Cr, Zn, Ni and Mn. Surficial accumulations of Fe(III) minerals in the inter-tidal zone were poorly crystalline (up to 38% FeR) and comprised mainly of schwertmannite (Fe8O8(OH)6SO4) with minor quantities of goethite (α-FeOOH) and lepidocrocite (γ-FeOOH). These Fe (III) mineral accumulations provide an effective substrate for the adsorption/co-precipitation and accumulation of trace metals. Arsenic displayed contrary behaviour to trace metals with peak concentrations (∼60 μg g−1) near the redox minima. Changes in the abundance and fractionation of the various metals can be primarily explained by the shift in the geochemical regime from oxic–acidic to reducing-circumneutral conditions, combined with the enrichment of reactive Fe near the soil surface. Whilst increasing sequestration of trace metals via sulfidisation is likely to occur over the long-term, the current abundance of reactive Fe near the sediment–water interface favours a dynamic environment with respect to metals in the tidally inundated areas. 相似文献
12.
Twelve goethite samples with different degrees of substitution of Al for Fe were synthesized at 22-48 °C and pH values of 1.5-14 under closed system conditions and used to study the effects of Al substitution on the hydrogen isotopic fractionation between goethite and its ambient water. The syntheses followed two pathways: (1) Fe3+ hydrolysis in high pH aqueous solutions; (2) oxidation of Fe2+ to Fe3+ in mid to low pH solutions. XRD and SEM analyses indicated that, irrespective of temperature and pH, goethite was the predominant product of the syntheses in all of the experiments (with degrees of Al substitution as high as ∼13 mol %). “High temperature nonstoichiometric” (HTN) water is present in all of the samples and rapidly exchanges D/H with ambient vapor at room temperature. Uncertainties in the value of the apparent D/H fractionation factor (αe-v) between HTN water and ambient exchange water at 22 °C lead to significant uncertainties in determinations of the δD values of structural hydrogen (δDs) in goethites which contain high proportions of HTN water. As determined for the samples of this study, αe-v has a nominal value of 0.942 (±0.02). δDs values determined using an αe-v value of 0.942 indicate that Al substitution increases the δD value of structural hydrogen in goethite by about 1.4 (±0.4)‰ for each increase in Al of 1 mol %. This dependence on Al is of the same sign as, but somewhat larger in magnitude than, the effect of Al predicted by a published model (∼0.7‰ per mol % Al). The overall uncertainties in the current results suggest that an increase of ∼1‰ per mol % Al, as adopted by previous studies, may be a reasonable estimate with which to adjust δ Ds values of natural goethites to those of the pure FeOOH endmember and could be valid for degrees of Al substitution of up to at least 15 mol %. These synthesis experiments also yield a hydrogen isotopic fractionation factor (DαG-W) between pure goethite (α-FeOOH) and liquid water of 0.900 (±0.006), which is analytically indistinguishable from the published value of 0.905 (±0.004). Thus, use of an DαG-W value of 0.905 in applications to the FeOOH component of natural goethites is supported by the current study. 相似文献
13.
Bjorn O. Mysen 《Geochimica et cosmochimica acta》2007,71(7):1820-1834
Solubility and solution mechanisms of H2O in depolymerized melts in the system Na2O-Al2O3-SiO2 were deduced from spectroscopic data of glasses quenched from melts at 1100 °C at 0.8-2.0 GPa. Data were obtained along a join with fixed nominal NBO/T = 0.5 of the anhydrous materials [Na2Si4O9-Na2(NaAl)4O9] with Al/(Al+Si) = 0.00-0.25. The H2O solubility was fitted to the expression, XH2O=0.20+0.0020fH2O-0.7XAl+0.9(XAl)2, where XH2O is the mole fraction of H2O (calculated with O = 1), fH2O the fugacity of H2O, and XAl = Al/(Al+Si). Partial molar volume of H2O in the melts, , calculated from the H2O-solulbility data assuming ideal mixing of melt-H2O solutions, is 12.5 cm3/mol for Al-free melts and decreases linearly to 8.9 cm3/mol for melts with Al/(Al+Si) ∼ 0.25. However, if recent suggestion that is composition-independent is applied to constrain activity-composition relations of the hydrous melts, the activity coefficient of H2O, , increases with Al/(Al+Si).Solution mechanisms of H2O were obtained by combining Raman and 29Si NMR spectroscopic data. Degree of melt depolymerization, NBO/T, increases with H2O content. The rate of NBO/T-change with H2O is negatively correlated with H2O and positively correlated with Al/(Al+Si). The main depolymerization reaction involves breakage of oxygen bridges in Q4-species to form Q2 species. Steric hindrance appears to restrict bonding of H+ with nonbridging oxygen in Q3 species. The presence of Al3+ does not affect the water solution mechanisms significantly. 相似文献
14.
The exchange kinetics of Cd, Cu, Pb, and Zn in seven mining and smelting-contaminated soils and the other two anthropogenically contaminated soils was investigated by using multi-elementary stable isotopic exchange kinetic (SIEK) method, and the experimental results were successfully interpreted by modelling using a sum of pseudo first order kinetics equations. SIEK results show that in the studied soils the isotopic exchange of Cd is a relatively fast process, and the exchange almost reaches an apparent plateau after 3-d equilibration; whereas for Cu, Pb, and Zn, the exchange is more sluggish, suggesting that it is important to understand the time-dependent metal mobility for risk assessment and management of contaminated soils. In most of the soils, the total isotopically exchangeable pool is divided, for all the metals, into two distinct pools: a fast exchangeable pool (E1) with a kinetic rate constant k1 having values around 1 min−1 and a much slower exchangeable pool (E2) with k2 ranging from 0.0001 min−1 to 0.001 min−1. The distribution of the two exchangeable pools varies significantly among metals. The amount of isotopically exchangeable Cd related to the fast pool is dominant, accounting for on average 60% of total isotopically exchangeable pool in the soils; whereas this pool is smaller for Cu, Zn, and Pb. The sequence of average k1 values is Cd > Pb ≈ Zn > Cu, consistent with the reported sequence of stability constants of metal-humic substances (HS) complexes while the average k2 values follow the order: Cd > Pb > Cu > Zn, probably controlled by the slow desorption of metal ions associated with soil organic matter (SOM) fraction. Our results imply that further study on the exchange kinetics of metals on each individual sorption surface in soils, especially SOM, is critical to help understanding the overall exchange kinetics of heavy metals in whole soils. 相似文献
15.
K. Mereiter 《Mineralogy and Petrology》1972,18(3):185-202
Zusammenfassung Die Kristallstruktur von künstlichem Voltait, K2Fe5
2+Fe3
3+Al[SO4]12· ·18 H2O, kubisch hexakisoktaedrisch,Fd3c–O
h
8,a
0=27,254 ,Z-16, wurde mittels photographischer Röntgendaten bestimmt. Die Aufklärung der Struktur erfolgte mit Patterson- und Fouriermethoden unter Zuhilfenahme des multiplen isomorphen Ersatzes. Die Verfeinerung nach der Methode der kleinsten Quadrate ergab mit anisotropen Temperaturfaktoren für 726 beobachteteF
hkl
R=0,033. Das Hauptmerkmal der Struktur ist ein 3dimensionales Gerüst aus [Fe3+O6]-Oktaedern, [Fe
5
6/2+
Fe
1
6/3+
O4(H2O)2]-Oktaedern und [K+O12]-Polyedern, die durch SO4-Tetraeder verknüpft werden. Hohlräume dieses Gerüstes werden von ungeordnet orientierten [Al(H2O)6]-Oktaedern eingenommen. Es wird gezeigt, daß Al als wesentlicher Bestandteil dieses Voltaits angesehen werden muß.
Mit 2 Abbildungen 相似文献
The crystal structure of voltaite, K2Fe5 2+Fe3 3+Al[SO4]12·18H2O
Summary The crystal structure of synthetic voltaite, K2Fe5 2+Fe3 3+Al[SO4]12· · 18 H2O, cubic hexakis-octahedral, space groupFd3c–O h 8,a 0=27.254 ,Z=16, was determined from photographic X-ray data. The structure was solved by Patterson and Fourier-methods with the aid of multiple isomorphic substitution. Least squares refinement with anisotropic temperature factors resulted inR=0.033 for 726 observedF hkl . The dominant structural feature is a continous framework composed of [Fe3+O6]-octahedra, [Fe 5 6/2+ Fe 1 6/3+ O4(H2O)2]-octahedra and [K+O12]-polyhedra linked by SO4-tetrahedra. The arrangement gives rise to cages occupied by disordered [Al(H2O)6]-octahedra. It is shown that Al must be considered to be a essential constituent of such voltaites.
Mit 2 Abbildungen 相似文献
16.
In Lake Cuicocha watershed, a young caldera lake, soils consist of volcanic deposits with a high SiO2 and Al2O3 content; these andisols are in an early stage of development; and in drainage water from the watershed, aluminium concentrations
reach 15.0 μmol L−1. Total aluminium concentrations in Lake Cuicocha water raises up to 7.2 μmol L−1, with nearly 70% occurring as filterable Al at neutral to weak alkaline conditions. Al polymerization to gelatinous aggregates
of a few hundred micrometres in diameter as well as the occurrence of Al microcrystals like gibbsite as an ageing product
of gelatinous Al polymers was noted in the lake water. The gelatinous Al leads to the formation of larger aggregates resulting
in flocs of bacteria, algae, microorganisms and detritus. 相似文献
17.
Diorite plutons at Al Hadah Saudi Arabia, which constitute part of the pan-African magmatic sequence (ca. 600 Ma), exhibit
extensive development of epidote. The epidote alteration is concentrated along veins and dyke margins, and is characterised
by transformation of plagioclase (Ab 67)+hornblende+biotite+quartz to epidote+hornblende+tremolite−actinolite+plagioclase
(Ab 99)±quartz. The reactions involve addition of CaO and total Fe2O3, depletion of MgO, Na2O and K2O, with variable gains or losses of SiO2. Epidotised alteration products are hydrated and oxidised relative to the diorite precursor. The whole rock δ18O of fresh diorite is + 8.2‰ to + 8.8‰, whereas epidote domains have δ18O whole rock of +9.8‰ to +10.48‰ and negative Δ18Oquartz-plagioclase, implying oxygen isotope exchange with fluids at low temperatures.
Epidotisation is considered to have accompanied influx of fluids into plutons during cooling and contraction. The fluids were
probably deep formation waters with relatively high Ca2+/Na+ ratios, moving up thermal gradient. 相似文献
18.
Ellen P.M.J. Fest Erwin J.M. Temminghoff Jasper Griffioen Bas Van Der Grift Willem H. Van Riemsdijk 《Applied Geochemistry》2007
Aluminium has received great attention in the second half of the 20th century, mainly in the context of the acid rain problem mostly in forest soils. In this research the effect of land use and depth of the groundwater on Al, pH and DOC concentration in groundwater under Dutch sandy soils has been studied. Both pH and DOC concentration play a major role in the speciation of Al in solution. Furthermore, the equilibrium with mineral phases like gibbsite, amorphous Al(OH)3 and imogolite, has been considered. Agricultural and natural land use were expected to have different effects on the pH and DOC concentration, which in turn could influence the total Al concentration and the speciation of Al in groundwater at different depths (phreatic, shallow and deep). An extensive dataset (n = 2181) from the national and some provincial monitoring networks on soil and groundwater quality was used. Land use type and groundwater depth did influence the pH, and Al and DOC concentrations in groundwater samples. The Al concentration ranged from <0.4 μmol L−1 at pH > 7 to 1941 μmol L−1 at pH < 4; highest Al concentrations were found for natural-phreatic groundwater. The DOC concentration decreased and the median pH increased with depth of the groundwater. Natural-phreatic groundwater showed lower pH than the agricultural-phreatic groundwater. Highest DOC concentrations were found for the agricultural-phreatic groundwater, induced by the application of organic fertilizers. Besides inorganic complexation, the NICA-Donnan model was used to calculate Al3+ concentrations for complexation with DOC. Below pH 4.5 groundwater samples were mainly in disequilibrium with a mineral phase. This disequilibrium is considered to be the result of kinetic constraints or equilibrium with organic matter. Log K values were derived by linear regression and were close to theoretical values for Al(OH)3 minerals (e.g. gibbsite or amorphous Al(OH)3), except for natural-phreatic groundwater for which lower log K values were found. Complexation of Al with DOC is shown to be an important factor for the Al concentrations, especially at high DOC concentrations as was found for agricultural-phreatic groundwater. 相似文献
19.
Frédéric Feder Fabienne Trolard Guilhem Bourrié 《Geochimica et cosmochimica acta》2005,69(18):4463-4483
A miniaturized Mössbauer spectrometer, adapted to the Earth’s conditions from the instrument developed for Mars space missions, has been used for the first time to study in situ variations with depth and transformations with time of iron minerals in a gleysol. The instrument is set into a PVC tube and can be moved up and down precisely (±1 mm) at the desired depth. Mössbauer spectra were obtained from 15 to 106 cm depth and repeated exactly at the same point at different times to follow mineralogical transformations with time. X-ray diffraction (XRD) and selective extraction techniques were performed on soil samples. The piezometric level of the water table was measured and the composition of the soil solution was monitored in situ and continuously, with a multiparametric and automatic probe. All the Mössbauer spectra obtained are characteristic of Fe(II)-Fe(III) green rust-fougerite, a natural mineral of the meixnerite group, that is, whose structural formula is: [Fe1 − xII Mgy FexIII (OH)2+2y]x+[xA, mH2O]x−, where x is the ratio Fe3+/Fetot. and A the intercalated anion. The name of fougerite has been formally approved by the Commission on New Minerals and Mineral Names of IMA (number 2003-057), on January 29, 2004. No other iron phases have been found by this way or by XRD. About 90% of total iron is extractible by dithionite-citrate-bicarbonate, and 60% by citratebicarbonate. In the horizons showing oximorphic properties that are in the upper part of the studied soil profile, x ratio in fougerite, deduced from Mössbauer spectra, is approximately 2/3. In the deepest horizons that show reductomorphic properties, x ratio is only 1/3. Fast mineralogical transformations were observed at well-defined points in soil, as evidenced by x ratio variations observed when Mössbauer spectra were acquired at different times at the same depth. Variations of the level of the water table and of pe and pH of the soil solution were simultaneously observed and could explain these mineralogical transformations. A ternary solid solution model previously proposed for OH-fougerite has been extended to chloride, sulphate, and carbonate green rusts to estimate the Gibbs free energies of formation of fougerite, providing for possible anions other than OH− in the interlayer and for Mg substitution. Soil solutions appear as largely oversaturated with respect to OH-fougerite, either oversaturated or undersaturated to “carbonate-fougerite” and “sulphate-fougerite”, and largely undersaturated with respect to “chloro-fougerite”. Fougerite forms most likely from oversaturated solutions by coprecipitation of Fe3+ with Fe2+ and Mg2+. Oxidation and reduction are driven by pH and pe variations, with both long timescale variations and short duration events. Exactly as synthetic green rusts are very reactive compounds in the laboratory, fougerite is thus a very reactive mineral and readily forms, dissolves, or evolves in soils. 相似文献
20.
Phosphate sorption and desorption experiments were conducted with four ferruginous soils (alfisols) of Eastern India, in view of the low native phosphate concentrations in tropical Indian soils. From the P-isotherm curve, standard P requirement (SPR) of the soils was determined. Phosphate sorption data were fitted to both Langmuir and Freundlich equations and mean sorption maximum values obtained for the different soil series were in the decreasing order as Matimahal > Anandapur > Mrigindih > Kashipur. The fraction of added P sorbed followed the same trend as SPR, P sorption maximum (Pmax), phosphate affinity constant (K), maximum phosphate buffering capacity (MPBC), Freundlich constant K′ and phosphate desorption values. Phosphate sorption maximum was significantly correlated with MPBC, Freundlich 1/n, SPR, clay and different forms of Fe and Al. The value of K (bonding energy) was significantly correlated with MPBC, Freundlich K′ and pyrophosphate extractable Fe and Al. The MPBC was significantly correlated with Freundlich K′, Freundlich constant 1/n, clay, oxalate and dithionite extractable, amorphous and crystalline form of Fe and Al. Freundlich K′ was significantly correlated with Freundlich 1/n, pHwater, clay, dithionite extractable and crystalline form of Fe and Al. The results suggested that the soils having higher amount of extractable and reactive Fe and Al shared higher P sorbtion capacity and such soils may need higher levels of P application 相似文献