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1.
Inherent chemical recalcitrance and association of organic matter (OM) with minerals are mechanisms responsible for the long term preservation of OM in soils. The structural characteristics of OM are also believed to control specific interactions between OM and soil minerals. However, the extent of the relationship between recalcitrance and mineral protection and the specificity of these chemically driven interactions are not clearly understood at the molecular level. To measure chemical patterns of OM sequestration in sand-, silt-, clay-size and light fractions, we analyzed three soils, which mainly differed in carbon content and overlying vegetation, but have similar clay mineralogy, using biomarker analysis and nuclear magnetic resonance (NMR). Despite differences in environmental controls, long chain aliphatic compounds generally accumulated in the fine fractions of all soils. This accumulation is likely due to the strong interaction between recalcitrant forms of OM and soil minerals. For example, polymethylene and >C20 organic acids accumulated in fine fractions, while lignin-derived phenols were protected from oxidation in silt-size fractions. Diffusion edited solution state 1H NMR suggested that contributions from microbial-derived OM was greater in finer fractions, which is likely due to the accumulation of microbial-derived compounds or higher microbial activity in clay micro-sites. Our data suggest that, for these Prairie soils, the specific structure of OM and not environmental factors is responsible for long term preservation of OM in mineral fractions. Further research is necessary to understand the interplay between these preservation mechanisms such that the long term fate of OM can be further elucidated. 相似文献
2.
Aggregation of particulate organic matter (POM) and mineral grains may result in physical protection of organic matter (OM). To test this, phytoplankton cells of the dinoflagellate Scrippsiella trochoidea were inoculated with a natural bacterial assemblage and incubated with or without the clay montmorillonite. Within 5 h, aggregation of phytoplankton OM and clay resulted in transfer of the majority (∼80%) of OM into the >1.6 g cm−3 density fraction. Degradation of particulate organic carbon (POC), particulate nitrogen (PN), dissolved organic carbon (DOC), and dissolved and particulate total hydrolyzable amino acids (THAA), were modeled with a multi-G approach. Quantity of resistant OM was between two and four times larger during clay incubation relative to clay-free incubation. The two incubations did not exhibit significant differences in degradation state of particulate amino acids nor were there indications of preferential sorption of basic amino acids. The results suggest that a considerable fraction of phytoplankton OM can become resistant, at least on a timescale of weeks, mostly due to aggregation of POM and clay mineral grains. 相似文献
3.
为了探索西南喀斯特地区土壤中黏土矿物组成及其含量的变异规律,以贵州省普定县和荔波县不同石漠化阶段典型土壤的黏土矿物为例,采用x-射线衍射仪图谱分析方法,计算得到黏土矿物组成及其含量,探讨不同石漠化阶段黏土矿物组成变化规律及其含量之间的线性关系。结果表明：不同石漠化阶段黏土矿物的组成是相同的,均为高岭石、蒙脱石和伊利石;在未石漠化、轻度石漠化、中度石漠化阶段,蒙脱石在剖面表层的质量分数分别为27．82％、29．34％、58．32％,高岭石分别为21．39％、31．81％、36．93％,伊利石分别为50．79％、38．85％、4．75％;在西南喀斯特地区,各石漠化阶段伊利石与蒙脱石的含量之间以及伊利石和高岭石的含量之间都呈显著的线性相关,相关系数分别为-0．9703、-0．9456;西南喀斯特地区土壤相似的成土作用和成土环境造成了黏土矿物相同的组成,而黏土矿物含量的差异说明各成土作用的程度或阶段是不同的;粉粒中的黏土矿物主要为石英和白云母,而砂砾中的黏土矿物主要为石英。 相似文献
4.
We examined relationships between the pore structure of microaggregates and the protection of organic matter (OM) within that structure. By using ultra-small angle X-ray scattering (USAXS) before and after combustion of microaggregates at 350 °C, we took advantage of differences in X-ray scattering contrast among soil minerals, OM, and air to evaluate the distribution of the total- and OM-filled porosity within microaggregates (53-250 μm in diameter). Systematic changes in microaggregate structure were observed for long-term field manipulations of land use (a chronosequence of tallgrass prairie restorations) and agricultural management (conventional tillage versus no-till at two levels of nitrogen fertilization). Our results imply that OM preservation arose from the evolution of the architectural system of microaggregates during their formation and stabilization. Soils and treatments with increasing OM in microaggregates were associated with encapsulation of colloidal OM by minerals, thereby creating protected OM-filled pores at the submicron scale within the microaggregate structure. For example, in the prairie chronosequence, microaggregates from the cultivated soil had the lowest concentration of OM, but 75% of the OM that had survived cultivation was in OM-filled pores. Following restoration, the concentration of OM in microaggregates increased rapidly, but the proportion of OM in OM-filled pores declined initially and then increased over time until 90% of the OM was in OM-filled pores. OM totally encapsulated within the pore structure can create spatial and kinetic constraints on microbial access to and degradation of OM. Encapsulation of OM increases the capacity for its protection relative to sorption on mineral surfaces, and comparison of its extent among treatments suggests important feedback loops. The use of USAXS, which has not previously been applied to the study of soil aggregate structures and the distribution of OM within those structures, provided new information on the mechanisms of OM protection in soil microaggregates, and insights relevant to strategies for enhancing carbon-sequestration in soil through changes in agricultural management practices and land use. 相似文献
5.
Aqueous solutions of increasing pH (7.0, 10.6 and 12.6) were used to extract exhaustively the organic matter (OM) from a pelo-stagnogley (heavy clay) soil in long term cultivation. OM yield was 1.7 times greater when the extracts were processed using an XAD-8 and XAD-4 resin-in-tandem procedure than that from the procedure of the International Humic Substances Society (IHSS). The substantial difference can be attributed to the amount retained by the XAD-4 resin, which is lost in the IHSS process. Elemental, δ13C, δ15N, cation exchange capacity, neutral sugars, amino acids and solid state CPMAS 13C NMR analyses indicated significant, but rational similarities and differences between the various fractions isolated. There was strong NMR evidence for material derived from lignin in all the humic and fulvic acid isolates. The signals were attenuated in the more transformed/oxidized fractions isolated at lower pH. Novel humic acid fractions enriched in carbohydrate/peptide functionalities were isolated from the more hydrophobic extracts at pH 10.6 and 12.6. Isolates from XAD-4, of microbial origin, were enriched in neutral sugars but not in amino acids, and had minimal aromaticity. Components isolated from the cultivated soil were broadly similar to those from a comparable soil in long term grassland. The compositions of fractions isolated from the drainage water were similar to those extracted from the soil but had higher carboxyl content. The amount and composition of the various organic fractions in grassland and the continuously cropped soil are discussed in terms of their potential to contribute to carbon sequestration by soil under similar management regimes. 相似文献
6.
Olaf Brockamp 《Geochimica et cosmochimica acta》1973,37(5):1339-1351
Clay minerals synthesized under surface conditions take up boron in proportion to the concentration of boron in the solution. A synthetic montmorillonite contained 2160 ppm B when precipitated from a solution containing 5 ppm B and having a pH of 8.5. The fixation of B by the synthetic clay mineral is greatly reduced by a high ?HCO3 concentration in the solution. Part of the fixed boron is incorporated into the tetrahedral sheet of the clay mineral structure, whereas the remainder is present in the form of a Mg borate-like complex. Mg borate-like complexes similar to those found in the synthetic clay may also occur in detrital clays. This possibility was examined experimentally using natural illite and montmorillonite suspended in solutions containing boron alone and magnesium-boron in combination at pH 8–9 and 10. The results show that more B was sorbed from solutions containing both Mg and B than from solutions containing B alone. For example, at pH 8, montmorillonite takes up 18 ppm B from the combination solution and 11 ppm from a solution containing only B. In a similar experiment, illite takes up 28 and 20 ppm B, respectively. It is suggested that B in natural clays is fixed partly as a Mg-borate-like complex. This complex probably formed as a first step by sorption of B to Mg(OH)2, which may be present in clays.These results should apply to the interpretation of the boron content of recent clayey sediments 相似文献
7.
Strong correlations between iron oxides (FeOx) and organic matter (OM) in soils have implied the importance of the former in stabilizing the latter. One mechanism thought to be important in this stabilization is sorption. We tested this possibility by reductively dissolving FeOx in a wide variety of soils and measuring the organic carbon (OC) that was solubilized. The OC dissolved from non-FeOx phases via anion exchange was corrected for by parallel control extractions. The resultant pool, reductively soluble OC, made up a minor amount of total soil OC in all but one of these soils, indicating that simple sorption reactions do not stabilize the bulk of soil OC in most mineral soils. OC:Fe ratios in the extracts from 2/3 of these soils were less than 0.22 (wt/wt), consistent with a sorbed state for this OC and showing that OC sorption by FeOx in these soils is limited by the amount of FeOx. The remaining soils had low pH and high OM concentrations; their higher OC:Fe ratios indicate inclusion of precipitated organo-Fe complexes in the extracts, which are likely only partially extracted by our method. The high volumetric ratios of OM to FeOx found in correlations between them from the literature are inconsistent with a dominant sorption control and point instead to stabilization to other mechanisms such as organo-Fe complexes or ternary associations among FeOx, OM and other minerals. 相似文献
8.
Interactions between organic matter (OM) and minerals are important for the preservation of organic material in marine sediments. Recent evidence suggests that these interactions may not be due to protection of the organic matter via simple sorption to minerals, but rather that the organic matter is acting as a glue between mineral particles resulting in aggregate formation. Density fractionation into multiple density intervals is a powerful approach for looking at the patchy nature of organic matter distribution (Bock, M.J., Mayer, L.M., 2000. Mesodensity organo-clay associations in a near-shore sediment. Marine Geology 163, 65–75), because isolates with varying organic matter loadings can be obtained. The aggregate surfaces can be examined using X-ray photoelectron spectroscopy (XPS), because this technique is restricted to the top 10 nm of the sample surface. XPS gives quantitative information on all the elements on the surface (except H and He) and, in addition, gives information on the chemical bonding of carbon and nitrogen. We used these techniques, along with more standard geochemical tools (CHN, surface area and amino acid analyses), to study a sediment sample of high organic matter content from the oxygen deficient zone off the western coast of Mexico. We found that amino acid composition indicates that the fractions get progressively more degraded as density increases, while the fraction of carbon bonded to oxygen suggests that the oxidation state of the organic matter is similar for all fractions. In addition, the comparison of surface carbon concentrations from XPS and OC:SA suggests that the OM is located in discrete spots on the surface and that as density increases (OC:SA decreases) the organic matter decreases in thickness while retaining the same proportional areal extent. 相似文献
9.
Maarten Nachtegaal André M. Scheidegger Rainer Dähn Gerhard Furrer 《Geochimica et cosmochimica acta》2005,69(17):4211-4225
The sorption capacity of montmorillonite clay minerals for small cations, such as Ni2+, can be greatly enhanced by modifying the clay mineral with Al(III). In this study, the mechanisms of Ni uptake by Al-modified montmorillonite were studied using extended x-ray absorption fine structure (EXAFS) spectroscopy of powders and polarized EXAFS spectroscopy of self-supporting clay films to delineate the binding structure of Ni formed as a function of the reaction conditions. Analysis of powder EXAFS spectra of wet pastes, collected from Ni-treated Al-modified montmorillonites reacted at pH 5-8, 25°C or 80°C (to accelerate the reaction process), and reaction times ranging from 1 month to 9 yrs, showed that Ni was surrounded on average by 6 O atoms at a distance of 2.05 Å and 6 Al atoms at 3.01 Å, suggesting the incorporation of Ni into a gibbsite-like structure. Only at pH 8, Ni-containing precipitates were congruently formed. Polarized EXAFS spectroscopy of self-supporting Ni-reacted Al-modified montmorillonite clay films showed a pronounced angular dependency of the spectra of the Ni-doped gibbsite, indicating that the orientation of this Ni-doped gibbsite coincided with the layering of the montmorillonite. Data analysis suggested that Ni is included slightly above and below the vacant octahedral sites of the postulated interstitial gibbsite monolayer. This newly identified mechanism of metal uptake by Al-modified montmorillonite provides a large metal sorption capacity and, because the metal is included in a monolayer gibbsite or gibbsite “islands” formed in the interstitial space of the clay mineral, it potentially leads to a permanent sequestration of the metal from the environment. 相似文献
10.
Robert Mikutta Gabriele E. Schaumann Steeve Bonneville Jon Chorover Georg Guggenberger 《Geochimica et cosmochimica acta》2009,73(7):2034-7005
Organic matter (OM) in mineral-organic associations (MOAs) represents a large fraction of carbon in terrestrial ecosystems which is considered stable against biodegradation. To assess the role of MOAs in carbon cycling, there is a need to better understand (i) the time-dependent biogeochemical evolution of MOAs in soil, (ii) the effect of the mineral composition on the physico-chemical properties of attached OM, and (iii) the resulting consequences for the stabilization of OM. We studied the development of MOAs across a mineralogical soil gradient (0.3-4100 kyr) at the Hawaiian Islands that derived from basaltic tephra under comparable climatic and hydrological regimes. Mineral-organic associations were characterized using biomarker analyses of OM with chemolytic methods (lignin phenols, non-cellulosic carbohydrates) and wet chemical extractions, surface area/porosity measurements (N2 at 77 K and CO2 at 273 K), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The results show that in the initial weathering stage (0.3 kyr), MOAs are mainly composed of primary, low-surface area minerals (olivine, pyroxene, feldspar) with small amounts of attached OM and lignin phenols but a large contribution of microbial-derived carbohydrates. As high-surface area, poorly crystalline (PC) minerals increase in abundance during the second weathering stage (20-400 kyr), the content of mineral-associated OM increased sharply, up to 290 mg C/g MOA, with lignin phenols being favored over carbohydrates in the association with minerals. In the third and final weathering stage (1400-4100 kyr), metastable PC phases transformed into well crystalline secondary Fe and Al (hydr)oxides and kaolin minerals that were associated with less OM overall, and depleted in both lignin and carbohydrate as a fraction of total OM. XPS, the N2 pore volume data and OM-mineral volumetric ratios suggest that, in contrast to the endmember sites where OM accumulated at the surfaces of larger mineral grains, topsoil MOAs of the 20-400-kyr sites are composed of a homogeneous admixture of small-sized PC minerals and OM, which originated from both adsorption and precipitation processes. The chemical composition of OM in surface-horizon MOAs, however, was largely controlled by the uniform source vegetation irrespective of the substrate age whereas in subsoil horizons, aromatic and carboxylic C correlated positively with oxalate-extractable Al and Si and CuCl2-extractable Al concentrations representing PC aluminosilicates and Al-organic complexes (r2 > 0.85). Additionally, XPS depth profiles suggest a zonal structure of sorbed OM with aromatic carbons being enriched in the proximity of mineral surfaces and amide carbons (peptides/proteins) being located in outer regions of MOAs. Albeit the mineralogical and compositional changes of OM, the rigidity of mineral-associated OM as analyzed by DSC changed little over time. A significantly reduced side chain mobility of sorbed OM was, however, observed in subsoil MOAs, which likely arose from stronger mineral-organic bindings. In conclusion, our study shows that the properties of soil MOAs change substantially over time with different mineral assemblages favoring the association of different types of OM, which is further accentuated by a vertical gradient of OM composition on mineral surfaces. Factors supporting the stabilization of sorbed OM were (i) the surface area and reactivity of minerals (primary or secondary crystalline minerals versus PC secondary minerals), (ii) the association of OM with micropores of PC minerals (via ‘sterically’ enhanced adsorption), (iii) the effective embedding of OM in ‘well mixed’ arrays with PC minerals and monomeric/polymeric metal species, (iv) the inherent stability of acidic aromatic OM components, and (iv) an impaired segmental mobility of sorbed OM, which might increase its stability against desorption and microbial utilization. 相似文献
11.
The lignin component of humic substances: Distribution among soil and sedimentary humic,fulvic, and base-insoluble fractions 总被引：1，自引：0，他引：1
Vanillyl, syringyl and cinnamyl phenols occur as CuO oxidation products of humic, fulvic and base-insoluble residual fractions from soils, peat and nearshore marine sediments. However, none of these lignin-derived phenols were released by CuO oxidation of deepsea sediment or its base-extractable organic fractions. Lignin analysis indicated that peat and coastal marine sediments contained significantly higher levels of recognizable vascular plant carbon (20–50%) than soils and offshore marine sediments (0–10%).Although accounting for less than 20% of the total sedimentary (bulk) lignin, lignin components of humic acid fractions compositionally and quantitatively resembled the corresponding bulk samples and baseinsoluble residues. Recognizable lignin, presumably present as intact phenylpropanoid units, accounted for up to 5% of the carbon in peat and coastal humic acids but less than 1% in soil humic acids. Fulvic acid fractions uniformly yielded less lignin-derived phenols in mixtures that were depleted in syringyl and cinnamyl phenols relative to the corresponding humic acid fractions.Within the vanillyl and syringyl families the relative distribution of acidic and aldehydic phenols is a sensitive measure of the degree of oxidative alteration of the lignin component The high acid/aldehyde ratios and the low phenol yields of soils and their humic fractions compared to peat and coastal sediments indicate extensive degradation of the lignin source material. Likewise, the progressively higher acid/aldehyde ratios and lower phenol yields along the sequence: plant tissues (plant debris)-humic acids-fulvic acids suggest that this pattern represents the diagenetic sequence for the aerobic degradation of lignin biopolymers. 相似文献
12.
M. M. Barbooti H. Su P. Punamiya D. Sarkar 《International Journal of Environmental Science and Technology》2014,11(1):69-76
This paper assesses the use of certified Iraqi montmorillonite clay as a potential sorbent for the removal of oxytetracycline (OTC) from aqueous solutions. The clay is characterized by a cation exchange capacity of 0.756 meq g?1 and a zero point charge at pH 8.7. Aqueous solutions of OTC were equilibrated with montmorillonite under various experimental conditions, such as OTC concentration, pH and clay content, for 24 h at fixed ionic strength. Two forms of montmorillonite were evaluated: regular and iron-modified form. The effect of pH was minor on OTC adsorption. Kinetic study revealed that the sorption follows a pseudo-second-order model. Sorption isotherm showed a good fit with the Freundlich model. OTC sorption onto Fe-saturated montmorillonite was analyzed statistically using a response surface design to study the effects of experimental conditions. The introduction of iron improved the adsorption characteristics of the clay due to the ability of ferric ions to make stable complexes with OTC. The most favorable operating conditions for the treatment were deemed as follows: clay content, 6.85 g L?1, oxytetracycline concentration, 1.0 mmol L?1 and pH, 5.5 for the iron-modified form. 相似文献
13.
《Geochimica et cosmochimica acta》2001,65(16):2709-2722
X-ray absorption spectroscopy (XAS) and adsorption-desorption measurements have been performed to assess the relationship between the structure and reversibility of copper complexes on montmorillonite clay. By varying the solution pH and background electrolyte concentration, the adsorption of copper on either the edge sites or permanent charge sites of montmorillonite was controlled. This allowed the structure and reversibility of copper complexes on each of these site types to be assessed independently of each other. XAS analysis of copper adsorbed on the permanent charge sites indicated outer-sphere surface complexes, with these complexes showing sorption reversibility. For copper complexes formed on the edge sites of montmorillonite, XAS data confirmed the presence of monomer and dimer copper surface complexes. Sorption irreversibility at edge sites was noted at copper coverages less than 20 μmoles/g clay at pH=4.2 and at coverages greater than 50 μmoles/g clay at pH=6.8. At pH=6.8, higher Cu-Cu coordination numbers indicated the copper sorption irreversibility may be due, in part, to the formation of dimer surface complexes. The coordination numbers at pH=4.2 indicated the irreversibility could be due to the formation of dimers or due to formation of surface complexes on high energy edge sites. 相似文献
14.
为探讨天然黏土矿物及有机质对纳米乳化油在多孔介质中迁移滞留的影响，本文选取高岭石和蒙脱石这两种黏土矿物以及有机质的典型代表腐殖酸，开展了单一矿物、有机质及有机矿质复合物对纳米乳化油的吸持批实验研究，并运用比表面积全分析、扫描电镜(SEM)、傅里叶红外光谱(FTIR)、X射线衍射(XRD)等技术手段探讨了吸持机理。实验结果表明，介质对纳米乳化油的吸持均符合Freundlich模型；单一矿物及腐殖酸对纳米乳化油的吸持能力表现为：蒙脱石>腐殖酸>高岭石，有机矿质复合样品的吸持能力表现为：蒙脱石-腐殖酸>高岭石-腐殖酸，且均大于其对应的单一样品，出现了“1+1>2”的现象，表明介质组成越复杂，对纳米乳化油的吸持滞留程度越大。进一步分析证实，纳米乳化油主要通过氢键和疏水作用吸持在矿物和腐殖酸表面，表面结构性质是高岭石和蒙脱石吸持过程中的主导因素，因此蒙脱石具有更强的吸持能力，而腐殖酸的吸持主要通过颗粒间聚集作用来实现；对于复合样品，吸持主要通过氢键、配体交换和疏水作用结合来实现。腐殖酸与矿物的复合会增加吸持位点并且增强矿物表面疏水性，从而促进吸持。腐殖酸与纳米乳化油的共吸... 相似文献
15.
The mobility of toxic metals in soils or sediments is of great concern to scientists and environmentalists since it directly affects the bioavailability of metals and their movement to surface and ground waters. In this study, a multi-surface soil speciation model for Cd (II) and Pb (II) was developed to predict the partition of metals on various soil solid components (e.g. soil organic matter (SOM), oxide mineral, and clay mineral). In previous study, the sorption of metal cations on SOM and oxide minerals has been evaluated by thermodynamically based surface complexation model. However, metal binding to soil clay fractions was normally treated in a simplistic manner: only cation exchange reactions were considered and exchange coefficient was assumed unity. In this study, the binding of metals onto clays was described by a two-site surface sorption model (a basal surface site and an edge site). The model was checked by predicting the adsorption behavior of Cd (II) and Pb (II) onto three selected Chinese soils as a function of pH and ionic strengths. Results showed that the proposed model more accurately predicted the metal adsorption on soils under studied condition, especially in low ionic strength condition, suggesting that adsorption of metals to soil clay fractions need to be considered more carefully when modeling the partition of trace elements in soils. The developed soil speciation model will be useful when evaluating the movement and bioavailability of toxic metals in soil environment. 相似文献
16.
17.
L. Grasset J. Martinod A.F. Plante A. Amblès C. Chenu D. Righi 《Organic Geochemistry》2009,40(1):70-78
Results of chemical treatments to isolate a pool of biochemically resistant soil organic matter (SOM) remain equivocal because they do not exhibit the expected relative increase in the proportion of resistant material with decrease in total SOM during long term biological mineralization. On the other hand, certain OM (considered to be enriched in aliphatic compounds) resists H2O2 oxidation as a result of association with minerals as well as its specific chemical recalcitrance, thereby protecting it against microbial degradation. Clay fractions isolated from soils under long term cultivation or long term bare fallow were examined using preparative thermochemolysis with TMAH (tetramethylammonium hydroxide, an alkylating agent) before and after peroxide treatment to characterise the molecular structure of the hydrophobic part (e.g. lipids). Results showed an increase in the proportion of some of the lipids after peroxide treatment, the lipids identified being mainly fatty acids (FAs) and hydrocarbons. The H2O2-resistant pools of lipids have an exclusively microbial signature but their quantity and relative distributions differed depending on land use. In the case of acids (as methyl esters), peroxide treatment appeared to mimic long term microbial oxidation, but this was not the case for n-alkanes. Chemical methods, such as H2O2, may not effectively mimic long term biological oxidation of clay-associated OM because, in isolation, they cannot account for the strong interaction between biochemical recalcitrance and physical protection, which exists even within the clay size fraction. 相似文献
18.
Ying Zhu Jingjing Liu Omanjana Goswami Ashaki A. Rouff Evert J. Elzinga 《Geochemical transactions》2018,19(1):3
We studied the effects of humic substances (HS) on the sorption of Fe(II) onto Al-oxide and clay sorbents at pH 7.5 with a combination of batch kinetic experiments and synchrotron Fe K-edge EXAFS analyses. Fe(II) sorption was monitored over the course of 4 months in anoxic clay and Al-oxide suspensions amended with variable HS types (humic acid, HA; or fulvic acid, FA) and levels (0, 1, and 4 wt%), and with differing Fe(II) and HS addition sequences (co-sorption and pre-coated experiments, where Fe(II) sorbate was added alongside and after HS addition, respectively). In the Al-oxide suspensions, the presence of HS slowed down the kinetics of Fe(II) sorption, but had limited, if any, effect on the equilibrium aqueous Fe(II) concentrations. EXAFS analyses revealed precipitation of Fe(II)–Al(III)-layered double hydroxide (LDH) phases as the main mode of Fe(II) sorption in both the HA-containing and HA-free systems. These results demonstrate that HS slow down Fe(II) precipitation in the Al-oxide suspensions, but do not affect the composition or stability of the secondary Fe(II)–Al(III)-LDH phases formed. Interference of HS with the precipitation of Fe(II)–Al(III)-LDH was attributed to the formation organo-Al complexes HS limiting the availability of Al for incorporation into secondary layered Fe(II)-hydroxides. In the clay systems, the presence of HA caused a change in the main Fe(II) sorption product from Fe(II)–Al(III)-LDH to a Fe(II)-phyllosilicate containing little structural Al. This was attributed to complexation of Al by HA, in combination with the presence of dissolved Si in the clay suspension enabling phyllosilicate precipitation. The change in Fe(II) precipitation mechanism did not affect the rate of Fe(II) sorption at the lower HA level, suggesting that the inhibition of Fe(II)–Al(III)-LDH formation in this system was countered by enhanced Fe(II)-phyllosilicate precipitation. Reduced rates of Fe(II) sorption at the higher HA level were attributed to surface masking or poisoning by HA of secondary Fe(II) mineral growth at or near the clay surface. Our results suggest that HS play an important role in controlling the kinetics and products of Fe(II) precipitation in reducing soils, with effects modulated by soil mineralogy, HS content, and HS properties. Further work is needed to assess the importance of layered Fe(II) hydroxides in natural reducing environments. 相似文献
19.
扬子地台寒武系泥页岩甲烷吸附特征 总被引：4，自引：0，他引：4
对采自扬子地区寒武系黄柏岭组、幕府山组和牛蹄塘组的泥页岩进行了甲烷吸附性能及影响因素研究。所分析页岩的TOC含量在1.08%～4.16%之间;粘土矿物含量在36.7%～62.3%之间。页岩样品甲烷吸附量测定结果显示,寒武系页岩甲烷最大理论吸附量与页岩TOC含量之间总体上呈正相关性,表明有机质丰度是控制页岩甲烷吸附能力的重要因素。而粘土矿物总含量与页岩甲烷最大理论吸附量之间缺乏相关性,仅蒙脱石含量与页岩甲烷最大理论吸附量呈正相关性,显示个别粘土矿物具有较强的甲烷吸附及影响页岩吸附性能的作用。寒武系不同地区页岩吸附性能存在显著差异,遵义牛蹄塘组页岩甲烷最大理论吸附量在2.76～5.30mL/g之间;南京幕府山组页岩甲烷最大理论吸附量在1.36～4.35mL/g之间;池州黄柏岭组泥页岩甲烷最大理论吸附量在1.63～2.72mL/g之间。此外,寒武系不同地区页岩有机碳含量与甲烷吸附量之间关系变化很大,显示页岩吸附量不仅受有机质丰度类型的影响,而且受有机质成熟度、区域地质演化以及粘土矿物吸附等多种因素制约。 相似文献
20.
Terra Preta de Índio (TPI) and Terra Mulata (TM) are anthropogenic soils from the Amazon region and are rich in stable organic matter (OM). The formation and incorporation of OM in these soils has recently been under investigation. Organic geochemical analysis is an appropriated tool for the assessment of the sources of OM. Therefore, we have used the distribution of different acid classes preserved in the free and bound soil fractions of 12 samples from two contrasting anthropogenic soils (TPI, TM) and an adjacent soil, in order to infer the sources of OM and the magnitude of non-cultural influence on the formation of anthropogenic soils. The major acids in both fractions (i.e. free and bound) were n-saturated, branched and unsaturated alkanoic acids, hydroxyalkanoic acids, bile acids and lignin/suberin derived aromatic acids. In general, the acids in the free and bound fractions appeared to be complementary and together provided valuable information about OM incorporation into anthropogenic soils. Different incorporation of ω-hydroxyalkanoic acids (C22, C24 and C28) and 9(10),16-dihydroxyhexadecanoic acid, and presence/absence of bile acid showed a distinct genesis for the soils. The influence of modern vegetation was revealed by bound ω-hydroxyalkanoic acid (C22, C24 and C28) distributions only in the topsoil profiles of TPI and TM, indicating that organic geochemical analysis is a useful approach in the investigation of ancient human deposits in tropical archaeological soils. 相似文献