The oxidation of surface functional groups on biochar increases its reactivity and may contribute to the cation exchange capacity of soil. In this study, two Eucalyptus wood biochars, produced at 450 °C (B450) and 550 °C (B550), were incubated separately in each of the four contrasting soils for up to 2 years at 20 °C, 40 °C and 60 °C. Carbon functional groups of the light fraction (< 1.8 g/cm3) of the control and biochar amended soils (fresh and aged for 1 and 2 years at 20 °C, 40 °C and 60 °C) were investigated using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS). The spectra of biochar and light fractions of the control and biochar amended soils showed two distinct peaks at ∼285.1 eV and 288.5 eV, which were attributed to the C1s-π1CC transitions of aromatic C and C1s-π1CO transitions of carboxylic C, carboxyamide C and carbonyl C. The proportion of aromatic C was substantially greater in the light fraction of the biochar amended soils than the corresponding light fraction of the control soils. Also, the proportion of aromatic C was much higher in the light fraction of the B550 amended soils than in the corresponding B450 amended soils. Neither NEXAFS nor XPS results show any consistent change in the proportion of aromatic C of biochar amended soils after 1 year ageing. However, XPS analysis of hand-picked biochar samples showed an increase in the proportion of carboxyl groups after ageing for 2 years, with an average value of 8.9% in the 2 year aged samples compared with 3.0% in the original biochar and 6.4% in the control soil. Our data suggest that much longer ageing time will be needed for the development of a significant amount of carboxyl groups on biochar surfaces. 相似文献
On the basis of on-site measured data of the newly constructed Gonghe-Yushu Highway in a permafrost region, this paper analyzed thermal conditions of the subgrade with XPS insulated board according to different selected monitoring sections in various locations. We also summarized the geothermal distribution and change rules of subgrade with XPS insulation board under the asphalt pavement in summarized a high temperature frozen soil region. It is suggested that the shoulder of subgrade with XPS insulation board be widen to a reasonable width so as to keep the subgrade stable. 相似文献
The behaviour of Fe-oxides was investigated during precipitation and co-precipitation, phase transformation and dissolution, while their ability to adsorb and incorporate trace components was examined. Some samples were synthesised and studied under controlled laboratory conditions and other samples were taken from experiments designed to test the effectiveness of waste treatment strategies using iron. Surface-sensitive and high-resolution techniques were used to complement information gathered from classical, macroscopic methods.
Adsorption isotherms for Ni2+ uptake on synthetic ferrihydrite (Fe5HO8·4H2O, often written simply Fe(OH)3), goethite (-FeOOH), hematite (-Fe2O3) and magnetite (Fe3O4) were all similar, increasing as expected at higher pH. Desorption behaviour was also similar, but one third or more of the Ni2+ failed to return to solution. In the past, “irreversible sorption” has been blamed on uptake into micro-fractures or pores, but during examination (using Atomic force microscopy, AFM) of hundreds of Fe-oxide particles, no evidence for such features could be found, leading to the conclusion that Ni2+ must become incorporated onto or into the solids. When solutions of Fe(II) are oxidised in controlled laboratory conditions or during treatment of ash from municipal waste incinerators, two-line ferrihydrite forms rapidly and on never-dried samples, AFM shows abundant individual particles with diameter ranging from 0.5 to several tens of nanometers. Aging in solution at 70°C promotes growth of the particles into hematite and goethite and their identification (by X-ray powder diffraction, XRPD, with Rietveld refinement) becomes possible at the same aging stage as mineral morphology becomes recognisable by AFM. In other experiments that were designed to mimic natural attack by organic acids, colloidal lepidocrocite (γ-FeOOH) was observed in situ by AFM, while reductive dissolution removed material on specific crystal faces. Lath ends are eroded fastest while basal planes are more stable.
In order to help elucidate mechanisms of contaminant immobilisation by Fe-oxides, we examined samples from a reactive barrier made with 90% quartz sand, 5% bentonite and 5% zero-valent iron filings that had reacted with a solution typical of leachate from coal-burning fly ash using time-of-flight secondary ion mass spectroscopy (TOF-SIMS). Fe(0) oxidised to Fe(III), while soluble and toxic Cr(VI) was reduced to insoluble Cr(III). Chemical maps show Fe-oxide coatings on bentonite; Cr is associated with Fe-oxides to some extent but its association with Ca in a previously undescribed phase is much stronger. Other samples taken from municipal waste incinerator ash that had been treated by aeration in Fe(II) solutions were examined with transmission electron microscopy (TEM), selected area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDS). Pb and some Zn are seen to be dispersed throughout two-line ferrihydrite aggregates, whereas Sn and some Zn are incorporated simply as a result of entrainment of individual ZnSn-oxide crystallites.
Geochemical speciation models that fail to account for contaminant uptake in solid solutions within major phases or as thin coatings or entrained crystals of uncommon phases such as those described here risk to underestimate contaminant retardation or immobilisation. 相似文献
X-ray photoelectron spectra have been obtained under the same experimental conditions for synthetic α-NiS and natural β-NiS in order to establish any difference in S electronic environment, and to test the proposition that S core electron binding energies increase measurably with coordination number when the same metal is in different sulfide structures or lattice sites. The Ni and S electronic environments in the two NiS structures have been further probed by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and the NEXAFS spectra interpreted by reference to spectra simulated by ab initio calculations. The photoelectron and NEXAFS spectra for freshly prepared surfaces of α-NiS and β-NiS were found to be similar, with only subtle differences in electronic environment evident in the experimental and simulated NEXAFS spectra. The measured and calculated core electron binding energies did not support the previously postulated relationship between S coordination number and electron binding energies. 相似文献
A number of freshly abraded surfaces of pentlandite have been characterised by X-ray photoelectron spectroscopy to establish whether the initial intensity of the S 2p component near 161.4 eV, previously assigned to the 25% of S atoms in fourfold coordination by metal atoms in pentlandite, was always at least 25% of the total S 2p intensity. It was found that the intensity of this S 2p component could be lower than 20% for surfaces that were not significantly oxidised. To assess whether the proposed 0.75–0.8 eV 2p binding energy difference for the two sulfur environments in pentlandite was justified, ab initio calculations of the difference in core electron binding energies and of the densities of unfilled states have been carried out. The corresponding simulated S K near-edge X-ray absorption fine structure (NEXAFS) spectra have been compared with experimental spectra. The calculated S 2p and S 1s binding energy differences were 0.45 and 0.5 eV at most, in agreement with the experimental NEXAFS spectra. It was concluded that the S 2p component near 161.4 eV arises entirely from violarite present at the pentlandite surface rather than from 4-coordinate S in pentlandite itself. Ab initio calculations of the difference in S 2p binding energies for the 2- and 3-coordinate S in stibnite have also been carried out and found to be quite small, in agreement with previously reported experimental values. Nevertheless, for both pentlandite and stibnite, calculations have confirmed that an increase in coordination number is associated with an increase in sulfur core electron binding energies, even although that increase is barely measurable for the latter sulfide. 相似文献