Predicting C aromaticity of biochars based on their elemental composition

Three models were examined to predict C aromaticity (f_a) of biochars based on either their elemental composition (C, H, N and O) or fixed C (FC) content. Values of f_a from solid state ¹³C nuclear magnetic resonance (NMR) analysis with Bloch-decay (BD) or direct polarisation (DP) techniques, concentrations of total C, H, N, and organic O, and contents of FC of 60 biochars were either compiled from the literature (dataset 1, n = 52) or generated in this study (dataset 2, n = 8). Models were first calibrated with dataset 1 and then validated with dataset 2. All models were able to fit dataset 1 when atomic H to C ratio (H/C) < 1 (except two ash rich biochars) and to estimate f_a of HF treated biochars (H/C < 1). Model 1, which was based on values of H/C only and calibrated with a root mean square of error (RMSE) of 0.04 f_a-unit (n = 41), could predict the experimental data with a RMSE = 0.02 f_a-unit (n = 6). Model 2, which was based on biochar elemental composition data, showed the most accurate prediction, with a RMSE of 0.03 f_a-unit (n = 41) for the calibration data, and of 0.02 f_a-unit (n = 6, H/C < 1) for the validation data. Model 3, which was based on contents of FC and C, and modified with a correction factor of 0.96, displayed the highest RMSE (0.06 f_a-unit, n = 19) among the three models. Models 1 and 2 did not work properly for samples having either an H/C ratio > 1, high concentrations of carbonate or high inorganic H. These models need to be further tested with a wider range of biochars before they can be recommended for classification of biochar stability.     

Surface complexation model for strontium sorption to amorphous silica and goethite

Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25°C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr²⁺ and SrOH⁺ complexes on the β-plane and a monodentate Sr²⁺complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH⁺ complexes and a tetradentate binuclear Sr²⁺ species on the β-plane. The binuclear complex is needed to account for enhanced sorption at hgh strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr²⁺ and SrOH⁺ carbonate surface complexes on the β-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS) on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces.     

Characterization of biochars produced from oil palm and rice husks and their adsorption capacities for heavy metals

The objectives of this study were to determine the selected physicochemical properties of two biochars, one commercially produced from rice husks and the other from oil palm empty fruit bunches, and to evaluate their adsorption capacities for Zn, Cu, and Pb using a batch equilibrium method. The results showed that there was no significant difference between the carbon content of biochars formed from empty fruit bunches (EFBB) and rice husks (RHB). However, the EFBB did present higher quantities of O, H, S, N, and K, compared to the RHB. Although the EFBB had a much lower surface area than the RHB, the former adsorbed much more Zn, Cu, and Pb than the RHB. The higher adsorption capacity of the EFBB over the RHB was a result of the EFBB having higher amounts of oxygen-containing functional groups, a higher molar ratio of O/C, and a higher polarity index [(O + N)/C]. This suggests that the biochar’s chemical properties were more important than its surface area in the adsorption of Zn, Cu, and Pb.     

Physicochemical characteristics for adsorption of MTBE and cadmium on clay minerals

Physicochemical characteristics relevant to the adsorption of MTBE and Cd on three types of clay minerals were investigated. The characteristics were examined through batch adsorption tests conducted under various experimental conditions such as adsorption time, ratio of solution-to soil, concentration of solutes, concentration of organic matters, pH, and zeta potential. The adsorption efficiency of MTBE or Cd on three types of clays decreased in response to an increase of the ratio of solution-to-soil; nevertheless, the adsorbed amounts inversely increased. MTBE was adsorbed on clays in an increasing order of vermiculite, bentonite, and CTAB-bentonite. However, Cd was adsorbed in a different order of bentonite, vermiculite, and CTAB-bentonite. The adsorption of MTBE was well fitted with the Freundlich model, whereas the Cd was more closely suited to a Langmuir equation. By adding humic acids of 1 and 5%, MTBE was significantly adsorbed on bentonite and vermiculite, respectively, but beyond that, its adsorption was diminished. In comparison, the adsorption on CTAB-bentonite was increased in proportion to the humic acids addition. Likewise, the addition of humic acids acted to increase the adsorption of Cd regardless of the types of adsorbent, where up to 90% of Cd was removed at pH 10. Further increase of pH declined the degree of zeta potential, while increasing Cd concentration also lowered the zeta potential, which consequently contributes in enhancing the adsorption efficiency of Cd on clays.     

Hydrothermal synthesis of pyrochlores and their characterization

Pyrochlores, microlites, and U-betafites of pyrochlore group minerals were obtained from mixing experiments of the corresponding oxides and fluorides by hydrothermal synthesis at T = 800 °C and P = 200 MPa in the solution of 1.0 M NaF. The presence of U⁴⁺ in pyrochlore does not affect the cell parameter, which for the phases of pyrochlore–microlite series is 10.42 ± 0.01 Å. In a system with an excess of UO₂, pyrochlores and microlites, containing uranium up to 0.2–0.3 atoms per formula unit (apfu), are formed. In the uranium-free system of betafites composition, perovskites and Ti-bearing pyrochlores are formed. U-pyrochlores of betafite series, containing 2Ti = Nb + Ta in moles, have cubic cell parameters of 10.26 ± 0.02 Å and U⁴⁺ isomorphic capacity of 0.4–0.5 apfu. In the pyrochlore structure, U⁴⁺ may substitute for Ca²⁺ and Na⁺ cations in the eightfold site. In pyrochlores of pyrochlore–microlite series, Ca²⁺ is replaced by U⁴⁺, while in pyrochlores of betafite series, U⁴⁺ replaces Na⁺. Phases with pyrochlore structure, containing U⁵⁺ and U⁶⁺ in the sixfold site, usually occupied by Nb⁵⁺, Ta⁵⁺, and Ti⁴⁺, are formed under oxidizing conditions (Cu–Cu₂O buffer). They are characterized by low content of Nb⁵⁺, Ta⁵⁺ (<0.1 apfu), and anomalous behavior of the crystal lattice (compression, instead of expansion). Under natural conditions, the formation of pyrochlores containing a significant amount of U⁵⁺ and U⁶⁺ is unlikely.     

苯、甲苯碳同位素组成作为气源对比新指标的研究

利用热模拟与在线同位素分析技术研究了天然气与源岩中的苯和甲苯的央同位素组成变化特征,发现热成熟度和运移效应对苯、甲苯碳同位素组成影较小,同一类型气源岩热模拟产物中苯、甲苯同位素组成受热成熟度的影响不大。在４００～６００℃热模拟实验中,除个别点外,变化小于１‰,说明它们基本上不受热成熟度的影响。不同层位气源岩苯、甲苯碳同位素组成有明显区别,大多相差３‰以上。甲苯脱吸附实验表明,甲苯同位素组成在脱吸附     

Surface complexation and precipitate geometry for aqueous Zn(II) sorption on ferrihydrite: II. XANES analysis and simulation

X-ray absorption near-edge spectroscopy (XANES) analysis of sorption complexes has the advantages of high sensitivity (10- to 20-fold greater than extended X-ray absorption fine structure [EXAFS] analysis) and relative ease and speed of data collection (because of the short k-space range). It is thus a potentially powerful tool for characterization of environmentally significant surface complexes and precipitates at very low surface coverages. However, quantitative analysis has been limited largely to “fingerprint” comparison with model spectra because of the difficulty of obtaining accurate multiple-scattering amplitudes for small clusters with high confidence.In the present work, calculations of the XANES for 50- to 200-atom clusters of structure from Zn model compounds using the full multiple-scattering code Feff 8.0 accurately replicate experimental spectra and display features characteristic of specific first-neighbor anion coordination geometry and second-neighbor cation geometry and number. Analogous calculations of the XANES for small molecular clusters indicative of precipitation and sorption geometries for aqueous Zn on ferrihydrite, and suggested by EXAFS analysis, are in good agreement with observed spectral trends with sample composition, with Zn-oxygen coordination and with changes in second-neighbor cation coordination as a function of sorption coverage. Empirical analysis of experimental XANES features further verifies the validity of the calculations. The findings agree well with a complete EXAFS analysis previously reported for the same sample set, namely, that octahedrally coordinated aqueous Zn²⁺ species sorb as a tetrahedral complex on ferrihydrite with varying local geometry depending on sorption density. At significantly higher densities but below those at which Zn hydroxide is expected to precipitate, a mainly octahedral coordinated Zn²⁺ precipitate is observed. An analysis of the multiple scattering paths contributing to the XANES demonstrates the importance of scattering paths involving the anion sublattice. We also describe the specific advantages of complementary quantitative XANES and EXAFS analysis and estimate limits on the extent of structural information obtainable from XANES analysis.     

Welded tuff porosity characterization using mercury intrusion,nitrogen and ethylene glycol monoethyl ether sorption and epifluorescence microscopy

Porosity of welded tuff from Snowshoe Mountain, Colorado, was characterized by mercury intrusion porosimetry (MIP), nitrogen sorption porosimetry, ethylene glycol monoethyl ether (EGME) gas phase sorption and epifluorescence optical microscopy. Crushed tuff of two particle-size fractions (1-0.3 mm and less than 0.212 mm), sawed sections of whole rock and crushed tuff that had been reacted with 0.1 N hydrochloric acid were examined. Average MIP pore diameter values were in the range of 0.01–0.02μm. Intrusion volume was greatest for tuff reacted with 0.1 N hydrochloric acid and least for sawed tuff. Cut rock had the smallest porosity (4.72%) and crushed tuff reacted in hydrochloric acid had the largest porosity (6.56%). Mean pore diameters from nitrogen sorption measurements were 0.0075–0.0187 μm. Nitrogen adsorption pore volumes (from 0.005 to 0.013 cm³/g) and porosity values (from 1.34 to 3.21%) were less than the corresponding values obtained by MIP. More than half of the total tuff pore volume was associated with pore diameters < 0.05μm. Vapor sorption of EGME demonstrated that tuff pores contain a clay-like material. Epifluorescence microscopy indicated that connected porosity is heterogeneously distributed within the tuff matix; mineral grains had little porosity. Tuff porosity may have important consequences for contaminant disposal in this host rock.     

NEXAFS and XPS characterisation of carbon functional groups of fresh and aged biochars

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-π¹_CC transitions of aromatic C and C1s-π¹_CO 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.     

Surface complexation and precipitate geometry for aqueous Zn(II) sorption on ferrihydrite I: X-ray absorption extended fine structure spectroscopy analysis

“Two-line” ferrihydrite samples precipitated and then exposed to a range of aqueous Zn solutions (10⁻⁵ to 10⁻³ M), and also coprecipitated in similar Zn solutions (pH 6.5), have been examined by Zn and Fe K-edge X-ray absorption spectroscopy. Typical Zn complexes on the surface have Zn-O distances of 1.97(.02) Å and coordination numbers of about 4.0(0.5), consistent with tetrahedral oxygen coordination. This contrasts with Zn-O distances of 2.11(.02) Å and coordination numbers of 6 to 7 in the aqueous Zn solutions used in sample preparation. X-ray absorption extended fine structure spectroscopy (EXAFS) fits to the second shell of cation neighbors indicate as many as 4 Zn-Fe neighbors at 3.44(.04) Å in coprecipitated samples, and about two Zn-Fe neighbors at the same distance in adsorption samples. In both sets of samples, the fitted coordination number of second shell cations decreases as sorption density increases, indicating changes in the number and type of available complexing sites or the onset of competitive precipitation processes. Comparison of our results with the possible geometries for surface complexes and precipitates suggests that the Zn sorption complexes are inner sphere and at lowest adsorption densities are bidentate, sharing apical oxygens with adjacent edge-sharing Fe(O,OH)₆ octahedra. Coprecipitation samples have complexes with similar geometry, but these are polydentate, sharing apices with more than two adjacent edge-sharing Fe(O,OH)₆ polyhedra. The results are inconsistent with Zn entering the ferrihydrite structure (i.e., solid solution formation) or formation of other Zn-Fe precipitates. The fitted Zn-Fe coordination numbers drop with increasing Zn density with a minimum of about 0.8(.2) at Zn/(Zn + Fe) of 0.08 or more. This change appears to be attributable to the onset of precipitation of zinc hydroxide polymers with mainly tetrahedral Zn coordination. At the highest loadings studied, the nature of the complexes changes further, and a second type of precipitate forms. This has a structure based on a brucite layer topology, with mainly octahedral Zn coordination. Amorphous zinc hydroxide samples prepared for comparison had a closely similar local structure. Analysis of the Fe K-edge EXAFS is consistent with surface complexation reactions and surface precipitation at high Zn loadings with little or no Fe-Zn solid solution formation. The formation of Zn-containing precipitates at solution conditions two or more orders of magnitude below their solubility limit is compared with other sorption and spectroscopic studies that describe similar behavior.     

煤系固废基绿色充填材料制备及其性能研究

充填技术是绿色开采的重要组成部分,研发成本低廉、性能可靠、低碳环保的充填材料,是发展充填技术的关键。采用煤矸石(CG)和煤系偏高岭土(MK)为原材料制备煤系固废基绿色充填材料,探讨配合比和碱激发剂对充填材料强度以及流动度的影响,并结合X射线衍射(XRD)、傅里叶变换红外吸收光谱仪(FTIR)、热重分析(TG)和扫描电镜能谱分析(SEM-EDS)等表征手段,揭示充填强度发展机理。综合强度、流动性和环境指标,优化充填材料配比。研究结果表明：绿色充填材料体系中,煤系偏高岭土通过碱激发水化反应起到胶凝作用,体系强度随偏高岭土的增加呈线性增长,磨细的煤矸石充当惰性填料,协同Na₂SiO₃改善流动性。该充填材料主要水化产物为N―A―S―H和沸石,Si―O―Si发生聚解,随即四面体Al―O键部分取代Si―O键,由(SiO₄)^4-变成(AlO₄)^4-,进一步聚合形成Si―O―Al基团。当碱激发剂中Na₂SiO₃与NaOH比例为1...     

Surface complexation modeling of Uranium(VI) sorption on quartz in the presence and absence of alkaline earth metals

Surface complexation models (SCMs) are widely utilized as a tool to study the mobility of radionuclide to the environment. In this study, two SCMs, electrostatic (ES) and non-electrostatic (NES) models are employed in order to simulate the sorption behavior of U(VI) on quartz in the absence of Mg, Ca, and Sr and ES model in the presence of alkaline earth metals. The surface reaction constants (log K) for ES and NES models were fitted to experimental data by coupling PEST with PHREEQC. The SCM prediction of U(VI) sorption on quartz in the absence of alkaline earth metals is in good agreement with the experimental data in the pH range 6.5–9. The estimated log K values are sensitive to both ES and NES model calculations. In U(VI)-Mg-quartz, U(VI)-Ca-quartz, and U(VI)-Sr-quartz systems, only the ES model shows the general trend of the experimental data. The estimated log K values are sensitive with respect to the surface reactions. Hence, the ES model is more suitable for model calculations of the U(VI)-Mg-quartz, U(VI)-Ca-quartz, and U(VI)-Sr-quartz systems.     

Leaching behavior of Li and Ga from granitic rocks and sorption on kaolinite: Implications for their enrichment in the Jungar Coalfield,Ordos Basin

The granite collected from the Yinshan Mountain and kaolinite has been selected for the leaching and adsorption experiment,respectively,aiming to clarify the enrichment processes of Li and Ga during the deposition.Results suggest both Li and Ga could be leached out from granite by using different acid solutions of different p H and kaolinite can adsorb Li and Ga with varying degrees.Lithium and Ga had the highest leaching ratio when p H=1.Special geological events(e.g.volcanic eruptions and wildfires),which could result in very low p H values of water in peatland,may have accelerated the release of Li and Ga from the source rocks.Kaolinite has the highest adsorption fraction was obtained at p H=8.The different characteristics of Li and Ga displayed in the leaching and adsorption experiments probably result from the different occurrences and enrichment processes of Li and Ga in the coals.Lithium was probably enriched before the Li carriers(e.g.kaolinite)had been transported into paleomires because of its high leaching ratio and high adsorption fraction under neutral and alkaline conditions,whereas Ga was more likely concentrated by kaolinite and other carriers after it had been transported into the peat mires.     

矿山岩层和地表变形规律及其与地质因素的关系

矿山地下开采引起的岩层和地表变形,是矿区的严重公害之一。研究岩层和地表变形规律,对矿井安全生产及矿区地面环境保护都具有重要的现实意义。岩层和地表变形的基本形式和特征,首先取决于矿层的开采技术因素,而地质和水文地质条件也起着重要作用。     

Surface and groundwater quality characterization of Deoria District,Ganga Plain,India

A water quality investigation was carried out in the Deoria district, Ganga plain, to assess the suitability of surface and groundwaters for domestic, agricultural, and industrial purposes. As much as 50 representative samples from river and groundwater were collected from various stations to monitor the water chemistry of various ions, comprising Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ⁻, SO₄ ²⁻, NO₃ ⁻, Cl⁻, F⁻, and trace metals, such as Fe, Cu, Mn, Zn, Cd, and Pb. The results showed that electrical conductance (EC), total dissolved solids (TDS), HCO₃ ⁻, Mg²⁺, Na⁺, and total hardness (TH) are above the maximum desirable limit, and apart from Fe and Mn all other trace metals are within the maximum permissible limit for drinking water. The calculated values for sodium absorption ratio (SAR), salinity, residual sodium carbonate (RSC), and permeability index (PI) indicate well to permissible use of water for irrigation. High values of Na%, RSC, and Mg-hazard (MH) at some stations restrict its use for agricultural purpose. Anthropogenic activities affect the spatial variation of water quality. Economic and social developments of the study area is closely associated with the characteristics of the hydrological network.     

湛江湾海域表层沉积物稀土元素特征及其物源指示意义

通过对湛江湾近海海域表层沉积物样品粒度和稀土元素(RE E)测试分析,系统地研究海域沉积物稀土元素地球化学特征并探讨其物质来源.结果表明,研究区沉积物的稀土元素含量变化较大,平均值为163.23μg/g,湾外的REE含量(168.61μg/g)高于湾内的REE含量(142.17μg/g);不同类型沉积物的稀土元素含量存...     

Molecular characterization of uranium(VI) sorption complexes on iron(III)-rich acid mine water colloids

A mixing of metal-loaded acid mine drainage with shallow groundwater or surface waters usually initiates oxidation and/or hydrolysis of dissolved metals such as iron (Fe) and aluminum (Al). Colloidal particles may appear and agglomerate with increasing pH. Likewise chemical conditions may occur while flooding abandoned uranium mines. Here, the risk assessment of hazards requires reliable knowledge on the mobility of uranium (U). A flooding process was simulated at mesocosm scale by mixing U-contaminated acid mine water with near-neutral groundwater under oxic conditions. The mechanism of U-uptake by fresh precipitates and the molecular structure of U bonding were determined to estimate the mobility of U(VI). Analytical and spectroscopic methods such as Extended X-ray Absorption Fine-Structure (EXAFS) spectroscopy at the Fe K-edge and the U L_III-edge, and Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy were employed. The freshly formed precipitate was identified as colloidal two-line ferrihydrite. It removed U(VI) from solution by sorption processes, while surface precipitation or structural incorporation of U was not observed. EXAFS data suggest a mononuclear inner-sphere, edge-sharing complex of U(VI) with ferrihydrite in the absence of dissolved carbonate. By employing a novel EXAFS analysis method, Monte Carlo Target Transformation Factor Analysis, we could for the first time ascertain a 3-D configuration of this sorption complex without the necessity to invoke formation of a ternary complex. The configuration suggests a slightly tilted position of the adsorbed unit relative to the edge-sharing Fe(O, OH)₆ octahedra. In the presence of dissolved carbonate and at pH ∼8.0, a distal carbonate O-atom at ∼4.3 Å supports formation of ternary U(VI)-carbonato surface complexes. The occurrence of these complexes was also confirmed by ATR-FTIR. However, in slightly acidic conditions (pH 5-6) in equilibrium with atmospheric CO₂, the U(VI) sorption on ferrihydrite was dominated by the binary complex species Fe(O)₂UO₂, whereas ternary U(VI)-carbonato surface complexes were of minor relevance. While sulfate and silicate were also present in the mine water, they had no detectable influence on U(VI) surface complexation. Our experiments demonstrate that U(VI) forms stable inner-sphere sorption complexes even in the presence of carbonate and at slightly alkaline pH, conditions which previously have been assumed to greatly accelerate the mobility of U(VI) in aqueous environments. Depending on the concentrations of U(VI) and carbonate, the type of surface complexes may change from binary uranyl-ferrihydrite to ternary carbonato-uranyl-ferrihydrite complexes. These different binding mechanisms are likely to influence the binding stability and retention of U(VI) at the macroscopic level.