Molecular weight distribution,analytical and spectroscopic characterization of humic fractions sequentially isolated by organic solvents from a brown coal humic acid

A sequential fractionation procedure employing a series of selected mild organic solvents of different polarity has been applied for the isolation of chemically different organic fractions from a brown coal humic acid. Elemental composition, molecular weight distribution, i.r. and electron spin resonance analysis were carried out on the isolated humic fractions. They were characterized by: (a) a low polydispersity, (b) a decreasing aliphatic and increasing aromatic character along the series, (c) very different molecular weight which significantly correlated with E₄/E₆ ratios (particle aggregation and molecular association) and free radical concentrations (chemical and biochemical activity). Significant correlations were found between physico-chemical parameters of the isolated humic fractions, i.e. M_n, M_w, E₄/E₆ ratios, spins/g contents and the dielectric constants of the solvents used. This suggested the efficiency of the applied procedure in isolating chemically different organic fractions from the bulk, original humic acid.     

Numerical estimates of mechanical energy transfer from the atmosphere to the Indian ocean

The field of mechanical energy transfer from the atmosphere to the ocean is computed for the first time. The numerical simulation of waves within the Indian Ocean (IO) water area for the period of 1998?C2009 is used. Mechanical energy transfer is described by two integrated parameters calculated per area unit: the speed of complete energy flux from wind to waves, I _E (x, t), and the speed of complete losses in the energy of wind waves, D _E (x, t). In order to solve this problem, the wind field W(x, t) (the NCEP/NOAA data) is used; the I _E (x, t) and D _E (x, t) fields are calculated on the basis of the WAM numerical model containing a modified source function. The results obtained allow us, first, to assess the characteristic spatial distribution of zones ??pumped?? by the wind with mechanical energy for both the wave field and the upper layer of the ocean by seasons, years, and the whole period discussed, second, to determine the extreme and average zonal values of I _E (x, t) and D _E (x, t), the degree of their shift spacing and balance B _E = (I _E + D _E ); and third, to define the characteristic time scales of variations in the wind field and wave field energies, caused by energy transfer from the wind to waves in the zones and within the Indian ocean as a whole. These results significantly specify the climatic estimates obtained earlier.     

Contribution of bacteria to redox potential (E h) measurements in sediments

Increasing evidence suggests that bacteria are capable of creating specific redox conditions which are visible as species-specific continuous redox potential (E _h) measurements. It has been demonstrated that continuous measurements of E _h are valuable for tracking bacterial metabolic activities of bacterial species in liquid cultures. However, it remains uncertain whether this phenomenon is widespread among bacterial species and whether E _h measurements reflect similar mechanisms in more complex systems such as soils and sediments. The purpose of this study is therefore to evaluate whether bacteria that naturally occur in sediments have the capacity to control E _h and assess the relative partitioning of biological processes involved in E _h in natural sediments. To this end, continuous E _h measurements are linked to growth of bacteria in liquid cultures and bacterial metabolic activity in aquatic sediment microcosms containing the bioturbator Tubifex spp., in which we evaluate bacterial partitioning in microcosms treated with the bacteriocide formalin. The tested bacterial species (Micrococcus luteus, Paracoccus pantotrophus and Aminobacter aminovarans) appeared to have specific stable E _h signals during linear-exponential growth phase, suggesting that these species are capable of exerting an extracellular control on E _h measurements, thereby supporting the notion that species-specific E _h signals may be widespread among bacterial species. Formalin treatment reduced temporal variability of E _h in sediment microcosms. This outcome suggests that bacterial metabolism and inherent relative contributions of members of bacterial community principally determine development of E _h in sediment systems and that quantitation of sediment electrochemical properties may offer a potential indicator that characterizes bacterial processes.     

Sorption of metals on humic acid

The sorption on humic acid (HA) of metals from an aqueous solution containing Hg(II). Fe(III), Pb, Cu, Al, Ni, Cr(III), Cd, Zn, Co and Mn, was investigated with special emphasis on effects of pH, metal concentration and HA concentration. The sorption efficiency tended to increase with rise in pH, decrease in metal concentration and increase in HA concentration of the equilibrating solution. At pH 2.4. the order of sorption was: Hg? Fe? Pb? CuAl ? Ni ? CrZnCdCoMn. At pH 3.7. the order was: Hg and Fe were always most readily removed, while Co and Mn were sorbed least readily. There were indications of competition for active sites (CO₂H and phenolic OH groups) on the HA between the different metals. We were unable to find correlations between the affinities of the eleven metals to sorb on HA and their atomic weights, atomic numbers, valencies, and crystal and hydrated ionic radii. The sorption of the eleven metals on the HA could be described by the equation $\text{Y =}\text{100}\text{[1 + exp ? (A + BX)]}$, where Y = % metal removed by HA; X = mgHA; and A and B are empirical constants.     

过硫酸钠氧化-流动注射化学发光法在地下水腐植酸含量测定中的应用

在碱性条件下过硫酸钠能氧化腐植酸发生化学发光反应。本研究以过硫酸钠-腐植酸化学发光体系为基础,建立了腐植酸的过硫酸钠氧化-流动注射化学发光测定方法,同时对测定方法的负高压及增益、泵速、过硫酸钠浓度、氢氧化钠浓度等影响因素进行了优化实验。方法的线性范围为0.1～500 mg/L(相关系数为0.9985),检出限为0.076 mg/L,对浓度为0.5 mg/L的腐植酸进行11次平行测定,相对标准偏差(RSD)为3.47%。利用该方法对5种不同地区地下水中的腐植酸进行测定,样品的加标回收率在98.33%～107.50%之间。该方法无需分离,简单易行,对实际样品测定结果满意。     

Photochemical activity and characterization of the complex of humic acids with iron(III)

This study examined the effects of humic acids (HA) and Fe(III)–HA complex on the photodegradation of atrazine, one of the most widely used herbicides. It was shown that the photolysis of atrazine proceeded via first-order reaction kinetics and that atrazine photodegradation was inhibited by the presence of HA, whereas the rate for atrazine photolysis was promoted in solutions containing both HA and Fe(III). Interactions of Fe(III) with HA were characterized by SEM, EDX, UV–Vis and FTIR, revealing that Fe(III)–HA complex was formed by ligand exchange between oxygen groups of HA and Fe(III). Using fluorescence spectrometry the stability constant (K_c) and the fraction of fluorophores available for complexation (f) were obtained as log K_c = 4.28 and f = 74%. Photoformed Fe(II) by ligand-to-metal charge-transfer (LMCT) within the Fe(III)–HA complex was the most important factor involved in photolysis of atrazine, since Fe(II) was the reactant to generate hydroxyl radical. Thus, the rate of atrazine photodegradation in natural sunlit waters is dependent on both the amount of iron present and the interaction between HA and iron.     

Expansion properties and creep tests for a new type of solidified expansive sealing material for gas drainage boreholes in underground mines

This study was conducted to find the optimal expansion for a new type of solidified expansive sealing (SES) material. The aim was to better meet the requirements for sealing gas extraction boreholes in underground coal mines by examining the expansion and creep properties of the material. The effect of different proportions of expansion agent on expansion time, expansion mechanisms, and creep properties of the SES material was investigated using an electronic universal testing machine and other systems. Based on the results of step loading creep tests, the Kelvin–Voigt viscoelastic model was selected to further analyze the mechanical properties of the material. The analysis showed that when the proportion of expansion agent in the SES is increased to 2.0%, the final expansion percentage increases to 11.5%, and the rapid expansion time and expansion preparation time quickly decreases to 18 and 12 min, respectively. In addition, the step loading displacement and constant force load displacement increase sharply. The creep parameters E₀, E₁, and η₁ of the Kelvin–Voigt model reflect the gradually weakening of the compressive capacity and anti-deformation ability of the SES material. Based on the analysis of the experimental results and field application on sealing boreholes using SES material, it was possible to establish the optimum amount of expansion agent that should be added to the SES material. The optimized proportions can meet the requirements of good flowability, high compressive capacity, and anti-deformation ability for borehole sealing in a mine.     

The effects of soil sand contents on characteristics of humic acids along soil profiles

It is generally accepted that the compositions and properties of soil organic matter (SOM) are influenced by many factors. In order to reveal the effects of soil texture on characteristics and dynamics of SOM and its sub-fraction, humic acid (HA), along two soil profiles, a yellow soil profile and a purplish soil profile, under the same climate and vegetation conditions were determined. Results indicate that the decomposition and humification degrees of SOM and HA of the purplish soils are higher than those of the corresponding yellow soils indicated by A/O–A ratios of HAs, TOCs and HA yields of bulk soil samples, nevertheless, the development degree of the purplish soil is lower than that of the yellow soil. The variations of E₄/E₆ ratios of HAs along the soil profiles indicate the overall molecular sizes of HAs decreased downward along the soil profiles. A/O–A ratios of HAs decreased downward along both the soil profiles indicate that humification processes decrease downward along both the soil profiles. Leaching of SOM shows significant effects on the distribution and characteristics of HAs in the yellow soil profile but the purplish soil profile, which is consistent with the higher hydrophobicity of HAs in purplish soils, shows that the distribution characteristics of SOM along the soil profiles are a complex result of the combination of soil texture and characteristics of SOM itself. The remarkably different sand contents are concluded tentatively as one of reasons to the different distributions and dynamics of HAs along the soil profiles, however, to profoundly understand the evolution and transport of SOM along soil profiles needs more researches.     

Fracture systems in normal fault zones crosscutting sedimentary rocks,Northwest German Basin

Field studies of fracture systems associated with 58 normal fault zones crosscutting sedimentary rocks were performed in the Northwest German Basin. Fracture orientations, densities, apertures and lengths, as well as fault zone structural indices, were analysed separately for fault damage zones and host rocks. The results show a pronounced difference between carbonate and clastic rocks: mainly in carbonate rocks we found presence of clear damage zones, characterized by higher fracture densities than in the host rocks. While the maximum aperture is similar for both units, the percentage of fractures with large apertures is much higher in the damage zones than in the host rocks.Based on laboratory measurements of Young's moduli and field measurements of fracture densities, we calculate effective stiffnesses E_e, that is the Young's moduli of the in situ rock masses, within the normal fault zones. Compared with carbonate rocks, E_e computed for clastic-rock damage zones decreases significantly less due to lower fracture densities. We conclude that normal fault zones in carbonate rocks have more profound effects on enhancing permeability in fluid reservoirs than those in clastic rocks. The results are of great importance for modelling the hydromechanical behaviour of normal fault zones in subsurface fluid reservoirs.     

Nonaqueous titration of functional groups in humic acid

Humic acid was titrated by sodium methoxide in dimethylsulfoxide using platinum-calomel electrode systems. Adding benzoic acid and phenol as internal standards to humic acid yielded two inflections. The titer at the first inflection point was equivalent to the carboxyl groups whose pK_a (H₂O) values were less than 7. The difference between the titers at the two inflection points was equivalent to the phenolic hydroxyl groups whose pK_a (H₂O) values were 7–10. Calculated results for the carboxyl and phenolic hydroxyl groups in humic acid obtained by the nonaqueous titration method agreed closely with those obtained by conventional methods.     

Short-range order and frustration in omphacite: Comparison of three CVM approximations

We compare three cluster variation method (CVM) models for order-disorder in omphacite (Al_0.5Mg_0.5)[Na_0.5Ca_0.5]Si₂O₆: the generalized point approximation (GPA), generalized pair approximation (GPaA) and an approximation that is based on two eight-body clusters (2X8A). The same Hamiltonian (set of pairwise interactions) is used for all three approximations. Pair probabilities predicted by the GPA obey the geometric constraints of the crysal structure (the frustration constraint), but the exclusion of short-range order (SRO) leads to overestimates of the configurational internal energy (〈E〉), and the critical temperature for cation order-disorder (T _c ). The GPaA violates the frustration constraint, and it therefore fails to predict a P2 ₁/n → C2/c order-disorder transition and yields values for 〈E〉 and SRO that are inconsistent with the omphacite crystal structure. The 2X8A predicts SRO that is consistent with the frustration constraint, and it yields improved (lower) estimates of 〈E〉 and T _c relative to the GPA: 〈E〉_2X8A<〈E〉_GPA, and T _c (2X8A)≈0.741 T _c (GPA).     

Chemistry of metal–humic complexes contained in Megalopolis lignite and potential application in modern organomineral fertilization

Lignite samples from two deposits located in the Megalopolis Basin, Southern Greece, were evaluated for their potential applicability as raw materials for the production of organomineral fertilizers. Fundamental chemical analyses were carried out to demonstrate high humic substances and metal contents. To determine their relative distribution in the Megalopolis lignite extract, eight elements, namely Na, K, Cd, Mn, Mg, Pb, Zn, and Cu, were studied both in H₂O and in Na₄P₂O₇/NaOH solutions. The behavior of these metals showed significant variations; Zn, Pb, Cd, and Cu associate mostly to the humic substances and proved scarce in the water extract. Contrarily, K and Mg gave a significantly low total yield in the Na₄P₂O₇/NaOH solution, while Mn was classified among the least extracted elements. Further enrichment of Megalopolis humic substances in these metals was achieved; Pb and Mg proved the most and least retained metal, respectively. Decomplexation titration curves of humic matter saturated with these metal ions demonstrated that novel organomineral fertilizing materials may develop based on optimized metal ion and humate contents, which can retain metals in a soluble form within a wide pH range. Formation of complexes between humic substances and Zn, Cd, and Mg was clearly indicated.     

Dynamic Systems of Petroleum Accumulation in the Nanpu Depression,Bohai Bay Basin,China

<正>It is significant to distinguish the dynamic systems of petroleum accumulation(DSPA) for the understanding of petroleum accumulation and distribution.According to the formation pressure framework,genetic types of petroleum and characteristics of conduit systems,three dynamic systems of petroleum accumulation were identified in the vertical profile in the Nanpu depression,Bohai Bay basin.The deeper DSPA(including formations Es_3 to Es_2) is a sealed system with high-overpressure and high-mature self-sourced oil.Most of the crude oil in the system accumulated in the periods of late Oligocene(23.5 Ma) and late Pliocene(2.4 Ma).The middle DSPA(including formations Es_1 to Ed_1) is an overpressured half-sealed system with mature or lower-mature self-sourced oil.The accumulation of oil in the system also occurred in the late Oligocene(23.5 Ma) and late Pliocene(2.4 Ma).The shallower DSPA(including formations Ed_2 to Q) is a hydrostatic system with lower-mature aliensourced oil from the middle system.Oil within this system accumulated only in the late Pliocene period.The oil in the shallower system migrated vertically along the faults from the formerly accumulated oil in the middle system by lateral migration along the sandbodies,whereas petroleum accumulation in the deeper system was mainly derived from the system itself by lateral migration along the sandbodies and rarely migrated out of the system.In this case,it seems that the deeper system is a more potential exploration prospect in addition to the other two proved favorable systems.     

Empirical modeling of plate load test moduli of soil via gene expression programming

New empirical models were developed to predict the soil deformation moduli using gene expression programming (GEP). The principal soil deformation parameters formulated were secant (E_s) and reloading (E_r) moduli. The proposed models relate E_s and E_r obtained from plate load-settlement curves to the basic soil physical properties. The best GEP models were selected after developing and controlling several models with different combinations of the influencing parameters. The experimental database used for developing the models was established upon a series of plate load tests conducted on different soil types at depths of 1–24 m. To verify the applicability of the derived models, they were employed to estimate the soil moduli of a part of test results that were not included in the analysis. The external validation of the models was further verified using several statistical criteria recommended by researchers. A sensitivity analysis was carried out to determine the contributions of the parameters affecting E_s and E_r. The proposed models give precise estimates of the soil deformation moduli. The E_s prediction model provides considerably better results in comparison with the model developed for E_r. The simplified formulation for E_s significantly outperforms the empirical equations found in the literature. The derived models can reliably be employed for pre-design purposes.     

Electron Transfer Between Sulfide and Humic Acid: Electrochemical Evaluation of the Reactivity of Sigma-Aldrich Humic Acid Toward Sulfide

Little is known of potential reactivity and redox properties of reduced dissolved organic matter (DOM), although DOM in anoxic environments, e.g., groundwater, peat soils, or lake sediments, can be expected to differ from DOM of oxidized environments. We therefore investigated the impact of electrochemical and wet chemical [hydrogen (H₂)/Pd catalyst] reduction in Sigma-Aldrich humic acid (HA) as a model DOM for high salinity, high ionic strength, or iron-rich systems on its reactivity toward sulfide. Mediated electrochemical measurement showed that the reactivity of HA toward sulfide decreased in the order non-reduced HA > electrochemically reduced (?0.1 V) HA > H₂/Pd-reduced HA > electrochemically reduced (?0.4 V) HA. Results indicated that measured initial values of electron-accepting capacities of HA had a strongly positive correlation with the sulfide transformation, except for the H₂/Pd treatment of HA. This latter treatment obviously changed HA structures and lead to a different reactivity toward sulfide, limiting a direct comparison to electrochemically reduced organic matter. Our result confirmed that reduced HA was still reactive toward sulfide, although to a lower extent compared with oxidized HA. Compared to electrochemical reduction, H₂/Pd pre-treatment of HA alters redox properties and reactivity of organic matter and may therefore lead to results that cannot be transferred to natural systems.     

Extraction of heavy metals in Sydney Harbour sediments using 1M HCl and 0.05M EDTA and implications for sediment‐quality guidelines

Sixty sediment samples with a wide range of heavy‐metal concentrations and sediment textures were collected from Sydney Harbour. The samples were extracted with 1M HCl, 0.05M EDTA and HClO₄/HNO₃ and analysed by flame atomic absorption spectrometry for Zn, Pb, Cu and Cd. 1M HCl extracted a large proportion of heavy metals in oxic sediments (60–100%), whereas the extractability of metals with 0.05M EDTA was generally lower (by ～20%). Extractability was unrelated to the level of contamination or to sediment texture. The extractability of Cu in anoxic sediments was substantially lower with 1M HCl (～20%) and 0.05M EDTA (～10%) than with HClO₄/HNO₃. The extractability of Pb with 0.05M EDTA was also reduced in anoxic sediments (to ～70%). The use of weak extractants, in particular 1M HCl, is recommended by the recently introduced ANZECC and ARMCANZ interim sediment‐quality guidelines. These extractants are believed to provide a better measure of the bioavailable metal content than strong acid extractants. In this study, anoxic, sulfidic environments had a major influence on metal extractability with weak extractants. The implication of this is that the number of samples requiring further testing, as stipulated by the guidelines, would be significantly reduced in anoxic sediments.     

The ionic model: Extension to spatial charge distributions,derivation of an interaction potential for silica polymorphs

An interatomic interaction potential for silica polymorphs is derived based on the SCD model (cfr. Tijskens et al. 1994). This interaction potential incorporates all classical electrostatic interactions arising from the spherical part of the spatial extent of the atoms including many body interactions. The potential is derived from Hartree-Fock energies and electron densities for a set 72 [SiO₄]^4-- and [Si₂O₇]^6--clusters with variable configuration. The long range impact of the surroundings on these clusters in the infinite system has been successfully mimicked by embedding the clusters in a finite three-dimensional array of point charges. This three-dimensional array of point charges is optimized as to reproduce the average site potential and its gradient occurring in II–IV-coordinated silica polymorphs at the central atoms of the clusters. The resulting interaction potential consists of two functions of the configurational coordinates, ?, describing spherical “atomic” electron densities, σ_a(x, ?) for A=Si, O. All classical electrostatic interactions are derived from these densities. A Born-Mayer type correction term ΔE _qm(?) models the quantum mechanical interactions and the electrostatic interactions arising from the non-spherosymmetrical component of the electron density. The new interaction potential model shows a slightly improved reproduction of the potential surface with respect to the classical Born-Mayer ionic model and demonstrates the importance of many body interactions as charge transfer and expansion/contraction of the atomic electron densities in these systems. Also the dependence of the quantum mechanical correction term ΔE _qm(?) on the Si-O-Si-bond angle proves covalent effects to be larger than suggested by the classical Born-Mayer ionic model thereby clarifying the controversy in literature on the importance of covalent effects in silica polymorphs and polymerised silicates in general.     

Factors affecting earthquake recovery: the Yao’an earthquake of China

Households vary in their ability to deal with disasters, and this may lead to different recovery results. Aiming to examine this differentiation, this paper studied the 2009 Yao??an earthquake in China. Surveys of 200 destroyed rural households were conducted in field investigations and follow-ups at 1?month, 1?year, and 1.5?years after the earthquake. The results showed a clear difference in recovery, the households observably being classified into five groups. These are the O group, which has different recovery time and economic cost from the other four; and the special group, comprising E _L T _O and E _O T _L (vulnerable during recovery); E _H T _O (strong during recovery); and E _L T _S (neither vulnerable nor strong). Logistic regression analysis revealed that differentiation in recovery patterns arose from the combined effect of demographic factors and external assistance provided to households. Lower income is the root cause of vulnerability in some households during the recovery process. However, other factors cause recovery differences between the two vulnerable groups, causing the economic recovery cost of the E _L T _O group to be lower, and the recovery time of the E _O T _L group to be longer. There was consensus that external assistance had an impact on all households. The more provided and the earlier it arrived, the lower the cost for recovery and the shorter the recovery time. This study shows that research on group differentiation of recovery is useful in understanding post-earthquake recovery processes and calls for taking group differentiation considerations into account in post-disaster recovery resource allocation practices.     

Optimization of headspace single-drop microextraction technique for extraction of light hydrocarbons (C6-C12) and its potential applications

In this study, headspace single-drop microextraction (HS-SDME) coupled with gas chromatography-flame ionization detection (GC-FID) was tested to determine C₆-C₁₂ light hydrocarbons (LHs) in petroleum and aqueous samples. Several significant experimental parameters, such as drop solvent type, drop volume, sample solution ionic strength, agitation speed and extraction time were optimized. Under optimum extraction conditions, specifically, a 1.5 μl microdrop of n-hexadecane, 30 min extraction of a 5 ml aqueous sample placed in a 10 ml vial, and stirring at 1000 rpm at room temperature, the reproducibility and accuracy of this method were found to be satisfactory. Two examples using this method indicated that HS-SDME is a simple, efficient and promising technique for the determination of volatile C₆-C₁₂ LHs in complex matrices.     

Effects of age on the chemical structure of paleosol humic acids and fulvic acids

Humic acids and fulvic acids were extracted from six paleosols in Southern Italy. Humic acids (HAs) constituted between 96.5 and 99.2% of the total extracts; the remaining materials consisted of fulvic acids (FAs). Radiocarbon ages of the HAs ranged from about 6,000 to close to 29,000 years B.P., δ¹³C values averaged $\text{?25.6 ± 0.3‰}$ The HAs were characterized by chemical (elemental and functional group analyses) and spectroscopic (IR, ESR, ¹³CNMR, E₄/E₆ ratios) methods. FAs were characterized by chemical methods, E₄/E₆ ratios and IR spectra.The chemical and spectroscopic analyses showed practically no differences in the chemical structure and composition of the six HAs and FAs, so that age appeared to have little effect on these parameters. The paleosols were found to be closed systems with low polysaccharide and protein contents, thus providing unfavorable substrates for microbial activity. The preservation of the humic materials in the paleosols may have been due to low biological activity and/or to retention by amorphous minerals. The HAs did not appear to be affected by temperatures higher than 170–200°C over the 23,000 year period which we observed.