Abundance and Chemical Speciation of Phosphorus in Sediments of the Mackenzie River Delta, the Chukchi Sea and the Bering Sea: Importance of Detrital Apatite

Utilizing a sequential extraction technique this study provides the first quantitative analysis on the abundance of sedimentary phosphorus and its partitioning between chemically distinguishable phases in sediments of the Bering Sea, the Chukchi Sea and the Mackenzie River Delta in the western Arctic Ocean. Total sedimentary phosphorus (TSP) was fractionated into five operationally defined phases: (1) adsorbed inorganic and exchangeable organic phosphorus, (2) Fe-bound inorganic phosphorus, (3) authigenic carbonate fluorapatite, biogenic apatite and calcium carbonate-bound inorganic and organic phosphorus, (4) detrital apatite, and (5) refractory organic phosphorus. TSP concentrations in surface sediments increased from the Chukchi Sea (18 μmol g⁻¹ of dried sediments) to the Bering Sea (22 μmol g⁻¹) and to the Mackenzie River Delta (29 μmol g⁻¹). Among the five pools, detrital apatite phosphorus of igneous or metamorphic origin represents the largest fraction (~43%) of TSP. The second largest pool is the authigenic carbonate fluorapatite, biogenic apatite as well as CaCO₃ associated phosphorus (~24% of TSP), followed by the Fe-bound inorganic phosphorus, representing ~20% of TSP. The refractory organic P accounts for ~10% of TSP and the readily exchangeable adsorbed P accounts for only 3.5% of TSP. Inorganic phosphorus dominates all of phosphorus pools, accounting for an average of 87% of the TSP. Relatively high sedimentary organic carbon and total nitrogen contents and low δ¹³C values in the Mackenzie River Delta together with the dominance of detrital apatite in the TSP demonstrate the importance of riverine inputs in governing the abundance and speciation of sedimentary phosphorus in the Arctic coastal sediments.     

Expansivity and compressibility of strontium fluorapatite and barium fluorapatite determined by in situ X-ray diffraction at high-T/P conditions: significance of the M-site cations

Strontium fluorapatite (SrF-Ap) and barium fluorapatite (BaF-Ap) were synthesized by using a piston-cylinder apparatus at 1.0 GPa and 800 °C. Their thermal expansivity and compressibility were subsequently investigated by using in situ high-T powder X-ray diffraction method (up to 1,000 °C at ambient P) and by using a diamond-anvil cell coupled with synchrotron X-ray radiation (up to about 5 GPa at room T), respectively. The derived thermal expansion coefficients and bulk moduli were combined with the literature data for calcium fluorapatite (CaF-Ap) and lead fluorapatite (PbF-Ap) to constrain the influence of the M-site cations on the elasticity of the fluorapatites (MF-Ap). The results show that both the size of the M cations and their polarizability affect the thermal expansion coefficients of the MF-Ap. For the axial and volumetric bulk moduli, the size of the M cations plays a dominant role, with some crystallographic features of the MF-Ap being potentially important as well.     

Calcite formation in microbial mats: modeling and quantification of inhomogeneous distribution patterns by a cellular automaton model and multifractal measures

The evolution of early diagenetic calcite cements in microbial mats of recent supratidal sediments of the southern North Sea is modeled in a two-dimensional microscale approach by a cellular automaton model (CAM). Calcite is traced out in the model by virtual calcium distribution patterns obtained from runs under different assumptions concerning sediment-intrinsic conditions. For justification of the CAM, real calcium distribution patterns, documented by scanning electron microscopy coupled with energy-dispersive X-ray spectrometry (SEM/EDX), are quantitatively compared with the virtual patterns on the basis of multifractal analyses. The formation of high magnesian calcite as a consequence of biogenic anaerobic decomposition of organic matter starts at certain initial calcite domains. In this stage an inhomogeneous and multifractal calcium distribution is characteristic. Nearly complete remineralization of organic matter leads to monofractal behavior of generalized fractal dimensions (D_B(q) ±1.84). The CAM results confirm that calcite formation is a self-determining morphogenetical process and diffusive transport processes of reactants within the mat affect the biogenic calcite formation.     

A computer modelling study of the interaction of organic adsorbates with fluorapatite surfaces

Computer modelling techniques were employed to investigate the adsorption of a selection of organic surfactant molecules to a range of fluorapatite surfaces, and new interatomic potential models for the apatite/adsorbate interactions are presented. The adsorbates coordinate mainly to the surfaces through interaction between their oxygen (or nitrogen) atoms to surface calcium ions, followed by hydrogen-bonded interactions to surface oxygen ions and, to a much lesser extent, surface fluorides. Bridging between two surface calcium ions is the preferred mode of adsorption, when the geometry of the adsorbates allows it, and multiple interactions between surfaces and adsorbate molecules lead to the largest adsorption energies. All adsorbates containing carbonyl and hydroxy groups interact strongly with the surfaces, releasing energies between approximately 100 and 215 kJ mol⁻¹, but methylamine containing only the –NH₂ functional group adsorbs to the surfaces to a much lesser extent (25–95 kJ mol⁻¹). Both hydroxy methanamide and hydroxy ethanal prefer to adsorb to some surfaces in an eclipsed conformation, which is a requisite for these functional groups. Sorption of the organic material by replacement of pre-adsorbed water at different surface features is calculated to be mainly exothermic for methanoic acid, hydroxy methanamide and hydroxy ethanal molecules, whereas methyl amine would not replace pre-adsorbed water at the fluorapatite surfaces. The efficacy of the surfactant molecules is calculated to be hydroxy aldehydes > alkyl hydroxamates > carboxylic acids ≫ alkyl amines. The results from this study suggest that computer simulations may provide a route to the identification or even design of particular organic surfactants for use in mineral separation by flotation.     

沁水煤田15号煤中氟的赋存状态及其沉积环境分析

氟是煤中有害元素之一,燃煤型氟排放造成的污染已经对人类的健康安全构成威胁。研究煤中氟赋存状态及其沉积环境,对掌握高氟煤分布规律及控制燃煤造成的氟排放具有重要意义。通过对沁水煤田内6座煤矿15号煤样品的分析发现:煤中氟含量与灰分显著相关,与黄铁矿硫、有机硫无相关关系,表明煤中氟主要以无机物形式赋存,且与含硫矿物无关;与钾、镁、硅、铝等元素含量具有显著的相关关系,表明氟有可能的主要赋存形式为金云母、氟金云母等矿物,以及以吸附存在于高岭石、勃姆石、伊蒙混层等黏土矿物中;与钙、磷元素含量无显著相关性,表明氟不以氟磷灰石、含氟羟基磷灰石等矿物大量赋存。此外,通过对沁水煤田15号煤的沉积环境分析发现,弱还原环境、较低盐度、偏酸性、较强的水动力条件有利于该区域煤中氟的富集。     

Kerogen-mineral reactions at raised temperatures in the presence of water

Kerogen has been artificially matured under “hydrous pyrolysis” conditions in the presence of various minerals in order to investigate the influence of the latter on the organic products. In addition to three clay minerals (montmorillonite, illite, kaolinite), calcium carbonate and limonite were also employed as inorganic substrates. Kerogen (Type II) isolated from the Kimmeridge Blackstone band was heated in the presence of water and a 20-fold excess of mineral phase at two different temperatures (280 and 330°C) for 72 hr. Control experiments were also carried out using kerogen and water only and kerogen under anhydrous conditions. This preliminary study describes the bulk composition of the pyrolysates with detailed analyses of the aliphatic hydrocarbon distributions being provided by gas chromatography and combined gas chromatography-mass spectrometry.In the 280°C experiments, considerably more organic-soluble pyrolysate (15% by weight of original kerogen) was produced when calcium carbonate was the inorganic phase. At 330°C, all samples generated much greater amounts of organic-soluble products with calcium carbonate again producing a large yield (40% wt/wt). Biomarker epimerisation reactions have also proceeded further in the 330°C pyrolysate formed in the presence of calcium carbonate than with other inorganic phases. Implications of these and other observations are discussed.     

Bacterial genesis of calcium phosphates in human organism and nature

Comparison of natural marine (nodular and granular) carbonate-apatites and pathogenic mineral structures formed in human cardiac valves by methods of scanning electron and high-resolution transmission microscopy revealed common morphological features corresponding to the bacterial origin of calcium phosphates. These features may be considered typomorphic ones regardless of their formation environments (in vivo or in nature).     

Ultrastructural Evidence for a Novel Accumulation of Ca in a Microbial Mat from a Slight Acidic Hot Spring

<正>Microbial mats are ecosystems that can control or induce the precipitation of calcium(Ca) carbonate on Earth through geological time.In the present study,we report on a novel accumulation of Ca,together with iron(Fe),in a microbial mat collected from a slight acidic hot spring(pH=5.9) in south China.Combining an array of approaches,including environmental scanning electron microscopy,X-ray microanalysis,transmission electron microscopy,and selected area electron diffraction,we provide ultrastructral evidence for amorphous acicular aggregates containing Ca and Fe associated with cyanobacteria precipitating in the microbial mats.Cyanobacterial photosynthesis and exopolymeric organic matrixes are considered to be responsible for the precipitation of Ca.These amorphous acicular aggregates might imply the early stage of calcification occurring in microbial mats.Ca and Fe coprecipitation indicates another potential important way of inorganic element precipitation in hot spring microbial mats.Our results provide insight into the possible mechanism of cyanobacterial calcification and microfossil preservation in slight acidic hot spring environments.     

Morphologic and spectral investigation of exceptionally well-preserved bacterial biofilms from the Oligocene Enspel formation, Germany

The fossilised soft tissues of a tadpole and an associated coprolitic structure from the organic-rich volcanoclastic lacustrine Upper Oligocene Enspel sediments (Germany) were investigated using high-resolution imaging techniques and nondestructive in situ surface analysis. Total organic carbon analysis of the coprolite and the sediment revealed values of 28.9 and 8.9% respectively. The soft tissues from the tadpole and the coprolite were found to be composed of 0.5 to 1 μm-sized spheres and rod shapes. These features are interpreted as the fossil remains of bacterial biofilms consisting probably of heterotrophic bacteria and fossilised extracellular polymeric substances. They became fossilised while in the process of degrading the organic matter of the organism and the coprolite. Comparison with a modern marine biofilm revealed morphologic details identical to those observed in the fossil bacterial biofilms. Although the fossil biofilms on both macrofossils exhibited identical microtextures, their mode of preservation was inhomogeneous and varied between calcium phosphate and an as yet unidentified mineral phase consisting mainly of Si, Ca, Ti, P, and S, but also showing the presence of Mg, Al, and Fe. The coprolite consists purely of fossilised bacterial cells in a densely packed arrangement and associated fossilised extracellular polymeric substances.In addition to preliminary imaging and energy-dispersive X-ray analysis, both the fossil biofilms and the sediment were investigated by nondestructive in situ analysis using time of flight-secondary ion mass spectroscopy (ToF-SIMS). The mass spectra obtained on the coprolite in mass-resolved chemical mapping mode allowed the tentative identification of a number of organic secondary ion species. Some spectra appear to indicate the presence of bacterial hopanoids, but further work using standard techniques such as gas chromatography mass spectroscopy is needed to conclusively verify the presence of these substances. Nevertheless, ToF-SIMS chemical maps were successfully correlated with electron microscopy images, allowing the correlation of molecular spectra, the spatial distribution of individual organic species, and specific morphologic features to demonstrate the potential of this approach in the analysis of microfossils.     

Phosphorus fractions in the surface sediments of three mangrove systems of southwest coast of India

The phosphorus fractions in three tropical mangrove systems of Cochin region were analysed by sequential extraction method. Iron-bound phosphorus was the major fraction in the first two stations, while station 3 was exclusively dominated by calcium-bound phosphorus. Compared to other stations, about tenfold increase in total phosphorus content was observed at station 3. This station is a congregation of communally breeding birds, and there is accumulation of bird guano. Mineralogical analysis showed the presence of monetite, a thermodynamically metastable calcium phosphate mineral, in this unique system. The excreta and carcass of the birds in this sanctuary seems to be the reason for the formation of monetite, which is favoured by periodic fluctuations in redox potential. The high mass percentages of calcium and phosphorus by XRF and SEM–EDS analysis confirm the existence of calcium phosphate mineral at station 3. First two stations did not show any noticeable difference in phosphorus fractions and inorganic fractions constituted to about 65% of total phosphorus. But at station 3, inorganic fractions were about 92%. Low C:P ratios and low organic phosphorus content indicated active mineralisation of phosphorus at station 3. Bioavailable fractions of phosphorus at stations 1 and 2 were about 75%, whereas 98% of the total phosphorus was bioavailable at station 3. Since the bulk of the total phosphorus is bioavailable, these mangrove sediments have the potential to act as source of phosphorus to the overlying waters.     

Investigating pathways of diagenetic organic matter sulfurization using compound-specific sulfur isotope analysis

We present the results of compound-specific sulfur isotope analyses performed on organic sulfur compounds (OSCs) isolated from sediments deposited in the euxinic Cariaco Basin, Venezuela. Individual OSCs (sulfurized highly branched isoprenoids and malabaricatriene) have sulfur isotope compositions of ca. −15‰, which is ³⁴S enriched by 5-15‰ relative to coeval bulk organic and inorganic sulfur pools. These observed differences in the sulfur isotope composition of bulk organic sulfur in the kerogen and bitumen pools and individual OSCs demonstrate that there are multiple pathways of organic sulfur formation operating simultaneously in marine sediments. Comparison of our measured compound-specific sulfur isotope data with values predicted using simple isotopic mass balance assumptions suggests that the sulfurization process likely involves multiple sources of inorganic sulfur. Further, the isotopic composition of these various precursor inorganic sulfur species and the specific pathway of sulfur incorporation into organic matter (OM) impart distinct isotopic compositions to the resulting organic sulfur compounds. These data represent the first compound-specific sulfur isotope measurements made in marine sediments, and demonstrate the utility of compound-specific sulfur isotope analysis in identification of inorganic sulfur sources for OM sulfurization and tracking pathways of sulfur incorporation, which will lead to a more complete understanding of diagenetic sulfurization of OM.     

Pore Types and Quantitative Evaluation of Pore Volumes in the Longmaxi Formation Shale of Southeast Chongqing,China

The common microscale to nanoscale pore types were introduced and divided into organic and inorganic pores to estimate their contributions to porosity in the Lower Silurian Longmaxi Formation shale of southeast Chongqing. Following the material balance principle, the organic porosity values, which changed with formation subsidence and thermal evolution, were calculated using chemical kinetics methods and corrected via the organic porosity correction coefficient, which was obtained from field emission scanning electron microscopy. Grain density values were determined using the contents and true densities of compositions in the shale samples. The total porosity was calculated based on the grain and bulk densities. The inorganic porosity was determined from the difference between the total porosity and organic porosity at the same depth. The results show that inorganic pores mainly contain microfractures, microchannels, clay intergranular pores, intercrystalline pores and intracrystalline pores in the Lower Silurian Longmaxi Formation shale of southeast Chongqing. Organic pores mainly include organopore and fossil pore. The total porosity, organic porosity and inorganic porosity of organic-rich shale samples can be quantitatively evaluated using this method. The total porosity, organic porosity and inorganic porosity values of the Longmaxi Formation shale samples from the well Py1 in southeast Chongqing lie in 2.75%–6.14%, 0.08%–2.52% and 1.41%–4.92% with average values of 4.34%, 0.95% and 3.39%, respectively. The contributions of the inorganic pores to the total porosity are significantly greater than those of the organic pores.     

云南元谋盆地干润变性土中次生方解石特征及形成

土壤新生体对于研究区域环境变化、营养元素释放以及次生成矿作用具有重要意义。利用化学分析、X射线衍射、偏光显微镜和扫描电子显微镜等探讨云南省元谋盆地干润变性土钙质结核中的次生方解石的特征和形成过程。结果表明，钙质结核中次生方解石含量高，晶形完整；钙质结核以及次生方解石形成既取决于气候，也与微地形有关。次生方解石的形成过程及特征反映了自全新世以来元谋盆地主要处于干热气候环境中。     

水库现代沉积过程沉积磷的早期成岩作用模型研究

在沉积磷形态分析、孔隙水化学、核素计年以及吸附解吸实验等的基础上,运用一维“反应-平流-扩散”模型,研究了红枫湖现代沉积过程中磷的沉积改造。结果表明:红枫湖现代沉积过程中,有机态磷的矿化分解和铁结合态磷的络合/溶解,是控制沉积物磷迁移转化动力学的主要机制。沉积物-水界面附近有机磷的快速降解,可能克服沉积界面上铁氧化物对溶解磷的吸附缓冲,而形成向水体的磷酸盐迁移通量;自生磷灰石的沉积改造相对不明显,沉积磷向稳定形态含磷矿物(钙氟磷灰石)的转化过程同样不能影响红枫湖现代沉积过程中磷转化的质量平衡。     

花石嘴元墓出土化妆品的初步研究

运用红外光谱、X射线衍射、拉曼光谱、X射线荧光光谱等分析手段对花石嘴元墓出土的化妆品进行了初步的定性分析和定量分析。结果表明,其主要成分为无机物,以碳酸铅最多,其次为磷氯铅矿,另含有少量石英;有机物含量则非常低,可能为油脂。根据古代文献的记载及相关的研究,推测该化妆品应作肤用增白之用。     

Formation of monazite and xenotime inclusions in fluorapatite megacrysts, Gloserheia Granite Pegmatite, Froland, Bamble Sector, southern Norway

Xenotime and monazite inclusions in fluorapatite megacrysts from a granitic pegmatite, Gloserheia, Froland, Bamble Sector, southern Norway are described utilizing high contrast backscattered electron imaging of cross sections of a selection of fluorapatite crystals. Electron microprobe analysis is then used to further characterize the xenotime and monazite, as well as (Y+REE) normal and depleted regions in the fluorapatite. In the (Y+REE) normal regions Y₂O₃ ranges from 0.4 to 1.3 whereas it ranges from below the electron microprobe detection limit to around 0.4 in the depleted regions. Low Y values in monazite (X_Y?=?0.01?0.05) co-existing with xenotime indicates that inclusion formation in the originally (Y+REE)-enriched fluorapatite must have occurred below 300°C. Formation of the xenotime and monazite inclusions is attributed to fluid-aided coupled dissolution-reprecipitation processes during the later stages of subsolidus cooling of the pegmatite. The fluorapatite megacrysts are hypothesized to have under gone two major fluid-induced alteration events. The first occurred sometime after crystallization was complete at temperatures below 300°C and resulted in the initial formation of the xenotime and monazite inclusions. The second occurred at some later time as the product of a relatively limited fluid infiltration, also under T?<?300°C. This resulted in the formation of (Y+REE)-depleted regions along lattice and cleavage planes while at the same time promoting Ostwald ripening of the xenotime inclusions resulting in larger grains in the (Y+REE)-depleted areas.     

CaCO3生物矿化的研究进展——有机质的控制作用

生物CaCO₃是自然界分布最广泛的一类生物矿物,其组成除了无机相的CaCO₃外,还含有少量的有机质,包括水可溶(SM)和水不可溶有机质(IM),SM富含阴离子基团,是控制CaCO₃结晶的重要因素之一。通过有机—无机界面分子识别,有机质选择性地与CaCO₃晶体特定方向的面网相互作用,从而对CaCO₃的生长、形貌、多型及结晶学定向等产生明显的控制作用。有机—无机界面的分子识别机制包括静电、晶格几何匹配和立体化学互补等。仿生矿化的研究为进一步深入了解生物矿化的机理及制造高级复合材料提供了新的方法。     

An experimental study of dissolution–reprecipitation in fluorapatite: fluid infiltration and the formation of monazite

In a series of timed experiments, monazite inclusions are induced to form in the Durango fluorapatite using 1 and 2 N HCl and H₂SO₄ solutions at temperatures of 300, 600, and 900°C and pressures of 500 and 1,000 MPa. The monazite inclusions form only in reacted areas, i.e. depleted in (Y+REE)+Si+Na+S+Cl. In the HCl experiments, the reaction front between the reacted and unreacted regions is sharp, whereas in the H₂SO₄ experiments it ranges from sharp to diffuse. In the 1 N HCl experiments, Ostwald ripening of the monazite inclusions took place both as a function of increased reaction time as well as increased temperature and pressure. Monazite growth was more sluggish in the H₂SO₄ experiments. Transmission electron microscopic (TEM) investigation of foils cut across the reaction boundary in a fluorapatite from the 1 N HCl experiment (600°C and 500 MPa) indicate that the reacted region along the reaction front is characterized by numerous, sub-parallel, 10–20 nm diameter nano-channels. TEM investigation of foils cut from a reacted region in a fluorapatite from the 1 N H₂SO₄ experiment at 900°C and 1,000 MPa indicates a pervasive nano-porosity, with the monazite inclusions being in direct contact with the surrounding fluorapatite. For either set of experiments, reacted areas in the fluorapatite are interpreted as replacement reactions, which proceed via a moving interface or reaction front associated with what is essentially a simultaneous dissolution–reprecipitation process. The formation of a micro- and nano-porosity in the metasomatised regions of the fluorapatite allows fluids to permeate the reacted areas. This permits rapid mass transfer in the form of fluid-aided diffusion of cations to and from the growing monazite inclusions. Nano-channels and nano-pores also serve as sites for nucleation and the subsequent growth of the monazite inclusions.     

Multiscale characterization of pyritized plant tissues in blueschist facies metamorphic rocks

Pyritized plant tissues with well-preserved morphology were studied in rocks from Vanoise (western Alps, France) that experienced high-pressure, low-temperature metamorphic conditions in the blueschist facies during the Alpine orogeny. Organic and inorganic phases composing these fossils were characterized down to the nanometer scale by Raman microspectroscopy, scanning transmission X-ray microscopy and transmission electron microscopy. The graphitic but disordered organic matter composing these fossils is chemically and structurally homogeneous and mostly contains aromatic functional groups. Its original chemistry remains undefined likely because it was significantly transformed by diagenetic processes and/or thermal degradation during metamorphism. Various mineral phases are closely associated with this organic matter, including sulphides such as pyrite and pyrrhotite, carbonates such as ankerite and calcite, and iron oxides. A tentative time sequence of formation of these diverse mineral phases relative to organic matter decay is proposed. The absence of traces of organic matter sulphurization, the pervasive pyritization of the vascular tissues and the presence of ankerite suggest that the depositional/diagenetic environment of these metasediments was likely rich in reactive iron. Fe-sulphides and ankerite likely precipitated early and might have promoted the preservation of the fossilized biological soft tissues by providing mechanical resistance to compaction during diagenesis and subsequent metamorphism. In contrast, iron oxides which form rims of 100-nm in thickness at the interface between organic matter and Fe-sulphides may result from metamorphic processes. This study illustrates that it may be possible in some instances to deconvolve metamorphic from diagenetic imprints and opens new avenues to better constrain processes that may allow the preservation of organic fossils during diagenesis and metamorphism.     

Study on identification of leather industry wastewater constituents and its photocatalytic treatment

The present research work was intended to find out the useful information on identification, separation and photocatalytic degradation of organic compounds present in leather industry wastewater. The separation of organic compounds present in leather industry wastewater was carried out by solvent extraction. The separated crude extracted products were purified through column chromatography and characterized by UV–vis spectrophotometer, gas chromatography–mass spectrophotometer, liquid chromatography–mass spectrophotometer, ¹H and ¹³C Fourier-transform nuclear magnetic resonance spectroscopy. The elemental analysis of wastewater and solid residue was carried out by inductively coupled plasma-optical emission and X-ray fluorescence spectroscopy. The organic compounds such as nonadec-1-ene, 2-phenylethanol, 2,4-di-tert-butylphenol and other organic compounds in the leather industry wastewater were identified. Out of these organic compounds, 2-phenylethanol was photocatalytically degraded using standard Degussa P-25 TiO₂ (100 mg) photocatalyst under the irradiation of UV light. Result has been shown that 2-phenylethanol was transformed into 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol then the prolonged time (30 h) irradiation leads to 100 % degradation of 2-phenylethanol. Further possible degradation mechanism of 2-phenylethanol was proposed based on the electrospray ionization mass spectrometry analysis of degraded samples. The degradation of 2-phenylethanol was confirmed by chemical oxygen demand analysis of degraded samples. The physicochemical parameters such as pH, color, chemical oxygen demand, total dissolved solids, electrical conductivity and ionic chromatography analysis of the leather industry wastewater were also measured.