Probing the oxidation-reduction properties of terrestrially and microbially derived dissolved organic matter

Dissolved organic matter (DOM) has been shown to be an integral component in biogeochemical electron transfer reactions due to its demonstrated ability to facilitate redox reactions. While the role of DOM as a facilitator of electron transfer processes has been demonstrated, greater knowledge would lead to better understanding of the structural components responsible for redox behavior, such as quinones and nitrogen and sulfur (N/S) functional groups. This investigation uses direct scan voltammetry (DSV) coupled with fluorescence and NMR spectroscopy as well as thermochemolysis gas chromatography mass spectrometry (GC-MS) and X-ray photoelectron spectroscopy (XPS) to elucidate the organic moieties responsible for facilitating electron transfer reactions. We contrast electrochemical properties and structural details of three organic matter isolates from diverse sources; Great Dismal Swamp DOM (terrestrially derived, highly aromatic), Pony Lake DOM (microbially derived, highly aliphatic) and Toolik Lake (terrestrially derived, photochemically and microbially altered) with juglone (a redox-active model quinone). Aromatic and phenolic constituents were detected (by ¹³C NMR) and recovered (by thermochemolysis GC-MS) from all three fulvic acid samples, highlighting the ubiquity of these compounds and suggesting that the quinone-phenol redox couple is not limited to DOM derived from lignin precursors. The range of hydroxy-benzene and benzoic acid derivatives may explain the lack of a single pair of well-defined oxidation and reduction peaks in the DSV scans. The presence of a wide-range of hydroxylated benzoic acid isomers and other redox-active aromatic residues implies that native DOM possesses overlapping redox potentials analogous to their characteristic range of pK_a values.     

星叶石族矿物红外光谱研究

在新测定的星叶石晶体结构资料的基础上,对星叶石矿物进行了详细和红外光谱研究,对比了单斜及三斜星叶石的红光谱特征,并对星叶石中工外吸收振动的归属问题进行了讨论。     

南秦岭横丹浊积岩系——晚古生代发育于扬子板块被动陆缘上的弧前盆地充填物

南秦岭横丹浊积岩系是一套巨厚的浊流沉积,以向南或南东倾的单斜构造产出。由下而上,该沉积层序包括深水盆地、深水浊积扇和斜坡水道3个相序。相应地,沉积物粒度变粗,厚度变大,火山质组分含量增加,凝灰层大量发育,表明横丹浊积岩系为活动型浊积岩;其古水流方向为NNW—NNE向,物源区为南侧的碧口火山岩系。另外,横丹浊积岩系内还见石英岩、重结晶大理岩成分的砾石,说明其物源还包括被动陆缘环境的沉积物。相序、组构、沉积特征和物源区综合分析表明,横丹浊积岩系为弧前盆地充填物。构筑这一弧前盆地的动力学机制是洋壳板块向南俯冲于扬子板块被动陆缘之下,时代可能晚于中晚泥盆世。     

Exploring the impact of diagenesis on (isotope) geochemical and microstructural alteration features in biogenic aragonite

For the Quaternary and Neogene, aragonitic biogenic and abiogenic carbonates are frequently exploited as archives of their environment. Conversely, pre‐Neogene aragonite is often diagenetically altered and calcite archives are studied instead. Nevertheless, the exact sequence of diagenetic processes and products is difficult to disclose from naturally altered material. Here, experiments were performed to understand biogenic aragonite alteration processes and products. Shell subsamples of the bivalve Arctica islandica were exposed to hydrothermal alteration. Thermal boundary conditions were set at 100°C, 175°C and 200°C. These comparably high temperatures were chosen to shorten experimental durations. Subsamples were exposed to different ¹⁸O‐depleted fluids for durations between two and twenty weeks. Alteration was documented using X‐ray diffraction, cathodoluminescence, fluorescence and scanning electron microscopy, as well as conventional and clumped isotope analyses. Experiments performed at 100°C show redistribution and darkening of organic matter, but lack evidence for diagenetic alteration, except in Δ₄₇ which show the effects of annealing processes. At 175°C, valves undergo significant aragonite to calcite transformation and neomorphism. The δ¹⁸O signature supports transformation via dissolution and reprecipitation, but isotopic exchange is limited by fluid migration through the subsamples. Individual growth increments in these subsamples exhibit bright orange luminescence. At 200°C, valves are fully transformed to calcite and exhibit purple‐blue luminescence with orange bands. The δ¹⁸O and Δ₄₇ signatures reveal exchange with the aqueous fluid, whereas δ¹³C remains unaltered in all experiments, indicating a carbonate‐buffered system. Clumped isotope temperatures in high‐temperature experiments show compositions in broad agreement with the measured temperature. Experimentally induced alteration patterns are comparable with individual features present in Pleistocene shells. This study represents a significant step towards sequential analysis of diagenetic features in biogenic aragonites and sheds light on reaction times and threshold limits. The limitations of a study restricted to a single test organism are acknowledged and call for refined follow‐up experiments.     

非饱和土抗剪强度理论的研究进展

非饱和土的工程性质是20世纪90年代以来国际岩土工程界研究的热点,非饱和土的抗剪强度是非饱和土的重要工程性质之一,在参阅了中、外文相关资料的基础上,总结了非饱和土抗剪强度理论的研究成果,提出了非饱和土抗剪强度有待进一步研究的问题。     

Rare-earth abundances in kimberlites from Greenland and Zambia

Ten rare-earth elements (La, Ce, Nd, Sm, Eu, Gd, Tb, Tm, Yb and Lu) and Ta, Th and Hf contents in eight kimberlites and inclusions from Greenland and Zambia have been determined by instrumental neutron activation. All the samples have highly fractionated rare-earth (REE) distribution patterns. La/Yb ratios in the Greenland kimberlites (hypabyssal facies) vary from 111.8 to 188.4, and the total rare-earth contents range from 204.8 to 380.3 ppm. No europium anomaly is present. The Zambian kimberlites (diatreme facies) are altered and carbonated. Rare-earth patterns in these are also light REE-enriched. A significant difference is shown to exist between the diatreme and hypabyssal facies of kimberlites.     

Density functional theory predictions of equilibrium isotope fractionation of iron due to redox changes and organic complexation

We present molecular orbital/density functional theory (MO/DFT) calculations that predict a greater isotopic fractionation in redox reactions than in reactions involving ligand exchange. The predicted fractionation factors, reported as 1000·ln(^56-54α), associated with equilibrium between Fe-organic and Fe-H₂O species were <1.6‰ in vacuo and <1.2‰ in solution when the oxidation state of the system was held constant. These fractionation factors were significantly smaller than those predicted for equilibrium between different oxidation states of Fe, for which 1000·ln(^56-54α) was >2.7‰ in vacuo and >2.2‰ in solution when the bound ligands were unchanged. The predicted ⁵⁶Fe/⁵⁴Fe ratio was greater in complexes containing Fe³⁺ and in complexes with shorter Fe-O bond lengths; both of these trends follow previous theoretical results. Our predictions also agree with previous experimental measurements that suggest that the largest biological fractionations will be associated with processes that change the oxidation state of Fe, and that identification of biologically controlled Fe isotope fractionation may be difficult when abiotic redox fractionations are present in the system. The models studied here also have important implications for future theoretical isotope calculations, because we have discovered the necessity of using vibrational frequencies instead of reduced masses when predicting reduced partition functions in aqueous-phase species.     

Late-Stage Mafic Injection and Thermal Rejuvenation of the Vinalhaven Granite, Coastal Maine

The Vinalhaven intrusive complex consists mainly of coarse-grainedgranite, inward-dipping gabbro–diorite sheets, and a fine-grainedgranite core. Small bodies of porphyry occur throughout thecoarse-grained granite. The largest porphyry body (roughly 0·5km by 2·5 km) occurs with coeval gabbro, hybrid rocks,and minor fine-grained granite in the Vinal Cove complex, whichformed during the waning stages of solidification of the coarse-grainedVinalhaven granite. Porphyry contacts with surrounding coarse-grainedgranite are irregular and gradational. Compositions of wholerocks and minerals in the porphyry and the coarse-grained graniteare nearly identical. Neighboring phenocrysts in the porphyryvary greatly in degree of corrosion and reaction, indicatingthat the porphyry was well stirred. Thermal rejuvenation ofa silicic crystal mush by a basaltic influx can explain thecomposition and texture of the porphyry. Comparable rejuvenationevents have been recognized in recent studies of erupted rocks.Weakly corroded biotite phenocrysts in the porphyry requirethat hydrous interstitial melt existed in the granite duringremelting. Field relations, along with thermal calculations,suggest that cooling and crystallization of coeval mafic magmacould have generated the porphyry by thermal rejuvenation ofgranite crystal-mush containing about 20% melt. Field relationsalso suggest that some of the porphyry matrix may representnew felsic magma that was emplaced during remelting. KEY WORDS: granite; magma chamber; mafic replenishment; rejuvenation     

Enhanced bioremoval of refractory compounds from dyeing wastewater using optimized sequential anaerobic/aerobic process

The upflow anaerobic sludge blanket process followed by the biological aerated filter process was employed to improve the removal of color and recalcitrant compounds from real dyeing wastewater. The highest removal efficiency for color was observed in the anaerobic process, at 8-h hydraulic retention time, seeded with the sludge granule. In the subsequent aerobic process packed with the microbe-immobilized polyethylene glycol media, the removal efficiency for chemical oxygen demand increased significantly to 75 %, regardless of the empty bed contact time. The average influent non-biodegradable soluble chemical oxygen demand was 517 mg/L, and the average concentration in effluent from the anaerobic reactor was 363 mg/L, suggesting the removal of some recalcitrant matters together with the degradable ones. The average non-biodegradable soluble chemical oxygen demand in effluent from the aerobic reactor was 87, 93, and 118 mg/L, with the removal efficiency of 76, 74, and 67 %, at 24-, 12-, and 8-h empty bed contact time, respectively. The combined anaerobic sludge blanket and aerobic cell-entrapped process was effective to remove the refractory compounds from real dyeing wastewater as well as in reducing organic loading to meet the effluent discharge limits. This integrated process is considered an effective and economical treatment technology for dyeing wastewater.     

The Timescales of Magma Mixing in the Plumbing System of Bezymianny Volcano (Kamchatka): Insights from Diffusion Chronometry

Intrusion of magma of contrasting composition into a magma chamber often triggers eruptions of arc volcanoes. Application of the diffusion chronometry method allowed us to determine the time when fresh magma was supplied to the shallow chamber of Bezymianny volcano in the case of six eruptions in 2006–2012 and to compare them to the recorded seismic activity of this volcano. Two types of eruptions of Bezymianny volcano were distinguished, with a contrasting orthopyroxene rim being formed in the respective magmas (a) up to 3 years and (b) up to 2 months before the beginning of an eruption. It was shown that these differences are caused by two different paths of magma supply to the shallow chamber of Bezymianny volcano.