Tracing suspended organic nitrogen from the Yangtze River catchment into the East China Sea   总被引：2，自引：0，他引：2  

Ying Wu  Thorsten Dittmar  Kai-Uwe Ludwichowski  Gerhard Kattner  Jing Zhang  Zhuo Y. Zhu  Boris P. Koch 《Marine Chemistry》2007

Total suspended matter was collected along the Yangtze River (Changjiang) and in the East China Sea in April to May and in September 2003, respectively, to study origin and fate of particulate organic nitrogen. Concentrations of particulate organic carbon (POC), nitrogen (PN) and hydrolyzable particulate amino acids (PAA; d- and l-enantiomers) were higher in the Yangtze Estuary than in the river and decreased offshore towards the shelf edge. In the coastal area, higher values of PAA were observed in the surface layer than in the bottom water. Stable carbon isotope ratios (δ¹³C) of POC increased from − 24.4‰ in the river to values around − 21‰ on the East China Sea Shelf. Dominant amino acids were aspartic acid + aspartine (Asx), glutamic acid + glutamine (Glx), glycine, alanine and serine. The proportions of Asx, Glx and isoleucine were higher in the marine than in the riverine samples contrary to the distributions of glycine, alanine, threonine and arginine. The proportions of d-amino acids were highest in the riverine suspended organic matter (6% of PAA) decreasing towards the shelf edge (1.5% of PAA). d-arginine, not reported in natural aquatic samples so far, was the most abundant d-amino acid in the river. The amino acid composition of the particulate organic matter (POM) in the Yangtze River indicates an advanced stage of degradation of POM. Highly degraded organic matter from soils is probably a main source of POM in the Yangtze River, but the relatively high δ¹³C values and low C/N ratios (7.7 ± 1.6) also indicate contribution from anthropogenic sources. The degraded riverine material was a dominant organic matter source in the estuary, where aquatic primary production had only a small overall contribution. In the East China Sea, gradual settling of riverine organic matter and the addition of fresher phytoplankton impacted the amino acid composition and δ¹³C values, and on the outer shelf relatively fresh phytoplankton-derived organic matter dominated.  相似文献   

Molecular characterization of uranium(VI) sorption complexes on iron(III)-rich acid mine water colloids   总被引：1，自引：0，他引：1  

Kai-Uwe Ulrich  André Rossberg  Harald Foerstendorf  Andreas C. Scheinost 《Geochimica et cosmochimica acta》2006,70(22):5469-5487

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.  相似文献   

Distribution of intact and core GDGTs in marine sediments   总被引：1，自引：0，他引：1  

Xiaolei LiuJulius Sebastian Lipp  Kai-Uwe Hinrichs 《Organic Geochemistry》2011,42(4):368-375

We conducted a survey of archaeal GDGT (glycerol dibiphytanyl glycerol tetraether) distributions in marine sediments deposited in a range of depositional settings. The focus was comparison of two pools presumed to have distinct geobiological significance, i.e. intact polar GDGTs (IP GDGTs) and core GDGTs (C GDGTs). The former pool has been suggested to be related to living communities of benthic archaea in marine sediments, while the latter is commonly interpreted to consist of molecular fossils from past planktonic archaeal communities that inhabited the surface ocean. Understanding the link between these two pools is important for assessment of the validity of current molecular proxies for sedimentary archaeal biomass and past sea surface temperatures. The relative distributions of GDGTs in the two pools in a core at a CH₄ rich site in the Black Sea provide evidence for in situ production of glycosidic IP GDGTs and their subsequent degradation to corresponding C GDGTs on timescales that are short in geological terms. In addition, we monitored the relationship between the IP GDGT and C GDGT pools in a sample set from various ocean basins with subseafloor depth from a few cm to 320 m and 0 to 4 Myr in age. Notable differences between the two pools can be summarized as follows: the GDGT with acyclic biphytanes, GDGT-0, and its analogues with two and three cyclopentane moieties (GDGT-2 and -3) are generally more abundant in the pool of IP GDGTs, while crenarchaeol tends to be more abundant in the C GDGT pool. Consequently, the ring index is generally higher for the C GDGTs while TEX₈₆, a molecular proxy ratio not considering the two major GDGTs, tends to be higher in the IP GDGT pool. These differences in the proportion of individual GDGTs in the two pools are probably due to in situ production of IP GDGTs with distributions differing from those of C GDGTs. Despite these differences, we observed significant correlation of these two ratios between the two pools. Specifically, in both pools TEX₈₆ is high in sediments from warm oceanic regimes and low in cold regimes. We discuss these relationships and suggest that recycling of core GDGTs by benthic archaea is an important mechanism linking both molecular pools.  相似文献   

A simple guideline to apply excitation-emission matrix spectroscopy (EEMs) for the characterization of dissolved organic matter (DOM) in anoxic marine sediments     

Shuchai Gan  Verena B.Heuer  Frauke Schmidt  Lars W?rmer  Kai-Uwe Hinrichs 《海洋学报(英文版)》2023,42(1):109-119

Marine sediments represent a major carbon reservoir on Earth. Dissolved organic matter(DOM) in pore waters accumulates products and intermediates of carbon cycling in sediments. The application of excitation-emission matrix spectroscopy(EEMs) in the analysis of subseafloor DOM samples is largely unexplored due to the redoxsensitive matrix of anoxic pore water. Therefore, this study aims to investigate the interference caused by the matrix on EEMs and propose a guideline to prepare pore water sam...  相似文献   

Advanced characterization of marine dissolved organic matter by combining reversed-phase liquid chromatography and FT-ICR-MS   总被引：1，自引：0，他引：1  

Boris P. Koch  Kai-Uwe Ludwichowski  Gerhard Kattner  Thorsten Dittmar  Matthias Witt 《Marine Chemistry》2008,111(3-4):233-241

Marine dissolved organic matter (DOM) was separated by reversed-phase (RP) liquid chromatography method and analyzed with fluorescence/absorption detection and Fourier transform ion cyclotron mass spectrometry (FT-ICR-MS). The three key characteristics of the RP method are: (a) The C18-RP column chosen provides enhanced separation when the aqueous phase is 100% buffer-free water, and it does not degrade over time; (b) the water eluent adjusted to pH 7 significantly improves the resolution of water soluble compounds; (c) the initial flow maintained at low levels improves the separation of polar compounds. In samples, containing “fresh” DOM, specific peaks were detected, which were absent in “old” DOM samples. The combination with size exclusion chromatography (SEC) also demonstrated the relation between polarity and molecular size of DOM. FT-ICR-MS was applied to evaluate the quality of separation on a molecular scale demonstrating that physico-chemical characteristics of DOM can be related to molecular formulas. Sample extracts were separated into 4 preparative fractions, and a large suite of the identified molecular formulas only occurred in specific fractions. This is an important basis for the application of further analytical techniques in order to perform a more target-oriented analysis aiming at the determination of source and process biomarkers for DOM.  相似文献   

Methane in shallow cold seeps at Mocha Island off central Chile     

Gerdhard L. JessenSilvio Pantoja  Marcelo A. GutiérrezRenato A. Quiñones  Rodrigo R. GonzálezJavier Sellanes  Matthias Y. KellermannKai-Uwe Hinrichs 《Continental Shelf Research》2011,31(6):574-581

We studied for the first time the intertidal and subtidal gas seepage system in Mocha Island off Central Chile. Four main seepage sites were investigated (of which one site included about 150 bubbling points) that release from 150 to 240 tonnes CH₄ into the atmosphere per year. The total amount of methane emitted into the atmosphere is estimated in the order of 800 tonnes per year. The gases emanated from the seeps contain 70% methane, and the stable carbon isotopic composition of methane, δ¹³C-CH₄ averaged −44.4±1.4‰ which indicates a major contribution of thermogenic gas. Adjacent to one of the subtidal seeps, rocky substrates support a diverse community of microbial filaments, macroalgae, and benthic organisms. While stable carbon isotopic compositions of marine benthic organisms indicate a dominant photosynthesis-based food web, those of some hard-substrate invertebrates were in the range −48.8‰ to −36.8‰, suggesting assimilation of methane-derived carbon by some selected taxa. This work highlights the potential subsidy of the trophic web by CH₄-C, and that its emission to the atmosphere justifies the need of evaluating the use of methane to support the energy requirements of the local community.  相似文献   

A surface structural model for ferrihydrite II: Adsorption of uranyl and carbonate     

Tjisse Hiemstra  Willem H. Van Riemsdijk  André Rossberg  Kai-Uwe Ulrich 《Geochimica et cosmochimica acta》2009,73(15):4437-19695

The adsorption of uranyl (UO₂²⁺) on ferrihydrite has been evaluated with the charge distribution (CD) model for systems covering a very large range of conditions, i.e. pH, ionic strength, CO₂ pressure, U(VI) concentration, and loading. Modeling suggests that uranyl forms bidentate inner sphere complexes at sites that do not react chemically with carbonate ions. Uranyl is bound by singly-coordinated surface groups present at particular edges of Fe-octahedra of ferrihydrite while another set of singly-coordinated surface groups may form double-corner bidentate complexes with carbonate ions. The uranyl surface speciation strongly changes in the presence of carbonate due to the specific adsorption of carbonate ions as well as the formation of ternary uranyl-carbonate surface complexes. Data analysis with the CD model suggests that a uranyl tris-carbonato surface complex, i.e. (UO₂)(CO₃)₃⁴⁻, is formed. This species is most abundant in systems with a high pH and carbonate concentration. This finding differs significantly from previous interpretations made in the literature. At high pH and low carbonate concentrations, as can be prepared in CO₂-closed systems, the model suggests the additional presence of a ternary uranyl-monocarbonato complex. The binding mode (type A or type B complex) is uncertain. At high uranyl concentrations, uranyl polymerizes at the surface of ferrihydrite giving, for instance, tris-uranyl surface complexes with and without carbonate. The similarities and differences between U(VI) adsorption by goethite and ferrihydrite are discussed from a surface structural point of view.  相似文献   

Structural diversity of diether lipids in carbonate chimneys at the Lost City Hydrothermal Field     

Alexander S. Bradley  Helen Fredricks  Kai-Uwe Hinrichs  Roger E. Summons 《Organic Geochemistry》2009,40(12):1169-1178

The Lost City Hydrothermal Field hosts a distinctive microbial ecosystem that is supported by the products of serpentinization reactions. The calcium carbonate chimneys here contain abundant isoprenoidal and non-isoprenoidal ether lipids, the structural diversity of which is similar to that found in carbonate crusts at cold seeps where anaerobic oxidation of methane (AOM) is the dominant biogeochemical process. The microbial community at Lost City includes abundant archaea, which largely belong to a single phylotype within the methanogenic Methanosarcinales. Isoprenoidal diethers derived from these archaea have polar head groups comprising phosphatidylglycerol or monoglycosyl moieties, although many isoprenoidal diethers detected in these carbonates lack head groups.The non-isoprenoidal diether lipids at Lost City are largely glycolipids. Glycosydic non-isoprenoidal diethers have not previously been reported from any environments or bacterial isolates. Glycolipids are common in archaea where they contain isoprenoidal hydrocarbon cores ether linked to glycerol. Glycolipids also occur in some bacteria and in these non-isoprenoidal fatty acid chains are ester linked to glycerol. However, the glycosylated non-isoprenoidal diether lipids at Lost City contain a previously undetected combination of archaeal and bacterial traits that might be an adaptive response to the vent environment. We hypothesize that utilization of glycosyl head groups instead of phosphatidyl head groups is a strategy for conservation of phosphate by organisms growing in fluids low in this essential nutrient.  相似文献   

Evaluation of terrestrial carbonaceous matter aromatization by Raman spectroscopy and its application to C chondrites     

Jaques S. Schmidt  Ruth Hinrichs 《Meteoritics & planetary science》2020,55(4):800-817

A Raman method to estimate the aromatization degree of carbonaceous matter (CM) was established, and calibrated by literature data respecting differences in acquisition procedures. The generated equations allowed a comparison of the G‐band width to vitrinite reflectance, and to additional structural organization parameter extracted from X‐ray powder diffraction. The relations between aromatization degree and peak temperatures from literature were then propagated to G‐band width parameter. The applicability of these geothermometers is demonstrated by the consistency of data obtained for carbonaceous chondrites with previous estimations. Since the CM aromatization is controlled by peak temperature and time span, it is possible to estimate the duration of chondrite’s heating events. The G‐band width relation to elemental ratio trends of organic matter in chondrites, interplanetary dust particles, glucose, and saccharose‐based semi‐coke favors synthesis by formose route. These findings provide new approaches for the future development of chemical kinetic models for organic matter of chondrites. A reliable chemical model may allow the external calibration of numerical models for accurately evaluating the peak temperatures and cooling durations of chondrites.  相似文献   

Spectral properties of angrites     

T. H. Burbine  T. J. McCoy  J. L. Hinrichs  P. G. Lucey 《Meteoritics & planetary science》2006,41(8):1139-1145

Abstract— Angrites are generally believed to be fragments of a basaltic asteroid that differentiated under relatively oxidizing conditions. Almost all angrites (e.g., D'Orbigny, Lewis Cliff [LEW] 86010, and Sahara 99555) are composed predominately of anorthite, Al‐Ti diopside‐hedenbergite, and Ca‐rich olivine, except for the type specimen, Angra dos Reis, which is composed almost entirely of Al‐Ti diopside‐hedenbergite. D'Orbigny, LEW 86010, and Sahara 99555 also have spectral properties very different from Angra dos Reis. These newly measured angrites all have broad absorption features centered near 1 μm with very weak to absent absorption bands at ?2 μm, which is characteristic of some clinopyroxenes. The spectrum of Angra dos Reis has the characteristic 1 and 2 μm features due to pyroxene. One asteroid, 3819 Robinson, has similar spectral properties to the newly measured angrites in the visible wavelength region, but does not appear to spectrally match these angrites in the near‐infrared.  相似文献