Characterization of stable isotope fractionation during methane production in the sediment of a eutrophic lake,lake dagow,germany

We measured delta C-13 of CO2, CH4, and acetate-methyl in profundal sediment of eutrophic Lake Dagow by incubation experiments in the presence and absence of methanogenic inhibitors chloroform, bromoethane sulfonate (BES), and methyl fluoride, which have different specificities. Methyl fluoride predominantly inhibits acetoclastic methanogenesis and affects hydrogenotrophic methanogenesis relatively little. Optimization of methyl fluoride concentrations resulted in complete inhibition of acetoclastic methanogenesis. Methane was then exclusively produced by hydrogenotrophic methanogenesis and thus allowed determination of the fractionation factors specific for this methanogenic pathway. Acetate, which was then no longer consumed, accumulated and allowed determination of the isotopic signatures of the fermentatively produced acetate. BES and chloroform also inhibited CH4 production and resulted in accumulation of acetate. The fractionation factor for hydrogenotrophic methanogenesis exhibited variability, e. g., it changed with sediment depth. The delta C-13 of the methyl group of the accumulated acetate was similar to the delta C-13 of sedimentary organic carbon, while that of the carboxyl group was by about 12 parts per thousand higher. However, the delta C-13 of the acetate was by about 5 parts per thousand lower in samples with uninhibited compared with inhibited acetoclastic methanogenesis, indicating unusual isotopic fractionation. The isotope data were used for calculation of the relative contribution of hydrogenotrophic vs. acetoclastic methanogenesis to total CH4 production. Contribution of hydrogenotrophic methanogenesis increased with sediment depth from about 35% to 60%, indicating that organic matter was only partially oxidized in deeper sediment layers.

Facile synthesis of polyaniline nanofibers using pseudo-high dilution technique

A new approach for the synthesis of polyaniline nanofibers under pseudo-high dilute conditions in aqueous system has been developed. High yield nanoscale polyaniline fibers with 18-110 nm in diameter are readily prepared by a high aniline concentration 0.4 M oxidation polymerization using ammonium persulfate (APS) as an oxidant in the presence of hydrochloric acid (HCl), perchloric acid (HClO4), (1S)-(+)-10-camphorsulfonic acid (CSA), acidic phosphate PAEG120 (PA120) and sulfuric acid (H2SO4) as the dopants. The novel pathway always produces polyaniline nanofibers of tunable diameters, high conductivity (from 10(0) to 10(1) S/cm) and crystallinity.

The synthesis of phenyl-capped trianiline and teraaniline by a modified-pseudo-high dilution technique and their UV-Vis spectral studies

Phenyl-capped trianiline and tetraaniline in the leucoemeraldine oxidation state were synthesized through a modified-pseudo-high-dilution technique. The chemical oxidation process of these compounds were studied by UV-Vis spectra. It was found that phenyl-capped trianiline in the leucoemeraldine oxidation state was oxidized to its EB form and then decomposed, Phenyl-capped tetraaniline was oxidized to its EB form and then to the pernigraniline oxidation state.

Kinetic isotope effects of proton transfer reaction for amines by ultrasonic relaxation methods: Unexpected evidence from the results in ethylamine solutions

Ultrasonic absorption coefficients for ethylamine in heavy water (D2O) and in light water (H2O) have been measured in the frequency range from 0.8 to 220 MHz at 25 degrees C. A single relaxational process has been observed in these two kinds of solutions. From the concentration dependence of the ultrasonic relaxation parameters, and following the reaction mechanism proposed by Eigen et al. for ethylamine in H2O, the causes of the relaxations have been attributed to a perturbation of an equilibrium associated with a deuteron or proton transfer reaction. The rate and equilibrium constants have been estimated from deuterioxide or hydroxide ion concentration dependence of the relaxation frequency, and the kinetic isotope effects have been determined. In addition, the standard volume changes of the reactions have been calculated from the concentration dependence of the maximum absorption per wavelength, and the adiabatic compressibility has also been determined from the density and sound velocity for ethylamine in D2O and in H2O, respectively. These results are compared with those for propylamine and butylamine and are discussed in relation to the different kinetic properties between D2O and H2O, the reaction radii derived by Debye theory, and the structural properties of the reaction intermediate.

Facile synthesis of phenyl-capped oligoanilines using pseudo-high dilution technique

Monodispersed phenyl-capped trianiline and tetraaniline were successfully synthesized by the reactions of diphenylamine with acetaldehyde-based Sckiff's bases of N-phenyl-1,4-phenylenediamine and 1,4-phenylenediamine, respectively, in the presence of ammonium persulfate and hydrochloric acid, subsequent deprotonation and reduction with phenylhydrazine. The reaction mechanism probably involves the slow hydrolysis of the Sckiff's bases and subsequent oxidative coupling reactions of the formed ammonium salts with diphenylamine at pseudo-high dilution condition of the salts.

Isotope effect in proton-transfer and association-dissociation reactions for butylamine by ultrasonic relaxation methods

Ultrasonic absorption coefficients were measured for butylamine in heavy water (D2O) in the frequency range from 0.8 to 220 MHz and at concentrations from 0.0278 to 2.5170 mol dm(-3) at 25 degrees C; two kinds of relaxation processes were observed. One was found in relatively dilute solutions (up to 0.5 mol dm(-3)), which was attributed to the hydrolysis of butylamine. In order to compare the results, absorption measurements were also carried out in light water (H2O). The rate and thermodynamic parameters were determined from the concentration dependence of the relaxation frequency and the maximum absorption per wavelength. The isotope effects on the diffusion-controlled reaction were estimated and the stability of the intermediate of the hydrolysis was considered while comparing it with the results for propylamine in H2O and D2O. Another relaxation process was observed at concentrations greater than 1 mol dm(-3) in D2O. In order to examine the solution characteristics, proton NMR measurements for butylamine were also carried out in D2O. The chemical shifts for the gamma- and delta-proton in butylamine molecule indicate the existence of an aggregate. From profiles of the concentration dependence of the relaxation frequency and the maximum absorption per wavelength of sound absorption, the source of the relaxation was attributed to an association-dissociation reaction, perhaps, associated with a hydrophobic interaction. The aggregation number, the forward and reverse rate constants and the standard volume change of the reaction were determined. It was concluded from a comparison with the results in H2O that the hydrophobic interaction of butylamine in D2O is stronger than that in H2O. Also, the isotope effect on this reaction was interpreted in terms of the solvent structure.

Helium, neon and argon isotope compositions of fluid inclusions in massive sulfides from the Jade hydrothermal field, the Oldnawa Trough

Helium, neon and argon isotope compositions of fluid inclusions have been measured in massive sulfide samples from the Jade hydrothermal field in the central Okinawa Trough. Fluid-inclusion He-3/He-4 ratios are between 6.2 and 10.1 times the air value (Ra), and with a mean of 7.8Ra, which are consistent with the mid-ocean ridge basalt values [He-3/He-4 approximate to (6Rasimilar to 11Ra)]. Values for Ne-20/Ne-22 are from 10.7 to 11.3, which are significantly higher than the atmospheric ratio (9.8). And the fluid-inclusion Ar-40/Ar-36 ratios range from 287 to 334, which are close to the atmosperic values (295.5). These results indicate that the noble gases of trapped hydrothermal fluids in massive sulfides are a mixture of mantle- and seawater-derived components, and the helium of fluid inclusions is mainly from mantle, the nelium and argon isotope compositions are mainly from seawater.

Nd isotope as the tracer of seawater evolution of early Miocene in the eastern Pacific Ocean

Fifty-six samples of nannofossil ooze were collected from Core PC5794 in the northern equatorial Pacific at 5 em intervals. With the methods of mass spectrometer (VG354) and ICP, the Nd isotopic compositions (epsilon(Nd)(t)), Mn contents and Mg/Sr ratios of carbonate phase have been analyzed. CaCO3 contents of bulk sediments were obtained by dissolution of 0.5 mol/L HCl. Based on these data, the high-resolution epsilon(Nd)(t) profile of seawater in early Miocene with core depth(or time) have been established. The values of epsilon(Nd)(t) range from -6.2 to -2.97 and 4 fluctuation cycles existed during 24.06-22.02 Ma. 4 low epsilon(Nd)(t) values (about -6.4) correspond to high CaCO3 contents, which implicates that there were 4 cold epochs or 4 times of Antarctic Bottom Water activity. They occurred at the time of 24.06 Ma, 23.85 Ma, 22.88 Ma and 22.26 Ma, respectively. High epsilon(Nd)(t) values correspond to the high Mn contents and high values of Mg/Sr ratio, which indicates the existence of 4 intense hydrothermal activity periods during 24.06-22 Ma, the durations of them are 4.05-23.98 Ma, 23.69-23.15 Ma, 22.74-22.37 Ma and 22.06-22.02 Ma, respectively.

Heinrich event imprints in the Okinawa Trough: evidence from oxygen isotope and planktonic foraminifera

Planktonic foraminiferal faunas, oxygen isotope and modern analog technique sea surface temperature records were obtained in piston core DGKS9603 (28degrees08.869'N, 127degrees16.238'E, water depth 1100 in) collected from the middle Okinawa Trough. During the last glaciation, four cold events were identified and correlate Heinrich events (HE) H2-5 of the last 45 ka. During the last deglaciation, core DGKS9603 has begun to be influenced by the Kuroshio since about 16 cal ka BP. Three weakenings of this warm current occurred at about 2.8-5.3, 11.4 and 15.5 cal ka BP respectively. Among the three fluctuations, the oldest one is synchronous with HE1 and could be a response to the strong cooling observed in the North Atlantic Ocean. The fluctuation occurring at about 11.4 cal ka ago corresponds to the Younger Dryas within the age error bars. Our observations provide new evidence that the HEs documented from Greenland and the northern North Atlantic had a global climatic impact. Changes in the intensity of the East Asian monsoon could be the main mechanism responsible for the paleoccanographic variations observed in the Okinawa Trough. (C) 2001 Elsevier Science B.V. All rights reserved.

He, Ne and Ar isotope compositions of fluid inclusions in hydrothermal sulfides from the TAG hydrothermal field, Mid-Atlantic Ridge

Helium, rieon and argon isotope compositions of fluid inclusions have been measured in hydrothermal sulfide samples from the TAG hydrothermal field at the Mid-Atlantic Ridge. Fluid-inclusion He-3/He-4 ratios are 2.2-13.3 times the air value (Ra), and with a mean of 7.2 Ra. Comparison with the local vent fluids (He-3/He-4=7.5-8.2 Ra) and mid-ocean ridge basalt values (He-3/He-4=6-11 Ra) shows that the variation range of He-3/He-4 ratios from sulfide-hosted fluid inclusions is significantly large. Values for Ne-20/Ne-22 are from 10.2 to 11.4, which are significantly higher than the atmospheric ratio (9.8). And fluid-inclusion Ar-40/Ar-36 ratios range from 287 to 359, which are close to the atmospheric values (295.5). These results indicate that the noble gases of fluid inclusions in hydrothermal sulfides are a mixture of mantle- and seawater-derived noble gases; the partial mantle-derived components of trapped hydrothermal fluids may be from the lower mantle; the helium of fluid inclusions is mainly from upper mantle; and the Ne and Ar components are mainly from seawater.

Os isotope dating and growth hiatuses of Co-rich crust from central Pacific

Up to now, accurate determination of the growth age and hiatuses of the Co-rich crust is still a difficult work, which constrains the researches on the genesis, growth process, controlling factors, regional tectonics, paleo-oceanographic background, etc. of the Co-rich crust. This paper describes our work in determining the initial growth age of the Co-rich crust to be of the late Cretaceous Campanian Stage (about 75-80 Ma), by selecting the Co-rich crust with clear multi-layer structures in a central Pacific seamount for layer-by-layer sample analysis and using a number of chronological methods, such as Co flux dating, dating by correlation with Os-187/Os-188 evolution curves of seawater, and stratigraphic division by calcareous nannofossils. We have also discovered growth hiatuses with different time intervals in the early Paleocene, middle Eocene, late Eocene and early-middle Miocene, respectively. These results have provided an important age background for further researches on the Co-rich crust growth process and the paleo-oceanographic environment evolution thereby revealed in the said region.

Major element, trace element, and Sr, Nd and Pb isotope studies of Cenozoic basalts from the South China Sea

The whole rock K-Ar ages of basalts from the South China Sea basin vary from 3.8 to 7.9 Ma, which suggest that intra-plate volcanism after the cessation of spreading of the South China Sea (SCS) is comparable to that in adjacent regions around the SCS, i.e., Leiqiong Peninsula, northern margin of the SCS, Indochina block, and so on. Based on detailed petrographic studies, we selected many fresh basaltic rocks and measured their major element, trace element, and Sr-Nd-Pb isotope compositions. Geochemical characteristics of major element and trace element show that these basaltic rocks belong to alkali basalt magma series, and are similar to OIB-type basalt. The extent of partial melting of mantle rock in source region is very low, and magma may experience crystallization differentiation and cumulation during the ascent to or storing in the high-level magma chamber. Sr-Nd-Pb isotopic data of these basaltic rocks imply an inhomogeneous mantle below the South China Sea. The nature of magma origin has a two end-member mixing model, one is EM2 (Enriched Mantle 2) which may be originated from mantle plume, the other is DMM (Depleted MORB Mantle). Pb isotopic characteristics show the Dupal anomaly in the South China Sea, and combined with newly found Dupal anomaly at Gakkel ridge in Arctic Ocean, this implies that Dupal anomaly is not only limited to South Hemisphere. In variation diagrams among Sr, Nd and Pb, the origin nature of mantle below the SCS is similar to those below Leiqiong peninsula, northern margin of the SCS and Indochina peninsula, and is different from those below north and northeast China. This study provides geochemical constraints on Hainan mantle plume.

Genesis of Th-230 excess in basalts from mid-ocean ridges and ocean islands: Constraints from the global U-series isotope database and major and rare earth element geochemistry

Based on Th-230-U-238 disequilibrium and major element data from mid-ocean ridge basalts (MORBs) and ocean island basalts (OIBs), this study calculates mantle melting parameters, and thereby investigates the origin of Th-230 excess. (Th-230/U-238) in global MORBs shows a positive correlation with Fe-8, P (o), Na-8, and F-melt (Fe-8 and Na-8 are FeO and Na2O contents respectively after correction for crustal fractionation relative to MgO = 8 wt%, P (o)=pressure of initial melting and F (melt)=degree of melt), while Th-230 excess in OIBs has no obvious correlation with either initial mantle melting depth or the average degree of mantle melting. Furthermore, compared with the MORBs, higher (Th-230/U-238) in OIBs actually corresponds to a lower melting degree. This suggests that the Th-230 excess in MORBs is controlled by mantle melting conditions, while the Th-230 excess in OIBs is more likely related to the deep garnet control. The vast majority of calculated initial melting pressures of MORBs with excess Th-230 are between 1.0 and 2.5 GPa, which is consistent with the conclusion from experiments in recent years that D (U)> D (Th) for Al-clinopyroxene at pressures of > 1.0 GPa. The initial melting pressure of OIBs is 2.2-3.5 GPa (around the spinel-garnet transition zone), with their low excess Ra-226 compared to MORBs also suggesting a deeper mantle source. Accordingly, excess Th-230 in MORBs and OIBs may be formed respectively in the spinel and garnet stability field. In addition, there is no obvious correlation of K2O/TiO2 with (Th-230/U-238) and initial melting pressure (P (o)) of MORBs, so it is proposed that the melting depth producing excess Th-230 does not tap the spinel-garnet transition zone. OIBs and MORBs in both (Th-230/U-238) vs. K2O/TiO2 and (Th-230/U-238) vs. P (o) plots fall in two distinct areas, indicating that the mineral phases which dominate their excess Th-230 are different. Ce/Yb-Ce curves of fast and slow ridge MORBs are similar, while, in comparison, the Ce/Yb-Ce curve for OIBs shows more influence from garnet. The mechanisms generating excess Th-230 in MORBs and OIBs are significantly different, with formation of excess Th-230 in the garnet zone only being suitable for OIBs.

Sources and preservation of organic matter in Plum Island salt marsh sediments (MA, USA): long-chain n-alkanes and stable carbon isotope compositions

Elemental (TOC, TN, C/N) and stable carbon isotopic (delta(13)C) compositions and n-alkane (nC(16-38)) concentrations were measured for Spartina alterniflora, a C-4 marsh grass, Typha latifolia, a C-3 marsh grass, and three sediment cores collected from middle and upper estuarine sites from the Plum Island salt marshes. Our results indicated that the organic matter preserved in the sediments was highly affected by the marsh plants that dominated the sampling sites. delta(13)C values of organic matter preserved in the upper fresh water site sediment were more negative (-23.0+/-0.3) as affected by the C-3 plants than the values of organic matter preserved in the sediments of middle (-18.9+/-0.8) and mud flat sites (-19.4+/-0.1) as influenced mainly by the C4 marsh plants. The distribution of n-alkanes measured in all sediments showed similar patterns as those determined in the marsh grasses S. alterniflora and T. latifolia, and nC(21) to nC(33) long-chain n-alkanes were the major compounds determined in all sediment samples. The strong odd-to-even carbon numbered n-alkane predominance was found in all three sediments and nC(29) was the most abundant homologue in all samples measured. Both delta(13)C compositions of organic matter and n-alkane distributions in these sediments indicate that the marsh plants could contribute significant amount of organic matter preserved in Plum Island salt marsh sediments. This suggests that salt marshes play an important role in the cycling of nutrients and organic carbon in the estuary and adjacent coastal waters. (C) 2003 Elsevier Ltd. All rights reserved.