Carbon isotopic composition of acetic acid generated by hydrous pyrolysis of macromolecular organic matter from the Murchison meteorite

Abstract— Low molecular weight monocarboxylic acids, including acetic acid, are some of the most abundant organic compounds in carbonaceous chondrites. So far, the ¹³C‐ and D‐enriched signature of water‐extractable carboxylic acids has implied an interstellar contribution to their origin. However, it also has been proposed that monocarboxylic acids could be formed by aqueous reaction on the meteorite parent body. In this study, we conducted hydrous pyrolysis of macromolecular organic matter purified from the Murchison meteorite (CM2) to examine the generation of monocarboxylic acids with their stable carbon isotope measurement. During hydrous pyrolysis of macromolecular organic matter at 270–330 °C, monocarboxylic acids with carbon numbers ranging from 2 (C₂) to 5 (C₅) were detected, acetic acid (CH₃COOH; C₂) being the most abundant. The concentration of the generated acetic acid increased with increasing reaction temperature; up to 0.48 mmol acetic acid/g macromolecular organic matter at 330 °C. This result indicates that the Murchison macromolecule has a potential to generate at least ?0.4 mg acetic acid/g meteorite, which is about four times higher than the amount of water‐extractable acetic acid reported from Murchison. The carbon isotopic composition of acetic acid generated by hydrous pyrolysis of macromolecular organic matter is ?‐27‰ (versus PDB), which is much more depleted in ¹³C than the water‐extractable acetic acid reported from Murchison. Intramolecular carbon isotope distribution shows that methyl (CH₃‐)‐C is more enriched in ¹³C relative to carboxyl (‐COOH)‐C, indicating a kinetic process for this formation. Although the experimental condition of this study (i.e., 270–330 °C for 72 h) may not simulate a reaction condition on parent bodies of carbonaceous chondrite, it may be possible to generate monocarboxylic acids at lower temperatures for a longer period of time.     

An experimental study on Fischer‐Tropsch catalysis: Implications for impact phenomena and nebular chemistry

Abstract— Fischer‐Tropsch catalysis, by which CO and H₂ are converted to CH₄ on the surface of transition metals, has been considered to be one of the most important chemical reactions in many planetary processes, such as the formation of the solar and circumplanetary nebulae, the expansion of vapor clouds induced by cometary impacts, and the atmospheric re‐entry of vapor condensate due to asteroidal impacts. However, few quantitative experimental studies have been conducted for the catalytic reaction under conditions relevant to these planetary processes. In this study, we conduct Fischer‐Tropsch catalytic experiments at low pressures (1.3 times 10^?4 bar ≤ P ≤ 5.3 times 10^?1 bar) over a wide range of H₂/CO ratios (0.25–1000) using pure iron, pure nickel, and iron‐nickel alloys. We analyze what gas species are produced and measure the CH₄ formation rate. Our results indicate that the CH₄ formation rate for iron catalysts strongly depends on both pressure and the H₂/CO ratio, and that nickel is a more efficient catalyst at lower pressures and lower H₂/CO ratios. This difference in catalytic properties between iron and nickel may come from the reaction steps concerning disproportionation of CO, hydrogenation of surface carbon, and the poisoning of the catalyst. These results suggest that nickel is important in the atmospheric re‐entry of impact condensate, while iron is efficient in circumplanetary subnebulae. Our results also indicate that previous numerical models of iron catalysis based on experimental data at 1 bar considerably overestimate CH₄ formation efficiency at lower pressures, such as the solar nebula and the atmospheric re‐entry of impact condensate.     

Physiological acclimation by phytoplankton explains observed changes in Si and N uptake rates during the SERIES iron-enrichment experiment

During the SERIES iron-enrichment experiment in the eastern subarctic Pacific, after addition of iron and its subsequent depletion, the Si:N drawdown ratio increased at approximately the time that diatoms became iron limited. Laboratory studies have reported that this results from a decrease in the rate of N uptake together with a more moderate decrease in the rate of Si uptake for iron-limited cultures compared to iron-replete cultures. However, for SERIES Boyd et al. (Limnol. Oceanogr. 50 (2005)) reported an unexplained increase in the rate of Si uptake at the onset of iron limitation and suggested that studies of nutrient uptake kinetics should be undertaken in search of an explanation. We compare the classic Michealis–Menten (MM) kinetics to the recently developed optimal uptake (OU) kinetics (the SPONGE: Smith and Yamanaka. Limnol. Oceanogr. 52 (2007)) within a variable-composition model, which employs cell quotas for each relevant nutrient, applied to the multi-element (C, N, Si, Fe) dynamics during SERIES. Using the Monte Carlo Markov Chain, we fit two versions of the model (differing only in the equations for nutrient uptake) to the available data for nutrient concentrations, chlorophyll, biogenic silica and particulate organic carbon and specific growth rates.With either uptake kinetics, the model reproduces observed concentrations well for nutrients and somewhat less well for chlorophyll. The different uptake kinetics yield greater differences in modeled elemental composition of phytoplankton and biomass of phytoplankton and zooplankton, which are not directly constrained by data. MM kinetics cannot reproduce the observed increase in Si uptake rate as a function of the decreasing trend in concentration of silicic acid, and it predicts Si limitation throughout nearly all of the experiment after iron-fertilization. In contrast, OU kinetics reproduces the increase in Si uptake rate and matches the observation-based estimate for the timing of the return to iron limitation. The key assumption of the SPONGE, that uptake rates of all nutrients depend on physiological acclimation by phytoplankton as a function of the ambient concentration of the growth-limiting nutrient, was originally formulated for modeling chemostat experiments. We show that it also agrees with the observations from this field experiment and provides an explanation for the increases in Si uptake rate and Si:N drawdown ratio.     

Influence of contamination on banded iron formations in the Isua supracrustal belt,West Greenland: Reevaluation of the Eoarchean seawater compositions

Banded Iron Formations(BIFs) are chemical sediments, ubiquitously distributed in the Precambrian supracrustal belts; thus their trace element compositions are helpful for deciphering geochemical evolution on the Earth through time. However, it is necessary to elucidate factors controlling the whole-rock compositions in order to decode the ancient seawater compositions because their compositions are highly variable. We analyzed major and trace element contents of the BIFs in the 3.8-3.7 Ga Isua supracrustal belt(ISB), southern West Greenland. The BIFs are petrographically classified into four types:Black-,Gray-, Green-and White-types, respectively. The Green-type BIFs contain more amphiboles, and are significantly enriched in Co, Ni, Cu, Zn, Y, heavy rare earth element(HREE) and U contents. However,their bulk compositions are not suitable for estimate of seawater composition because the enrichment was caused by secondary mobility of metamorphic Mg, Ca and Si-rich fluid, involvement of carbonate minerals and silicate minerals of olivine and pyroxene and/or later silicification or contamination of volcanic and clastic materials. The White-type BIFs are predominant in quartz, and have lower transition element and REE contents. The Gray-type BIFs contain both quartz and magnetite. The Black-type BIFs are dominated by magnetite, and contain moderate to high transition element and REE contents. But,positive correlations of V, Ni, Zn and U contents with Zr contents suggest that involvement of detrital,volcanic and exhalative materials influences on their contents. The evidence for significant influence of the materials on the transition element contents such as Ni in the BIFs indicates the transition element contents in the Archean ocean were much lower than previously estimated. We reconstructed secular variations of V,Co, Zn and U contents of BIFs through time, which show Ni and Co contents decreased whereas V, Zn and U contents increased through time. Especially, the Ni and Co contents drastically decreased in the Mesoarchean rather than around the Great Oxidation Event. On the other hand, the V,Zn and U contents progressively increased from the Mesoarchean to the Proterozoic. Stratigraphical trends of the BIFs show increase in Y/Ho ratios and decrease in positive Eu anomaly upwards, respectively. The stratigraphic changes indicate that a ratio of hydrothermal fluid to seawater component gradually decrease through the deposition, and support the Eoarchean plate tectonics, analogous to the their stratigraphic variations of seafloor metalliferous sediments at present and in the Mesoarchean.     

The Hayabusa Spacecraft Asteroid Multi-band Imaging Camera (AMICA)

The Hayabusa Spacecraft Asteroid Multi-band Imaging Camera (AMICA) has acquired more than 1400 multispectral and high-resolution images of its target asteroid, 25143 Itokawa, since late August 2005. In this paper, we summarize the design and performance of AMICA. In addition, we describe the calibration methods, assumptions, and models, based on measurements. Major calibration steps include corrections for linearity and modeling and subtraction of bias, dark current, read-out smear, and pixel-to-pixel responsivity variations. AMICA v-band data were calibrated to radiance using in-flight stellar observations. The other band data were calibrated to reflectance by comparing them to ground-based observations to avoid the uncertainty of the solar irradiation in those bands. We found that the AMICA signal was linear with respect to the input signal to an accuracy of ?1% when the signal level was <3800 DN. We verified that the absolute radiance calibration of the AMICA v-band (0.55 μm) was accurate to 4% or less, the accuracy of the disk-integrated spectra with respect to the AMICA v-band was about 1%, and the pixel-to-pixel responsivity (flat-field) variation was 3% or less. The uncertainty in background zero level was 5 DN. From wide-band observations of star clusters, we found that the AMICA optics have an effective focal length of 120.80 ± 0.03 mm, yielding a field-of-view (FOV) of 5.83° × 5.69°. The resulting geometric distortion model was accurate to within a third of a pixel. We demonstrated an image-restoration technique using the point-spread functions of stars, and confirmed that the technique functions well in all loss-less images. An artifact not corrected by this calibration is scattered light associated with bright disks in the FOV.     

Diel behavior of stable isotopes of dissolved oxygen and dissolved inorganic carbon in rivers over a range of trophic conditions,and in a mesocosm experiment

Rates of diel (24-h) biogeochemical processes in rivers and their effect on daily changes in the concentration of metals and metalloids have been well documented in the literature over the last 20 years. Investigations into the effects of these processes on aquatic systems and the underlying mechanisms that control the processes can significantly improve our understanding of how natural aquatic environments function and will respond to changing environmental conditions and anthropogenic impacts. Daily changes in the rates of biogeochemical processes have, more recently, been shown to influence the stable isotope composition of dissolved oxygen and dissolved inorganic carbon in natural waters. Here we present a comprehensive picture of the persistence and reproducibility of diel cycles of the ¹⁸O composition of dissolved molecular oxygen (δ¹⁸O-DO) and the ¹³C composition of dissolved inorganic carbon (δ¹³C-DIC) across five Montana, USA rivers investigated over a 4-year period. A mesocosm experiment showed the same behavior in δ¹⁸O-DO and δ¹³C-DIC as seen in riverine settings across light and dark periods.A cross plot of δ¹⁸O-DO and δ¹³C-DIC from each stream exhibits a clockwise elliptical pattern which is attributed to the daily changes in the balance of metabolic rates as well as air–water gas exchange. The amplitude of the change in the isotope composition is shown to be directly related to the trophic state of the river and a relationship between net productivity and diel changes in δ¹⁸O-DO and δ¹³C-DIC is presented. This relationship between trophic status with δ¹⁸O-DO, δ¹³C-DIC and production emphasizes the significance of how rates of biogeochemical processes in natural systems can influence the daily changes in the composition of surface waters.     

Temperature scaling pattern dependence on representative concentration pathway emission scenarios A letter

To preserve consistency among developed emission scenarios, the scenarios used in climate modeling, and the climate scenarios available for impact research, the pattern scaling technique is useful technique. The basic assumption of pattern scaling is that the spatial response pattern per 1 K increase in the global mean surface air temperature (SAT) (scaling pattern) is the same among emission scenarios, but this assumption requires further validation. We therefore investigated the dependence of the scaling pattern of the annual mean SAT on GHGs emission scenarios of representative concentration pathways (RCP) and the causes of that dependence using the Model for Interdisciplinary research on Climate 5 developed by Japanese research community. In particular, we focused on the relationships of the dependency with effects of aerosols and Atlantic meridional overturning circulation. We found significant dependencies of the scaling pattern on emission scenarios at middle and high latitudes of the Northern Hemisphere, with differences of >15 % over parts of East Asia, North America, and Europe. Impact researchers should take into account those dependencies that seriously affect their research. The mid-latitude dependence is caused by differences in sulfate aerosol emissions per 1 K increase in the global mean SAT, and the high-latitude dependence is mainly caused by nonlinear responses of sea ice and ocean heat transport to global warming. Long-term trends in land-use and land-cover changes did not significantly affect the scaling pattern of annual mean SAT, but they might have an effect at different timescales.     

Oxygen isotope fractionation of dissolved oxygen during reduction by ferrous iron

The oxygen isotope fractionation factor of dissolved oxygen gas has been measured during inorganic reduction by aqueous FeSO₄ at 10−54 °C under neutral (pH 7) and acidic (pH 2) conditions, with Fe(II) concentrations ranging up to 0.67 mol L⁻¹, in order to better understand the geochemical behavior of oxygen in ferrous iron-rich groundwater and acidic mine pit lakes. The rate of oxygen reduction increased with increasing temperature and increasing Fe(II) concentration, with the pseudo-first-order rate constant k ranging from 2.3 to 82.9 × 10⁻⁶ s⁻¹ under neutral conditions and 2.1 to 37.4 × 10⁻⁷ s⁻¹ under acidic conditions. The activation energy of oxygen reduction was 30.9 ± 6.6 kJ mol⁻¹ and 49.7 ± 13.0 kJ mol⁻¹ under neutral and acidic conditions, respectively. Oxygen isotope enrichment factors (ε) become smaller with increasing temperature, increasing ferrous iron concentration, and increasing reaction rate under acidic conditions, with ε values ranging from −4.5‰ to −11.6‰. Under neutral conditions, ε does not show any systematic trends vs. temperature or ferrous iron concentration, with ε values ranging from −7.3 to −10.3‰. Characterization of the oxygen isotope fractionation factor associated with O₂ reduction by Fe(II) will have application to elucidating the process or processes responsible for oxygen consumption in environments such as groundwater and acidic mine pit lakes, where a number of possible processes (e.g. biological respiration, reduction by reduced species) may have taken place.     

Elemental and isotope behavior of macromolecular organic matter from CM chondrites during hydrous pyrolysis

Abstract— A new insight into carbon and hydrogen isotope variations of insoluble organic matter (IOM) is provided from seven CM chondrites, including Murchison and six Antarctic meteorites (Y‐791198, Y‐793321, A‐881280, A‐881334, A‐881458 and B‐7904) as well as Murchison IOM residues after hydrous pyrolysis at 270–330 °C for 72 h. Isotopic compositions of bulk carbon (δ¹³C_bulk) and hydrogen (δD) of the seven IOMs vary widely, ranging from ?15.1 to ?7.6%₀ and +133 to +986%₀, respectively. Intramolecular carboxyl carbon (δ13C_COOH) is more enriched in ¹³C by 7.5. 11%₀ than bulk carbon. After hydrous pyrolysis of Murchison IOM at 330 °C, H/C ratio, δ13C_bulk, δ13C_COOH, and δD values decrease by up to 0.31, 3.5%₀, 5.5%₀, and 961%₀, respectively. The O/C ratio increases from 0.22 to 0.46 at 270 °C and to 0.25 at 300 °C, and decreases to 0.10 at 330 °C. δ13C_bulk‐δD cross plot of Murchison IOM and its pyrolysis residues shows an isotopic sequence. Of the six Antarctic IOMs, A‐881280, A‐881458, Y‐791198 and B‐7904 lie on or near the isotopic sequence depending on the degree of hydrous and/or thermal alteration, while A‐881334 and Y‐793321 consist of another distinct isotope group. A δ13C_bulk‐δ13C_COOH cross‐plot of IOMs, including Murchison pyrolysis residues, has a positive correlation between them, implying that the oxidation process to produce carboxyls is similar among all IOMs. These isotope distributions reflect various degree of alteration on the meteorite parent bodies and/or difference in original isotopic compositions before the parent body processes.