Low‐temperature catalytic CO2 hydrogenation with geological quantities of ruthenium: a possible abiotic CH4 source in chromitite‐rich serpentinized rocks

Metal‐catalysed CO₂ hydrogenation is considered a source of methane in serpentinized (hydrated) igneous rocks and a fundamental abiotic process germane to the origin of life. Iron, nickel, chromium and cobalt are the catalysts typically employed in hydrothermal simulation experiments to obtain methane at temperatures >200°C. However, land‐based present‐day serpentinization and abiotic gas apparently develop below 100°C, down to approximately 40–50°C. Here, we document considerable methane production in thirteen CO₂ hydrogenation experiments performed in a closed dry system, from 20 to 90°C and atmospheric pressure, over 0.9–122 days, using concentrations of non‐pretreated ruthenium equivalent to those occurring in chromitites in ophiolites or igneous complexes (from 0.4 to 76 mg of Ru, equivalent to the amount occurring approximately in 0.4–760 kg of chromitite). Methane production increased with time and temperature, reaching approximately 87 mg CH₄ per gram of Ru after 30 days (2.9 mgCH₄/g_ru/day) at 90°C. At room temperature, CH₄ production rate was approximately three orders of magnitude lower (0.003 mgCH₄/g_ru/day). We report the first stable carbon and hydrogen isotope ratios of abiotic CH₄ generated below 100°C. Using initial δ¹³C_CO2 of ‐40‰, we obtained room temperature δ¹³C_CH4 values as ¹³C depleted as ?142‰. With time and temperature, the C‐isotope separation between CO₂ and CH₄ decreased significantly and the final δ¹³C_CH4 values approached that of initial δ¹³C_CO2. The presence of minor amounts of C₂‐C₆ hydrocarbons is consistent with observations in natural settings. Comparative experiments at the same temperatures with iron and nichel catalysts did not generate CH₄. Ru‐enriched chromitites could potentially generate methane at low temperatures on Earth and on other planets.     

Ancient DNA in human bones from Neolithic and Bronze Age sites in Greece and Crete

Attempts were made to detect ancient DNA (aDNA) in samples of 88 human skeletons from eight Neolithic and Bronze Age sites in Greece and Crete. Ancient DNA was absent in specimens from Nea Nikomedia, Lerna, Karaviádena (Zakro), Antron Grave Circle A and Mycenae Grave Circle A. For each of three skeletons from Antron Grave Circle B that were sampled, polymerase chain reactions (PCRs) gave products for nuclear but not mitochondrial DNA, but amplicon yield was low and inconsistent with replicate PCRs failing to give reproducible results. With specimens from Mycenae Grave Circle B, evidence for mitochondrial aDNA was obtained for four of the 22 skeletons that were studied, and at Kouphovouno evidence for mitochondrial and/or nuclear aDNA was obtained with eight of the 20 skeletons that were examined. We conclude that, although aDNA might be present in some Eastern Mediterranean skeletons from later centuries of the Bronze Age, it is not commonly found in material from this period and is likely to be absent from older material.     

An experimental and modeling study of Na-rich hydrothermal alteration

Sodic alteration assemblages including clinoptilolite, mordenite, analcime and Na‐montmorillonite were locally observed in sediments in the eastern part of the Hachimantai geothermal region, northeast Japan. This study investigated the mechanisms of sodic enrichment in the sediments during alteration. Kinetic results for water/rock interaction experiments are reported here. Batch‐type experiments were conducted at 150–250°C under saturated vapor pressure. Pyroclastic rocks dissolved incongruently in these experiments, and the solubility and dissolution rates among elements varied as follows: the apparent steady‐state concentrations of major elements are Si > Na ? K > Ca > Al and the order of the dissolution rates is Si > Al > Na ? K > Ca. Na had the highest steady‐state concentration and fastest dissolution rate of the alkali and alkali earth metal ions. Based on surface analysis of plagioclase, dissolution was effected via a reaction layer of Na‐montmorillonite on the mineral surface. Additionally, a reaction model constructed based on the experimentally observed reaction mechanism quantitatively explains the dissolution behavior. These results show that Na‐montmorillonite can be precipitated by pyroclastic rock/meteoric water interactions without seawater involvement: the Na is derived from the host rocks.     

Chemical modification of pyroclastic rock by hot water: an experimental investigation of mass transport at the fluid–solid interface

Hydrothermal water–(pyroclastic) rock interactions were examined using flow-through experiments to deduce the effect of mass transport phenomena on the reaction process. A series of experiments were conducted over the temperature range 75–250°C, with a constant temperature for each experiment, and at saturated vapour pressure, to estimate the apparent rate constants as a function of temperature.
Based on the chemistry of analysed solutions, the water–rock interaction in the experiments was controlled by diffusion from the reaction surface and by the existence of a surface layer at the rock–fluid interface, which regulated the chemical reaction rate. The reaction progress depended to a high degree on flow velocity and temperature conditions, with element abundances in the fluid significantly affected by these factors. Mass transport coefficients for diffusion from the rock surface to the bulk solution have been estimated. Ca is selectively depleted under lower temperature conditions ( T  < 150°C), whereas Na is greatly depleted under higher temperature conditions ( T  > 150°C), and K reaction rates are increased when flow velocity increases. Using these conditions, specific alkali and alkali earth cations were selectively leached from mineral surfaces. The 'surface layer' comprised a 0.5–1.8 mm boundary film on the solution side (the thickness of this layer has no dependence on chemical character) and a reaction layer. The reaction layer was composed of a Si, Al-rich cation-leached layer, whose thickness was dependent on temperature, flow velocity and reaction length. The reaction layer varied in thickness from about 10⁻⁴ to 10⁻⁷ mm under high temperature/low fluid velocity and low temperature/high fluid velocity conditions, respectively.     

Bone reactions on a pliocene cetacean rib indicate short‐term survival of predation event

There is little osteological evidence of non‐lethal predation events in the archaeological or vertebrate paleontological record. A small section of Pliocene cetacean rib collected from the Yorktown Formation within the PCS Phosphate Mine (formerly Lee Creek Mine), Aurora, North Carolina, U.S.A., shows evidence of this kind of trophic interaction. In this case study, we offer a diagnosis of bone traumatic pathology in which three bone‐forming lesions on the partial rib are interpreted as the reaction to a bite inflicted by a macro‐predator, the first such report from a marine environment. In addition to the three well‐defined lesions, a thin layer of woven bone covers much of the remaining cortical bone. The combination of the three bone‐forming lesions and the thin layer of woven bone suggest the presence of an inflammatory process almost certainly caused by infection secondary to the trauma. Survival following the traumatic event was probably less than 6 weeks. The Neogene chondrichthyan fauna from this locality preserves several large predators, including Carcharocles megalodon, Carcharodon carcharias, Isurus xiphidon and Parotodus benedeni, which were all capable, at least in terms of their size, of having bitten the cetacean. Although most of the odontocetes known from the Yorktown Formation were too small to have inflicted this wound, some of the physeterids may have been large enough to have caused the lesions on the partial rib. This evidence of predation in Pliocene whale bone raises the possibility of similar lesions being found in whale bone recovered from archaeological sites. Copyright © 2010 John Wiley & Sons, Ltd.     

浙江瓯海出土一件西周青铜器腐蚀成因研究

为研究浙江温州瓯海M24墓出土的一件青铜器的腐蚀成因,采用扫描电镜（SEM）、X射线荧光光谱仪（XRF）、X射线衍射仪（XRD）、离子色谱分析仪（HPIC）等,对青铜剑腐蚀产物及其埋藏土壤进行了分析。结果表明,青铜剑已严重腐蚀,铜元素大量流失形成以锡元素为主的腐蚀产物。通过测量模拟瓯海土壤环境下的自腐蚀电位并参照CuH₂O体系的电位-pH图,推导出了浙江瓯海出土一件西周青铜器腐蚀反应历程。研究结果对类似出土文物有参考价值。     

铜及其合金的表面着色机理

根据表面着色的化学动力学原理论证了铜及铜合金表面人工仿古着色处理的某些必要过程。如为何要进行着色前的表面预处理;表面预处理的主要内容及着色反应的化学机理。并对目前众多的人工表面着色配方进行了归纳。     

唐代鎏金铜天王像的保护与研究

依据现代科学检测方法,对唐代鎏金铜天王像不同部位的锈蚀产物进行了系统分析。运用软硬酸碱之间相互反应规律的理论,制定了以EDTA为主的配位体参加除锈反应的方案。综合多年的工作经验,找出络合反应中的最佳反应条件,从理论和实践中总结出较为可行的鎏金器物保护方法。     

Kinetic effect of carbonic anhydrase enzyme on the carbonation reaction of lime mortar

The effect of carbonic anhydrase enzyme on the precipitation kinetics and phase transformations of calcium carbonate, and on the strength development of lime mortars has been investigated with saturated lime solutions, lime pastes and lime mortars under atmospheric conditions. The results clearly show that carbonic anhydrase catalyzes the reaction between carbon dioxide and aqueous lime, and increases the rate of calcium carbonate crystallization, the yield of the carbonation reaction and mortar strength at early ages. This is most likely a kinetic effect associated with the increased rate of carbonate ions supply to the solution by the enzyme. In addition, this enzyme favors the formation of stable calcite and significantly modifies its morphology by developing new crystal faces. These results suggest a novel approach for accelerating the hardening of lime mortars using carbonic anhydrase enzyme, which may offer a potentially novel approach with significant benefits on the applications of lime mortars in architectural heritage conservation as well as in construction.     

Rates of retrograde metamorphism and their implications for crustal rheology

The rate of reaction of a natural hornblende garnet granulite with water under a range of mid- to lower crustal conditions has been investigated experimentally. In runs of between 7 and 84 days small but measurable amounts of water were consumed, and sheet silicates (300°C, 300 MPa and 400°C, 400 MPa) and/or secondary actinolite (400°C, 400 MPa and 500°C, 500 MPa) were observed to have grown. When normalized to the surface area of the starting materials, hydration rates were in the range of 2–5 × 10⁻⁸ g m⁻² sec⁻¹. These reaction rates imply that a film of water that infiltrated a planar crack with a half width of 100 μm would be completely consumed within c. 100 years. These results imply that where water infiltrates the crust along faults or underlying shear zones in response to a deformation, it will remain as a free phase for only a finite period of time, which in some cases will be less than the repeat time for major earthquakes in the fault system. Thus, the rheology of fault zones and shear zones is likely to be cyclical, with the zone becoming stronger with time as water is consumed, and then weakened by infiltration of water after each rupture.