71 research outputs found
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Kinetic Prefactors of Reactions on Solid Surfaces
Adsorbed molecules are involved in many reactions on solid surfaces that are of great technological
importance. As such, there has been tremendous effort worldwide to learn how to theoretically
predict rates for reactions involving adsorbed molecules. Theoretical calculations of rate constants
require knowing both their activation energy and prefactor. Recent advances in ab initio computational
methods (e.g., density functional theory with periodic boundary conditions and van der
Waals corrections) promise to soon provide activation energies for surface reactions with sufficient
accuracy to have real predictive ability. However, to predict reaction rates, we also need accurate
predictions of prefactors. We recently discovered that the standard entropies of adsorbed molecules
(S[superscript 0] [subscript ad]) linearly track the entropy of the gas-phase molecule at the same temperature (T), such that
S[superscript 0] [subscript ad] (T)=0.70 S[superscript 0] [subscript gas](T)−3.3 R (R=the gas constant), with a standard deviation of only 2 R over
a range of 50 R. This correlation, which applies only to conditions where their surface residence
times are shorter than ∼1000 s, provides a powerful new method for estimating the partition
functions for adsorbates and the kinetic prefactors for their reactions. For desorption, we show that
the prefactors obtained with DFT using transition state theory (TST) and the harmonic oscillator
approximation to get the partition function predicts prefactors for desorption that are of order
10³ times larger than experimental values while our approach gives much better estimates. We
also explore the applications of this approach to estimate prefactors within TST for the main
classes of adsorbate reactions: desorption, diffusion, dissociation and association, and discuss its
limitations. We discuss general issues associated with applying TST to rate laws and multi-step
mechanisms in surface chemistry, and argue that rates of adsorbate reactions which are often taken
to be proportional to coverage (θ) might better be taken as proportional to θ/(1−θ) (unless the
adsorbate forms islands), to account for the configurational entropy or excluded volume effects on
the adsorbate’s chemical potential.This is the publisher’s final pdf. The published article is copyrighted by Walter de Gruyter GmbH and can be found at: http://www.degruyter.com/view/j/zpch.Keywords: Adsorbate, Kinetic Prefactors, Kinetics, Transition State Theory, Surface Reaction
Injection-induced surface deformation and seismicity at the Hellisheidi geothermal field, Iceland
Induced seismicity is often associated with fluid injection but only rarely linked to surface deformation. At the Hellisheidi geothermal power plant in south-west Iceland we observe up to 2 cm of surface displacements during 2011–2012, indicating expansion of the crust. The displacements occurred at the same time as a strong increase in seismicity was detected and coincide with the initial phase of geothermal wastewater reinjection at Hellisheidi. Reinjection started on September 1, 2011 with a flow rate of around 500 kg/s. Micro-seismicity increased immediately in the area north of the injection sites, with the largest seismic events in the sequence being two M4 earthquakes on October 15, 2011. Semi-continuous GPS sites installed on October 15 and 17, and on November 2, 2011 reveal a transient signal which indicates that most of the deformation occurred in the first months after the start of the injection. The surface deformation is evident in ascending TerraSAR-X data covering June 2011 to May 2012 as well. We use an inverse modeling approach and simulate both the InSAR and GPS data to find the most plausible cause of the deformation signal, investigating how surface deformation, seismicity and fluid injection may be connected to each other. We argue that fluid injection caused an increase in pore pressure which resulted in increased seismicity and fault slip. Both pore pressure increase and fault slip contribute to the surface deformation
MethCORR Modelling of Methylomes From Formalin-Fixed Paraffin-Embedded Tissue Enables Characterization and Prognostication of Colorectal Cancer
Transcriptional characterization and classification has potential to resolve the inter-tumor heterogeneity of colorectal cancer and improve patient management. Yet, robust transcriptional profiling is difficult using formalin-fixed, paraffin-embedded (FFPE) samples, which complicates testing in clinical and archival material. We present MethCORR, an approach that allows uniform molecular characterization and classification of fresh-frozen and FFPE samples. MethCORR identifies genome-wide correlations between RNA expression and DNA methylation in fresh-frozen samples. This information is used to infer gene expression information in FFPE samples from their methylation profiles. MethCORR is here applied to methylation profiles from 877 fresh-frozen/FFPE samples and comparative analysis identifies the same two subtypes in four independent cohorts. Furthermore, subtype-specific prognostic biomarkers that better predicts relapse-free survival (HR = 2.66, 95%CI [1.67-4.22], P value < 0.001 (log-rank test)) than UICC tumor, node, metastasis (TNM) staging and microsatellite instability status are identified and validated using DNA methylation-specific PCR. The MethCORR approach is general, and may be similarly successful for other cancer types
Integration of micro-gravity and geodetic data to constrain shallow system mass changes at Krafla Volcano, N Iceland
New and previously published micro-gravity data are combined with InSAR data, precise levelling and GPS measurements to produce a model for the processes operating at Krafla volcano, 20 years after its most recent eruption. The data have been divided into two periods: from 1990 to 1995 and from 1996 to 2003 and show that the rate of deflation at Krafla is decaying exponentially. The net micro-gravity change at the centre of the caldera is shown, using the measured Free Air Gradient, to be -85 μGal for the first and -100 μGal for the second period. After consideration of the effects of water extraction by the geothermal power station within the caldera, the net gravity decreases are -73 ± 17 μGal for the first and -65 ± 17 μGal for the second period. These decreases are interpreted in terms of magma drainage. Following a Mogi point source model we calculate the mass decrease to be ~2 x 1010 kg/yr reflecting a drainage rate of ~0.23 m3/s, similar to the ~0.13 m3/s drainage rate previously found at Askja volcano, N-Iceland. Based on the evidence for deeper magma reservoirs and the similarity between the two volcanic systems, we suggest a pressure-link between Askja and Krafla at deeper levels (at the lower crust or the crust-mantle boundary). After the Krafla fires, co-rifting pressure decrease of a deep source at Krafla stimulated the subsequent inflow of magma, eventually affecting conditions along the plate boundary in N-Iceland, as far away as Askja. We anticipate that the pressure of the deeper reservoir at Krafla will reach a critical value and eventually magma will rise from there to the shallow magma chamber, possibly initiating a new rifting episode. We have demonstrated that by examining micro-gravity and geodetic data, our knowledge of active volcanic systems can be significantly improved
Effects of present-day deglaciation in Iceland on mantle melt production rates
Ongoing deglaciation in Iceland not only causes uplift at the surface but also increases magma production at depth due to decompression of the mantle. Here we study glacially induced decompression melting using 3-D models of glacial isostatic adjustment in Iceland since 1890. We find that the mean glacially induced pressure rate of change in the mantle increases melt production rates by 100–135%, or an additional 0.21–0.23 km3 of magma per year beneath Iceland. Approximately 50% of this melt is produced underneath central Iceland. The greatest volumetric increase is found directly beneath Iceland's largest ice cap, Vatnajökull, colocated with the most productive volcanoes. Our models of the effect of deglaciation on mantle melting predict a significantly larger volumetric response than previous models which only considered the effect of deglaciation of Vatnajökull, and only mantle melting directly below Vatnajökull. Although the ongoing deglaciation significantly increases the melt production rate, the increase in melt supply rate at the base of the lithosphere is delayed and depends on the melt ascent velocity through the mantle. Assuming that 25% of the melt reaches the surface, the upper limit on our deglaciation-induced melt estimates for central Iceland would be equivalent to an eruption the size of the 2010 Eyjafjallajökull summit eruption every seventh year
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