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Kinetics of CO<inf>2</inf>-fluid-rock reactions in a basalt aquifer, Soda Springs, Idaho
The dissolution of silicate minerals by CO2–rich fluids and the subsequent precipitation of CO2 as carbonate minerals represent a means of permanently storing anthropogenic CO2 waste products in a solid and secure form. Modelling the progression of these reactions is hindered by our poor understanding of the rates of mineral dissolution-precipitation reactions and mineral surface properties in natural systems. This study evaluates the chemical evolution of groundwater flowing through a basalt aquifer, which forms part of the leaking CO2-charged system of the Blackfoot Volcanic Field in south-eastern Idaho, USA. Reaction progress is modelled using changes in groundwater chemistry by inverse mass balance techniques. The CO2-promoted fluid-mineral reactions include the dissolution of primary plagioclase, orthoclase, pyroxene and gypsum which is balanced by the precipitation of secondary albite, calcite, zeolite, kaolinite and silica. Mineral mole transfers and groundwater flow rates estimated from hydraulic head data are used to determine the kinetics of plagioclase and orthoclase feldspar dissolution. Plagioclase surface area measurements were determined using the evolution of the U-series isotope ratios in the groundwater and are compared to published surface area measurements. Calculated rates of dissolution for plagioclase range from 2.4 x 10-12 to 4.6 x 10-16 mol/m2/s and orthoclase from 2.0 x 10-13 to 6.8 x 10-16 mol/m2/s respectively. These feldspar reaction rates, correlate with the degree of mineral-fluid disequilibrium and are similar to the dissolution rates for these mineral measured in other natural CO2-charged groundwater systems.Carbon research at Cambridge is supported by Natural Environment Research Council grant NE/F004699/1, part of the UK CRIUS (Carbon Research Into Underground Storage) consortium and DECC through the ‘£20 million’ competition. Niko Kampman acknowledges financial support from Shell Global Solutions International.This is the final version of the article. It first appeared from Elsevier via http://dx.doi.org/10.1016/j.apgeochem.2015.06.01
Archaeological Geophysical Prospection in Peatland Environments: case studies and suggestions for future practice
Peatland environments, in contrast to ‘dry-land’ sites, preserve organic material, including anthropogenic objects, because they are anaerobic, and are therefore of great importance to archaeology. Peat also preserves macro- and micro- paleoenvironmental evidence and is the primary resource for understanding past climates and ecology. Archaeological sites often lie within or at the base of wet, deep, homogenous peat rendering them invisible to surface observers. As a result, they most often c..
Psychological distress and lower health-related quality of life are associated with need for dietary support among colorectal cancer survivors with overweight or obesity
Objective: Two-third of colorectal cancer (CRC) survivors are overweight or obese. Psychological distress and low health-related quality of life (HRQoL) may be barriers to improving diet. We aimed to assess associations between psychological distress and HRQoL and the need for dietary support in CRC survivors with overweight or obesity. Methods: All alive individuals diagnosed with CRC between 2000 and 2009, as registered by the Dutch population-based Eindhoven Cancer Registry, were eligible for participation and received a questionnaire. Multivariable logistic regression analyses were conducted to assess associations between HRQoL (EORTC QLQ-C30), symptoms of anxiety and depression (HADS), and self-reported need for dietary support (single-item). Results: A total of 1458 completed the questionnaire (response rate 82%), and 756 (43%) had a BMI of 25.0 or higher and complete data on “need for dietary support” and were included for analyses. BMI ranged between 25.0 and 60.6 (mean, 28.9; SD, 3.6). The majority (71.7%) was overweight (BMI ≥ 25), and 28.3% obese (BMI ≥ 30). Twenty-one percent reported a need for dietary support which was associated with more psychological distress and lower HRQoL. Those who experienced symptoms of anxiety or depression were more likely to report a need for dietary support (27.6% and 28.7%) than those who did not experience symptoms of anxiety (12.3%; OR 2.02; 95% CI 1.22–3.35) or depression (13.5%; OR 1.96; 95% CI 1.19–3.22). Conclusions: Results suggest that psychological distress and lower HRQoL should be taken into account while promoting a healthy diet in overweight or obese CRC survivors since these factors may hinder adherence to a healthy diet.</p
Coupled CO2-leakage and in situ fluid-mineral reactions in a natural CO2 reservoir, Green River, Utah
Spectroscopic studies and atomistic simulations of (hydr)oxide surfaces, which show that some aqueous cations bind to two or four surface oxygen atoms, have increased
interest in multi-dentate surface complexation models (SCMs) [1-3]. However, it remains unclear how the (fitted) values of
intrinsic equilibrium constants K int/m (referenced to infinite dilution) for δ-dentate M surface-binding reactions (δ >1) depend on the choice of concentration scale. In existing SCM codes, a surface complex may be treated in scales of either: molarity/molality ([]); site coverage fraction (Θ); surface mole fraction (x); molecular surface density (Γ, in mol•m-2); or
relative density Γ/Γo (o, where Γo = 2 •10-5 mol•m-2 is the reference adsorbed density [4]). Our aim was to investigate, for ‘denticities’ 1≤ δ ≤4, how to convert the K int,δ values fitted for a given titration data set (the same solid concentration cS, specific surface area As, and monolayer site density ΓC) between different concentration scales. For single-site monodentate surface binding reactions, K int/m expressed in all concentration scales ([], Θ, x, Γ, o) reduce to the same value K M int,1. For the binding with δ≤2, conversion factors from xKM int,δ to ΘKM int,δ are about δ. From []KM int,δ to any
other scale, they involve (csAsΓx)δ-1 which is ca. 10-5 for δ = 2 or 10-15 for δ = 4 at typical cS = 1 g•dm-3, As = 10 m2g-1, and ΓC
= 10-6 mol•m-2. Conversions of K/int from [], Θ and x scales into the Γ scale involve (ΓC)1-δ, which has a value ranging from 10/5
to 10/18 at 10-6 < ΓC < 10-5 mol•m-2. The K/int conversions from [], Θ and x to the o scale include (Γo/ΓC)δ-1 which vanishes if ΓC = Γo (then oKM int,δ = xKM int,δ).
Our findings show that the use of published KM int,δ (δ ≥ 2) in SCMs may lead to erroneous results, if concentration scales
are not precisely defined both in the original fitting and in the subsequent application. At trace ion concentrations, using formally monodentate surface species would be safe especially on ‘strong’ sites, for which the density is typically adjusted to reproduce multi-site isotherms. Our results from comparative fitting of KM/int,δ with SCM codes using different scales show the magnitudes of ‘denticity effects’; we discuss ways to correct for these effects in re-using, comparing or correlating
values of KM/int,δ. In a further thermodynamic treatment, e.g. deriving the entropy effect of the adsorption reaction from KM/int,δ fitted for different temperatures, the constants must first be made dimensionless and independent of δ and ΓC by converting them into the (o) scale.http://dx.doi.org/10.1016/j.gca.2010.04.036University of Tennessee; Oak Ridge National Laborator
The Green River Natural Analogue as a field laboratory to study the long-term fate of CO2 in the subsurface
Understanding the long-term response of CO2 injected into porous reservoirs is one of the most important aspects to demonstrate safe and permanent storage. In order to provide quantitative constraints on the long-term impacts of CO2-charged fluids on the integrity of reservoir-caprock systems we recovered some 300m of core from a scientific drill hole through a natural CO2 reservoir, near Green River, Utah. We obtained geomechanical, mineralogical, geochemical, petrophysical and mineralogical laboratory data along the entire length of the core and from non CO2-charged control samples. Furthermore, we performed more detailed studies through portions of low permeability layers in direct contact with CO2-charged layers. This was done to constrain the nature and penetration depths of CO2-promoted fluid-mineral reaction fronts. The major reactions identified include the dissolution of diagenetic dolomite cements and hematite grain coatings, and the precipitation of ankerite and pyrite and have been used as input for geochemical 1D reactive transport modelling, to constrain the magnitude and velocity of the mineral-fluid reaction front.
In addition, we compared geomechanical data from the CO2-exposed core and related unreacted control samples to assess the mechanical stability of reservoir and seal rocks in a CO2 storage complex following mineral dissolution and precipitation for thousands of years. The obtained mechanical parameters were coupled to mineralogy and porosity. Key aim of this work was to better quantify the effect of long-term chemical CO2/brine/rock interactions on the mechanical strength and elastic properties of the studied formations
Observational evidence confirms modelling of the long-term integrity of CO2-reservoir caprocks
Anthropogenic CO2 storage, where CO2 is injected into saline geological resevoirs, relies on an impermeable caprock to seal in the CO2, but caprock reaction rates to CO2 acid brines are unclear
Investigation of attentional bias in obsessive compulsive disorder with and without depression in visual search
Copyright: © 2013 Morein-Zamir et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are creditedWhether Obsessive Compulsive Disorder (OCD) is associated with an increased attentional bias to emotive stimuli remains controversial. Additionally, it is unclear whether comorbid depression modulates abnormal emotional processing in OCD. This study examined attentional bias to OC-relevant scenes using a visual search task. Controls, non-depressed and depressed OCD patients searched for their personally selected positive images amongst their negative distractors, and vice versa. Whilst the OCD groups were slower than healthy individuals in rating the images, there were no group differences in the magnitude of negative bias to concern-related scenes. A second experiment employing a common set of images replicated the results on an additional sample of OCD patients. Although there was a larger bias to negative OC-related images without pre-exposure overall, no group differences in attentional bias were observed. However, OCD patients subsequently rated the images more slowly and more negatively, again suggesting post-attentional processing abnormalities. The results argue against a robust attentional bias in OCD patients, regardless of their depression status and speak to generalized difficulties disengaging from negative valence stimuli. Rather, post-attentional processing abnormalities may account for differences in emotional processing in OCD.Peer reviewedFinal Published versio
Circulating tryptophan metabolites and risk of colon cancer: Results from case-control and prospective cohort studies
Summation of reinforcement rates when conditioned stimuli are presented in compound
Three experiments used delay conditioning of magazine approach in rats to examine the summation of responding when two conditioned stimuli (CSs) are presented together as a compound. The duration of each CS varied randomly from trial-to-trial around a mean that differed between the CSs. This meant that the rats’ response rate to each CS was systematically related to the reinforcement rate of that CS, but remained steady as time elapsed during the CS (Harris & Carpenter, in press; Harris, Gharaei, & Pincham, in press). When the rats were presented with a compound of two CSs that had been conditioned separately, they responded more during the compound than during either of the CSs individually. More significantly, however, in all three experiments, the rats responded to the compound at the same rate as they responded to a third CS that had been reinforced at a rate equal to the sum of the reinforcement rates of the two CSs in compound. We discuss the implications of this finding for associative models (e.g., Rescorla & Wagner, 1972) and rate-based models (Gallistel & Gibbon, 2000) of conditioning.Grant DP1092695 from the Australian Research Counci
New insights on the complex dynamics of two-phase flow in porous media under intermediate-wet conditions
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