Chemical fluxes from time series sampling of the Irrawaddy and Salween Rivers, Myanmar

The Irrawaddy and Salween rivers in Myanmar deliver water fluxes to the ocean equal to ~ 70% of the Ganges–Brahmaputra river system. Together these systems are thought to deliver about half the dissolved load from the tectonically active Himalayan–Tibetan orogen. Previously very little data was available on the dissolved load and isotopic compositions of these major rivers. Here we present time series data of 171 samples collected fortnightly at intervals throughout 2004 to 2007 from the Irrawaddy and Salween at locations near both the river mouths, the up-stream Irrawaddy at Myitkyina, the Chindwin, a major tributary of the Irrawaddy and a set of 28 small tributaries which rise in the flood plain of the Irrawaddy between Yangon and Mandalay. The samples have been analysed for major cation, anion and 87Sr/86Sr ratios. The new data indicates that the Irrawaddy has an annual average Na concentration only a third of the widely quoted single previously published analysis. The Irrawaddy and Salween drain about 0.5% of global continental area and deliver about 3.3% of the global silicate-derived dissolved Ca + Mg fluxes and 2.6% of the global Sr riverine fluxes to the oceans. This compares with Ganges and Brahmaputra which deliver about 3.4% of the global silicate-derived dissolved Ca + Mg fluxes and 3.2% of the global Sr riverine fluxes to the oceans from about 1.1% of global continental area. The discharge-weighted mean 87Sr/86Sr ratio of the Irrawaddy is 0.71024 and the Salween 0.71466. The chemistry of the Salween and the Irrawaddy waters reflects their different bedrock geology. The catchment of the Salween extends across the Shan Plateau in Myanmar through the Eastern syntaxis of the Himalayas and into Tibet. The Irrawaddy flows over the Cretaceous and Tertiary magmatic and metamorphic rocks exposed along the western margin of the Shan Plateau and the Cretaceous to Neogene Indo-Burma ranges. The 87Sr/86Sr compositions of the Salween and Upper Irrawaddy (between 0.7128 and 0.7176) are significantly higher than the downstream Irrawaddy (0.7095 to 0.7108) and the Chindwin (0.7082 to 0.7095). The Irrawaddy and the Chindwin exhibit lower 87Sr/86Sr and Na/Ca ratios during and immediately post-monsoon, interpreted to reflect higher weathering of carbonate at high flow. The Salween exhibits higher 87Sr/86Sr ratios but lower Na/Ca ratios during the monsoon, interpreted to reflect higher inputs from the upper parts of the catchment in the Himalayas.The research was funded by the UK Natural Environmental Research Council grant NE/C513850/1.This is the final published version. It first appeared at: http://www.sciencedirect.com/science/article/pii/S0009254115000510#

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..

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

Impact of target site distribution for Type I restriction enzymes on the evolution of methicillin-resistant Staphylococcus aureus (MRSA) populations.

A limited number of Methicillin-resistant Staphylococcus aureus (MRSA) clones are responsible for MRSA infections worldwide, and those of different lineages carry unique Type I restriction-modification (RM) variants. We have identified the specific DNA sequence targets for the dominant MRSA lineages CC1, CC5, CC8 and ST239. We experimentally demonstrate that this RM system is sufficient to block horizontal gene transfer between clinically important MRSA, confirming the bioinformatic evidence that each lineage is evolving independently. Target sites are distributed randomly in S. aureus genomes, except in a set of large conjugative plasmids encoding resistance genes that show evidence of spreading between two successful MRSA lineages. This analysis of the identification and distribution of target sites explains evolutionary patterns in a pathogenic bacterium. We show that a lack of specific target sites enables plasmids to evade the Type I RM system thereby contributing to the evolution of increasingly resistant community and hospital MRSA

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

An investigation of the structural requirements for ATP hydrolysis and DNA cleavage by the EcoKI Type I DNA restriction and modification enzyme

Type I DNA restriction and modification enzym

Dissolved noble gases and stable isotopes as tracers of preferential fluid flow along faults in the Lower Rhine Embayment, Germany

Groundwater in shallow unconsolidated sedimentary aquifers close to the Bornheim fault in the Lower Rhine Embayment (LRE), Germany, has relatively low δ2H and δ18O values in comparison to regional modern groundwater recharge, and 4He concentrations up to 1.7 × 10−4 cm3 (STP) g–1 ± 2.2 % which is approximately four orders of magnitude higher than expected due to solubility equilibrium with the atmosphere. Groundwater age dating based on estimated in situ production and terrigenic flux of helium provides a groundwater residence time of ∼107 years. Although fluid exchange between the deep basal aquifer system and the upper aquifer layers is generally impeded by confining clay layers and lignite, this study’s geochemical data suggest, for the first time, that deep circulating fluids penetrate shallow aquifers in the locality of fault zones, implying  that sub-vertical fluid flow occurs along faults in the LRE. However, large hydraulic-head gradients observed across many faults suggest that they act as barriers to lateral groundwater flow. Therefore, the geochemical data reported here also substantiate a conduit-barrier model of fault-zone hydrogeology in unconsolidated sedimentary deposits, as well as corroborating the concept that faults in unconsolidated aquifer systems can act as loci for hydraulic connectivity between deep and shallow aquifers. The implications of fluid flow along faults in sedimentary basins worldwide are far reaching and of particular concern for carbon capture and storage (CCS) programmes, impacts of deep shale gas recovery for shallow groundwater aquifers, and nuclear waste storage sites where fault zones could act as potential leakage pathways for hazardous fluids