Hydrogeochemistry of surface and spring waters in the surroundings of the CO2 injection site at Hontomín–Huermeces (Burgos, Spain)

In this paper the very first geochemical and isotopic data related to surface and spring waters and dissolved gases in the area of Hontomín–Huermeces (Burgos, Spain) are presented and discussed. Hontomín–Huermeces has been selected as a pilot site for the injection of pure (>99%) CO2. Injection and monitoring wells are planned to be drilled close to 6 oil wells completed in the 1980s for which detailed stratigraphical logs are available, indicating the presence of a confined saline aquifer at the depth of about 1500 m into which less than 100,000 tons of iquid CO2 will be injected, possibly starting in 2013. The chemical and features of the spring waters suggest that they are related to a shallow hydrogeological system as the concentration of the Total Dissolved Solids approaches 800 mg/L with a Ca2+(Mg2+)-HCO3− composition, similar to that of the surface waters. This is also supported by the oxygen and hydrogen isotopic ratios that have values lying between those of the Global and the Mediterranean Meteoric Water Lines. Some spring waters close to the oil wells are haracterized by relatively high concentrations of NO3− (up to 123 mg/L), unequivocally suggesting an anthropogenic source that adds to the main water–rock interaction processes. The latter can be referred to Ca-Mg-carbonate and, at a minor extent, Al-silicate dissolution, being the outcropping sedimentary rocks characterized by Palaeozoic to Quaternary rocks. Anomalous concentrations of Cl−, SO42−, As, B and Ba were measured in two springs discharging a few hundred meters from the oil wells and in the Rio Ubierna. These contents are significantly higher than those of the whole set of the studied waters and are possibly indicative of mixing processes, although at very low extent, between deep and shallow aquifers. No evidence of deep-seated gases interacting with the Hontomín–Huermeces waters was recognized in the chemistry of the disolved gases. This is likely due to the fact that they are mainly characterized by an atmospheric source as highlighted by the high contents of N2, O2 and Ar and by N2/Ar ratios that approach that of ASW (Air Saturated Water) and possibly masking any contribution related to a deep source. Nevertheless, significant concentrations (up to 63% by vol.) of isotopically negative CO2 (<−17.7‰ V-PDB) were found in some water samples, likely related to a biogenic source. The geochemical and isotopic data of this work are of particular importance when a monitoring program will be established to verify whether CO2 leakages, induced by the injection of this greenhouse gas, may be affecting the quality of the waters in the shallow hydrological circuits at Hontomín–Huermeces. In this respect, carbonate chemistry, the isotopic carbon of dissolved CO2 and TDIC (Total Dissolved Inorganic Carbon) and selected trace elements can be considered as useful parameters to trace the migration of the injected CO2 into near-surface environments.

(Table 1) Summary statistics of taxa in samples of ODP Hole 181-1123B

Planktonic foraminifera are used to identify late Pliocene-Quaternary near surface water masses on the northeastern flank of Chatham Rise by comparison with faunas in core-tops east of New Zealand. In an overview study, distance measures, ordinations, and discriminant analysis are applied to 32 faunas from Site 1123B to identify similar faunas among 35 core-tops between 35 and 61°S east of New Zealand. Many Site 1123B faunas in the 2.72 myr interval sampled compare with those in core-tops on the northern side of Chatham Rise from a similar latitude, and are identified as transitional zone assemblages now associated with the subtropical gyre. This result is consistent with studies of late Quaternary planktonic foraminifera from this region and suggests that, typically, the Subtropical Front was locked to Chatham Rise through glacial and interglacial periods, at least back to the late Pliocene. However, a fauna at ca. 1.17 Ma compares with subpolar assemblages in core-tops between 44 and 48°S and identifies cooler surface water. Expectedly, closer sampling may reveal additional periods when southern water moved over the northeastern flank of Chatham Rise. Although the dominance of Globorotalia inflata, a species typical of the southern margin of subtropical gyres, is a principal feature of Site 1123B faunas, in a minority it is replaced as the most abundant species by dextral populations of Neogloboquadrina pachyderma, particularly about the time of the middle Pleistocene transition. Close analogues of these variant transitional assemblages are not present in core-tops about Chatham Rise but sediment trap and coretop data from other regions suggest that they identify high fertility in the mixed layer associated with upwelling or mixing of water masses. The proportion of sinistrally coiled Neogloboquadrina pachyderma rises to ca. 0.6 between ca. 2.45 and 2.57 Ma, soon after the intensification of Northern Hemisphere glaciation. Although the coiling data indicate subantarctic near surface water, the species remains rare. As the faunas retain their transitional zone character, only minor entrainment of subantarctic water may have occurred.

High-resolution dynamical downscaling products for the North Slope of Alaska and surrounding areas, links to model result files

Climatic changes are most pronounced in northern high latitude regions. Yet, there is a paucity of observational data, both spatially and temporally, such that regional-scale dynamics are not fully captured, limiting our ability to make reliable projections. In this study, a group of dynamical downscaling products were created for the period 1950 to 2100 to better understand climate change and its impacts on hydrology, permafrost, and ecosystems at a resolution suitable for northern Alaska. An ERA-interim reanalysis dataset and the Community Earth System Model (CESM) served as the forcing mechanisms in this dynamical downscaling framework, and the Weather Research & Forecast (WRF) model, embedded with an optimization for the Arctic (Polar WRF), served as the Regional Climate Model (RCM). This downscaled output consists of multiple climatic variables (precipitation, temperature, wind speed, dew point temperature, and surface air pressure) for a 10 km grid spacing at three-hour intervals. The modeling products were evaluated and calibrated using a bias-correction approach. The ERA-interim forced WRF (ERA-WRF) produced reasonable climatic variables as a result, yielding a more closely correlated temperature field than precipitation field when long-term monthly climatology was compared with its forcing and observational data. A linear scaling method then further corrected the bias, based on ERA-interim monthly climatology, and bias-corrected ERA-WRF fields were applied as a reference for calibration of both the historical and the projected CESM forced WRF (CESM-WRF) products. Biases, such as, a cold temperature bias during summer and a warm temperature bias during winter as well as a wet bias for annual precipitation that CESM holds over northern Alaska persisted in CESM-WRF runs. The linear scaling of CESM-WRF eventually produced high-resolution downscaling products for the Alaskan North Slope for hydrological and ecological research, together with the calibrated ERA-WRF run, and its capability extends far beyond that. Other climatic research has been proposed, including exploration of historical and projected climatic extreme events and their possible connections to low-frequency sea-atmospheric oscillations, as well as near-surface permafrost degradation and ice regime shifts of lakes. These dynamically downscaled, bias corrected climatic datasets provide improved spatial and temporal resolution data necessary for ongoing modeling efforts in northern Alaska focused on reconstructing and projecting hydrologic changes, ecosystem processes and responses, and permafrost thermal regimes. The dynamical downscaling methods presented in this study can also be used to create more suitable model input datasets for other sub-regions of the Arctic.

Mixing Regimes in the Amundsen Basin of the Arctic Ocean

Thesis (Ph.D.)--University of Washington, 2016-06

Microstructural analysis of surface and interface zones in concrete

Several of OPC paste and concrete specimens, with different mix proportions, were cast against CPF and impermeable formwork (IF) and the profiles of pore structure, microhardness and scratch hardness of the cover zone were established. The chloride ingress and the depth of carbonation of the surface zone of concrete cast against CPF and IF were investigated. The main mechanisms controlling the ECR processes and the factors affecting such treatment were critically reviewed. Subsequently, as a means of restoring passivation of steel embedded in carbonated concrete, such HCP specimens were subjected to ECR. The influence of ECR on the chemistry of the pore solution and the microstructure of the surface and the steel/cement past interface zones were also studied. The main findings of this investigation were as follows: (a) The thickness of the microstructure gradient of cover concrete is significantly decreased with increasing period of water curing but is relatively unaffected by curing temperature, w/e ratio and the use of cement replacement materials. (b) The scratch hardness technique was shown to be potentially useful for characterising the microstructure and microhardness gradients of the surface zone. (c) A relationship between the microstructure gradient and mass transport properties of the surface zone was established. (d) The use of CPF resulted in a significant reduction in porosity of both the cement paste matrix and the aggregate/cement paste transition zone, and a marked improvement in the resistance of the surface zone to carbonation and the ingress of chloride ions. (e) The ECR treatment resulted in a marked densification of the pore structure and in changes to the pore solution chemistry and the cement phases of near-surface and steel/cement paste transition zones. This effect was more pronounced with current density, period of treatment and particularly with the use of sodium phosphate as an electrolyte.

A study of the formation of amorphous calcium phosphate and hydroxyapatite on melt quenched Bioglass(A (R)) using surface sensitive shallow angle X-ray diffraction

Melt quenched silicate glasses containing calcium, phosphorous and alkali metals have the ability to promote bone regeneration and to fuse to living bone. These glasses, including 45S5 Bioglass(A (R)) [(CaO)(26.9)(Na2O)(24.4)(SiO2)(46.1)(P2O5)(2.6)], are routinely used as clinical implants. Consequently there have been numerous studies on the structure of these glasses using conventional diffraction techniques. These studies have provided important information on the atomic structure of Bioglass(A (R)) but are of course intrinsically limited in the sense that they probe the bulk material and cannot be as sensitive to thin layers of near-surface dissolution/growth. The present study therefore uses surface sensitive shallow angle X-ray diffraction to study the formation of amorphous calcium phosphate and hydroxyapatite on Bioglass(A (R)) samples, pre-reacted in simulated body fluid (SBF). Unreacted Bioglass(A (R)) is dominated by a broad amorphous feature around 2.2 A...(-1) which is characteristic of sodium calcium silicate glass. After reacting Bioglass(A (R)) in SBF a second broad amorphous feature evolves similar to 1.6 A...(-1) which is attributed to amorphous calcium phosphate. This feature is evident for samples after only 4 h reacting in SBF and by 8 h the amorphous feature becomes comparable in magnitude to the background signal of the bulk Bioglass(A (R)). Bragg peaks characteristic of hydroxyapatite form after 1-3 days of reacting in SBF.

Multi-proxy record of planktonic and benthic foraminiferal d18O, and Mg/Ca-derived surface and lower thermocline temperatures in sediment core SO18471 (GIK18471), Timor Sea

Paleostudies of the Indonesian Throughflow (ITF) are largely based on temperature and salinity reconstructions of its near surface component, whereas the variability of its lower thermocline flow has rarely been investigated. We present a multi-proxy record of planktonic and benthic foraminiferal d18O, Mg/Ca-derived surface and lower thermocline temperatures, X-ray fluorescence (XRF)-derived runoff and sediment winnowing for the past 130 ka in marine sediment core SO18471. Core SO18471, retrieved from a water depth of 485 m at the southern edge of the Timor Strait close to the Sahul Shelf, sits in a strategic position to reconstruct variations in both the ITF surface and lower thermocline flow as well as to investigate hydrological changes related to monsoon variability and shelf dynamics over time. Sediment winnowing demonstrates that the ITF thermocline flow intensified during MIS 5d-a and MIS 1. In contrast during MIS 5e, winnowing was reduced and terrigenous input increased suggesting intensification of the local wet monsoon and a weaker ITF. Lower thermocline warming during globally cold periods (MIS 4 - MIS 2) appears to be related to a weaker and contracted thermocline ITF and advection of warm and salty Indian Ocean waters.

Time-series of snow spectral albedo and superficial snow specific surface area at Dome C in Antarctica, 2012-2015

Spectral albedo has been measured at Dome C since December 2012 in the visible and near infrared (400 - 1050 nm) at sub-hourly resolution using a home-made spectral radiometer. Superficial specific surface area (SSA) has been estimated by fitting the observed albedo spectra to the analytical Asymptotic Approximation Radiative Transfer theory (AART). The dataset includes fully-calibrated albedo and SSA that pass several quality checks as described in the companion article. Only data for solar zenith angles less than 75° have been included, which theoretically spans the period October-March. In addition, to correct for residual errors still affecting data after the calibration, especially at the solar zenith angles higher than 60°, we produced a higher quality albedo time-series as follows: In the SSA estimation process described in the companion paper, a scaling coefficient A between the observed albedo and the theoretical model predictions was introduced to cope with these errors. This coefficient thus provides a first order estimate of the residual error. By dividing the albedo by this coefficient, we produced the "scaled fully-calibrated albedo". We strongly recommend to use the latter for most applications because it generally remains in the physical range 0-1. The former albedo is provided for reference to the companion paper and because it does not depend on the SSA estimation process and its underlying assumptions.

Characteristics of samples obtained during Pokhodsk 2012-2013 campaigns in the joint Russian-German POLYGON Project

Polygonal tundra, thermokarst basins and pingos are common and characteristic periglacial features of arctic lowlands underlain by permafrost in Northeast Siberia. Modern polygonal mires are in the focus of biogeochemical, biological, pedological, and cryolithological research with special attention to their carbon stocks and greenhouse-gas fluxes, their biodiversity and their dynamics and functioning under past, present and future climate scenarios. Within the frame of the joint German-Russian DFG-RFBR project Polygons in tundra wetlands: state and dynamics under climate variability in Polar Regions (POLYGON) field studies of recent and of late Quaternary environmental dynamics were carried out in the Indigirka lowland and in the Kolyma River Delta in summer 2012 and summer 2013. Using a multidisciplinary approach, several types of polygons and thermokarst lakes were studied in different landscapes units in the Kolyma Delta in 2012 around the small fishing settlement Pokhodsk. The floral and faunal associations of polygonal tundra were described during the fieldwork. Ecological, hydrological, meteorological, limnological, pedological and cryological features were studied in order to evaluate modern and past environmental conditions and their essential controlling parameters. The ecological monitoring and collection program of polygonal ponds were undertaken as in 2011 in the Indigirka lowland by a former POLYGON expedition (Schirrmeister et al. [eds.] 2012). Exposures, pits and drill cores in the Kolyma Delta were studied to understand the cryolithological structures of frozen ground and to collect samples for detailed paleoenvironmental research of the late Quaternary past. Dendrochronological and ecological studies were carried out in the tree line zone south of the Kolyma Delta. Based on previous work in the Indigirka lowland in 2011 (Schirrmeister et al. [eds.] 2012), the environmental monitoring around the Kytalyk research station was continued until the end of August 2012. In addition, a classical exposure of the late Pleistocene permafrost at the Achchaygy Allaikha River near Chokurdakh was studied. The ecological studies near Pokhodsk were continued in 2013 (chapter 13). Other fieldwork took place at the Pokhodsk-Yedoma-Island in the northwestern part of the Kolyma Delta.

Stable isotope record of planktonic foraminifera of sediment core TR163-19

Stable isotope data from eastern equatorial Pacific (EEP) core TR163-19 (2°15'N, 90°57'W, 2348 m) are presented for the surface-dwelling foraminifers Globigerinoides ruber and G. sacculifer and thermocline-dwelling Globorotalia menardii and Neogloboquadrina dutertrei. Using species-specific normalization factors derived from experimental and plankton tow data, we reconstruct a 360 kyr record of water column hydrography across the past three glacial cycles. We demonstrate that G. ruber maintains a mixed layer habitat throughout the entire record, while G. sacculifer records a mixture of thermocline and mixed layer conditions and G. menardii and N. dutertrei record thermocline properties. We conclude that G. sacculifer is not appropriate for paleoceanographic applications in regions with steep vertical hydrographic gradients. Results suggest that this region of the EEP had a thicker mixed layer and deeper d13CDIC boundary between the surface and equatorial undercurrent during the last two glacial periods. A shift in N. dutertrei and G. sacculifer geochemistry prior to ~185 kyr suggests water column structure and chemocline gradients changed, possibly due to a shift in the position of the undercurrent relative to this site. The timing and magnitude of glacial-interglacial d13C variations between species indicates that near-surface carbon chemistry is controlled by changes in productivity, atmospheric circulation, and advected intermediate water sources north of the Antarctic polar front. These results demonstrate that when properly calibrated for species differences, multispecies geochemical data sets can be invaluable for reconstructing water column structure and properties in the past.

EUSAAR size distribution analysis database

Two years of harmonized aerosol number size distribution data from 24 European field monitoring sites have been analysed. The results give a comprehensive overview of the European near surface aerosol particle number concentrations and number size distributions between 30 and 500 nm of dry particle diameter. Spatial and temporal distribution of aerosols in the particle sizes most important for climate applications are presented. We also analyse the annual, weekly and diurnal cycles of the aerosol number concentrations, provide log-normal fitting parameters for median number size distributions, and give guidance notes for data users. Emphasis is placed on the usability of results within the aerosol modelling community. We also show that the aerosol number concentrations of Aitken and accumulation mode particles (with 100 nm dry diameter as a cut-off between modes) are related, although there is significant variation in the ratios of the modal number concentrations. Different aerosol and station types are distinguished from this data and this methodology has potential for further categorization of stations aerosol number size distribution types. The European submicron aerosol was divided into characteristic types: Central European aerosol, characterized by single mode median size distributions, unimodal number concentration histograms and low variability in CCN-sized aerosol number concentrations; Nordic aerosol with low number concentrations, although showing pronounced seasonal variation of especially Aitken mode particles; Mountain sites (altitude over 1000 m a.s.l.) with a strong seasonal cycle in aerosol number concentrations, high variability, and very low median number concentrations. Southern and Western European regions had fewer stations, which decreases the regional coverage of these results. Aerosol number concentrations over the Britain and Ireland had very high variance and there are indications of mixed air masses from several source regions; the Mediterranean aerosol exhibit high seasonality, and a strong accumulation mode in the summer. The greatest concentrations were observed at the Ispra station in Northern Italy with high accumulation mode number concentrations in the winter. The aerosol number concentrations at the Arctic station Zeppelin in Ny-Ålesund in Svalbard have also a strong seasonal cycle, with greater concentrations of accumulation mode particles in winter, and dominating summer Aitken mode indicating more recently formed particles. Observed particles did not show any statistically significant regional work-week or weekday related variation in number concentrations studied. Analysis products are made for open-access to the research community, available in a freely accessible internet site. The results give to the modelling community a reliable, easy-to-use and freely available comparison dataset of aerosol size distributions.

Sample locations, stratigraphic information and listing of carbon and oxygen isotope data of the measured planktonic foraminifera of surface sediments in the western South Atlantic Ocean (Table 1)

We explored the potential to use the stable isotopic compositions of planktonic foraminifera as a proxy for the position of the Brazil-Malvinas Confluence (BMC) in the Argentine Basin. For this purpose, we measured the oxygen and carbon isotopic compositions of Globigerinoides ruber (pink and white varieties measured separately), Globigerinoides trilobus, Globigerina bulloides, Globorotalia inflata and Globorotalia truncatulinoides (left- and right-coiling forms measured separately) from a latitudinal transect of 56 surface sediment samples from the continental slope off Brazil, Uruguay and Argentina between 20 and 48°S. Lowest oxygen isotopes values were found in G. ruber (pink), followed by G. ruber (white) and G. trilobus reflecting the highly stratified near surface water conditions north of the BMC. Globigerina bulloides was present mainly south of the BMC and records subsurface conditions supporting earlier plankton tow studies. Globorotalia inflata and G. truncatulinoides (left and right) were both available over the whole transect and calcify in the depth level with the steepest temperature change across the BMC. Accordingly, the delta18O of these species depict a sharp gradient of 2? at the confluence with remarkably stable values north and south of the BMC. Our data show that the oxygen isotopic composition of G. inflata and G. truncatulinoides (left and right) are the most reliable indicators for the present position of the BMC and can therefore be used to define the past migration of the front if appropriate cores are available.

Stone temperature and moisture variability under temperate environmental conditions: implications for sandstone weathering

Temperature and moisture conditions are key drivers of stone weathering processes in both natural and built environments. Given their importance in the breakdown of stone, a detailed understanding of their temporal and spatial variability is central to understanding present-day weathering behaviour and for predicting how climate change may influence the nature and rates of future stone decay.
Subsurface temperature and moisture data are reported from quarry fresh Peakmoor Sandstone samples exposed during summer (June–July) and late autumn / early winter (October–December) in a mid-latitude, temperate maritime environment. These data demonstrate that the subsurface thermal response of sandstone comprises numerous short-term (minutes), low magnitude fluctuations superimposed upon larger-scale diurnal heating and cooling cycles with distinct aspect-related differences. The short-term fluctuations create conditions in the outer 5–10 mm of stone that are much more ‘energetic’ in comparison to the more subdued thermal cycling that occurs deeper within the sandstone samples.
Data show that moisture dynamics are equally complex with a near-surface region (5–10 mm) in which frequent moisture cycling takes place and this, combined with the thermal dynamism exhibited by the same region may have significant implications for the nature and rate of weathering activity. Data indicate that moisture input from rainfall, particularly when it is wind-driven, can travel deep into the stone where it can prolong the time of wetness. This most often occurs during wetter winter months when moisture input is high and evaporative loss is low but can happen at any time during the year when the hydraulic connection between near-surface and deeper regions of the stone is disrupted with subsequent loss of moisture from depth slowing as it becomes reliant on vapour diffusion alone.
These data illustrate the complexity of temperature and moisture conditions in sandstone exposed to the ‘moderate’ conditions of a temperate maritime environment. They highlight differences in thermal and moisture cycling between near-surface (5–10 mm) and deeper regions within the stone and contribute towards a better understanding of the development of structural and mineralogical heterogeneity between the stone surface and substrate.

Pulling Back the Veil: The Characterization and Habitability of Enshrouded Worlds

Thesis (Ph.D.)--University of Washington, 2016-08

DopSCAT: A mission concept for simultaneous measurements of marine winds and surface currents

A radar scatterometer operates by transmitting a pulse of microwave energy toward the ocean's surface and measuring the normalized (per-unit-surface) radar backscatter coefficient (σ°). The primary application of scatterometry is the measurement of near-surface ocean winds. By combining σ° measurements from different azimuth angles, the 10 m vector wind can be determined through a Geophysical Model Function (GMF), which relates wind and backscatter. This paper proposes a mission concept for the measurement of both oceanic winds and surface currents, which makes full use of earlier C-band radar remote sensing experience. For the determination of ocean currents, in particular, the novel idea of using two chirps of opposite slope is introduced. The fundamental processing steps required to retrieve surface currents are given together with their associated accuracies. A detailed description of the mission proposal and comparisons between real and retrieved surface currents are presented. The proposed ocean Doppler scatterometer can be used to generate global surface ocean current maps with accuracies better than 0.2 m/s at a spatial resolution better than 25 km (i.e., 12.5 km spatial sampling) on a daily basis. These maps will allow gaining some insights on the upper ocean mesoscale dynamics. The work lies at a frontier, given that the present inability to measure ocean currents from space in a consistent and synoptic manner represents one of the greatest weaknesses in ocean remote sensing.