Detection of Mixing Dynamics During Pumping of a Flooded Coal Mine

In complex hydrogeological environments the effective management of groundwater quality problems by pump-and-treat operations can be most confidently achieved if the mixing dynamics induced within the aquifer by pumping are well understood. The utility of isotopic environmental tracers (C-, H-, O-, S-stable isotopic analyses and age indicators—14C, 3H) for this purpose is illustrated by the analysis of a pumping test in an abstraction borehole drilled into flooded, abandoned coal mineworkings at Deerplay (Lancashire, UK). Interpretation of the isotope data was undertaken conjunctively with that of major ion hydrochemistry, and interpreted in the context of the particular hydraulic setting of flooded mineworkings to identify the sources and mixing of water qualities in the groundwater system. Initial pumping showed breakdown of initial water quality stratification in the borehole, and gave evidence for distinctive isotopic signatures (d34S(SO4) ~= -1.6‰, d18O(SO4) ~= +15‰) associated with primary oxidation of pyrite in the zone of water table fluctuation—the first time this phenomenon has been successfully characterized by these isotopes in a flooded mine system. The overall aim of the test pumping—to replace an uncontrolled outflow from a mine entrance in an inconvenient location with a pumped discharge on a site where treatment could be provided—was swiftly achieved. Environmental tracing data illustrated the benefits of pumping as little as possible to attain this aim, as higher rates of pumping induced in-mixing of poorer quality waters from more distant old workings, and/or renewed pyrite oxidation in the shallow subsurface.

Lichen-induced biomodification of calcareous surfaces: Bioprotection versus biodeterioration

Studies demonstrate the active and passive capability of lichens to inhibit or retard the weathering of calcareous surfaces. Lichen coverage may actively protect a surface through shielding by the thallus and the binding and waterproofing of the rock surface and subsurface by fungal hyphae. Passive protection of rock surfaces may be induced by the formation of an insoluble encrustation, such as calcium oxalate, at the lichen-rock interface. Recent research suggests that the decay of hyphae, induced by changes in microenvironmental conditions, necrosis, parasitism or the natural physiological traits of particular lichen species, may expose a chemically and physically weakened substrate to dissolution triggering relatively rapid weathering-related surface lowering. Consequently, certain epilithic crustose and endolithic lichens may induce a period of surface stability throughout the course of their lifespan, followed by a phase of instability and rapid episodic microtopographical evolution after death and decay. A series of conceptual models is proposed to illustrate this idea over short (single lichen lifespan) and long (multiple lichen lifespans) timescales. The models suggest that the microscale biogeomorphological system of lichen-rock interaction is underpinned by nonlinear dynamical system theory as it exhibits dynamical instability and is consequently difficult to predict over a long timescale. Dominance by biodeterioration or bioprotection may be altered by changes in lichen species or in environmental conditions over time.

Experimental studies of near-surface temperature cycling and surface wetting of stone and its implications for salt weathering

It has long been accepted that thermal and moisture regimes within stonework exert a major influence upon patterns of salt movement and, subsequently, the type and severity of salt-induced decay. For example, it is suggested that slow drying is more likely to bring dissolved salts to the surface, whereas rapid drying could result in the retention of some salt at or near the frequent wetting depth. In reality however, patterns of heating, cooling and surface wetting regimes that drive them – are complex and inconsistent responses to a wide range of environmental controls. As a first step to understanding the complexity of these relationships, this paper reports a series of experiments within a climatic cabinet designed to replicate the effects of short-term temperature fluctuations on the surface and sub-surface temperature regimes of a porous Jurassic limestone, and how they are influenced by surface wetting, ambient temperature and surface airflow. Preliminary results confirm the significance of very steep temperature/stress gradients within the outer centimetre or less of exposed stone under short-duration cycles of heating and cooling. This is important because this is the zone in which many stone decay processes, particularly salt weathering, operate, these processes invariably respond to temperature and moisture fluctuations, and short-term interruptions to insolation could, for example,
trigger these fluctuations on numerous occasions over a day. The data also indicate that there are complex patterns of temperature reversal with depth that are influenced in their intensity and location by surface wetting and moisture penetration, airflow across the surface and ambient air temperature. The presence of multiple temperature reversals and their variation over the course of heating and cooling phases belies previous assumtions of smooth, exponential increases and decreases in subsurface temperatures in response, for example to diurnal patterns of heating and cooling

Characterizing Pb mobilization from upland soils to streams using (206)Pb/(207)Pb isotopic ratios

Anthropogenically deposited lead (Pb) binds efficiently to soil organic matter, which can be mobilized through hydrologically mediated mechanisms, with implications for ecological and potable quality of receiving waters. Lead isotopic ((206)Pb/(207)Pb) ratios change down peat profiles as a consequence of long-term temporal variation in depositional sources, each with distinctive isotopic signatures. This study characterizes differential Pb transport mechanisms from deposition to streams at two small catchments with contrasting soil types in upland Wales, U.K., by determining Pb concentrations and (206)Pb/(207)Pb ratios from soil core profiles, interstitial pore waters, and stream water. Hydrological characteristics of soils are instrumental in determining the location in soil profiles of exported Pb and hence concentration and (206)Pb/(207)Pb ratios in surface waters. The highest Pb concentrations from near-surface soils are mobilized, concomitant with high dissolved organic carbon (DOC) exports, from hydrologically responsive peat soils with preferential shallow subsurface flows, leading to increased Pb concentrations in stream water and isotopic signatures more closely resembling recently deposited Pb. In more minerogenic soils, percolation of water allows Pb, bound to DOC, to be retained in mineral horizons and combined with other groundwater sources, resulting in Pb being transported from throughout the profile with a more geogenic isotopic signature. This study shows that (206)Pb/(207)Pb ratios can enhance our understanding of the provenances and transport mechanisms of Pb and potentially organic matter within upland soils.

Field observation of sequestration of uranium in iron-rich sediments under sequential reduction-oxidation conditions at the DOE Oak Ridge IFRC

At the U.S. DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) site, the iron content of shallow subsurface materials (i.e. weathered saprolite) is relatively high (up to 5-6% as w/w), and therefore, the forms of the iron species present plays a critical role in the long-term sequestration of uranium. A long term pilot-scale study of the bioreduction and reoxidation of uranium conducted at the ORIFRC area 3 site, adjacent to the former S-3 disposal ponds (source zone), has provided us with the opportunity to study the impact of iron species on the sequestration of U(VI). The aqueous U(VI) concentrations at the site were decreased to below the EPA MCL through the intermittent injection of ethanol as the electron donor. Previous field tests indicated that both oxygen and nitrate could oxidize the bioreduced U(IV) and cause a short-term rebound of aqueous phase uranium concentration after the oxidative agents were delivered directly to the bioreduced zone.

A field test has been conducted to examine the long-term effect of exposure of bioreduced sediments to nitrate in contaminated groundwater for more than 1,380 days at the Area 3 site. Contaminated groundwater was allowed to invade the previously bioreduced zone via the natural groundwater gradient after an extended period in which reducing conditions were maintained and the bioreduced zone was protected from the influx of upgradient contaminated groundwater. The geochemical response to the invasion of contaminated groundwater was dependent on whether the monitoring location is in the middle or the fringe of the previously bioreduced zone. In general, the nitrate concentrations in the previously bioreduced area, increased gradually from near zero to ~50-300 mM within 200 days and then stabilized. The pH declined from bioreduced levels of 6.2-6.7 to below 5.0. Uranium concentrations rebounded in all monitoring wells but at different rates. At most locations U concentrations rebounded, declined and then rebounded again. Methane gas disappeared while a significant level (20,000 to 44,000 ppmv) N2O was found in the groundwater of monitoring wells after three years of reoxidization.

The U(IV) in sediments was mainly reoxidized to U(VI) species. Based on XANES analysis, the predominate uranium in all samples after re-oxidation was similar to a uranyl nitrate form. But the U content in the sediment remained as high as that determined after bioreduction activates were completed, indicating that much of the U is still sequestrated in situ. SEM observations of surged fine sediments revealed that clusters of colloidal-sized (200-500nm) U-containing precipitates appeared to have formed in situ, regardless from sample of FW106 in non-bioactivity control area or of pre-bioreduced FW101-2 and FW102-3. Additionally, SEM-EDS and microprobe analysis, showed that the U-containing precipitates (~1% U) in FW106 are notably higher in Fe, compared to the precipitates (~1-2.5% U) from FW101-2 and FW102-3. However, XRF analysis indicated that the U content was remained as high as 2180 and 1810 mg/kg with U/Fe ratio at 0.077 and 0.055 vs 0.037 g/g, respectively in pre-bioreduced FW101-2 and FW102-3, suggesting more U sequestrated by Fe in pre-bioreduced sediments.

Hydrobiogeochemical Interactions along “Flow Tubes” Controls: Watershed Scale Contaminant Flow and Transformation at the Oak Ridge IFRC

Geochemical,spectrographic, microbiological and hydrogeologic studies at the ORIFRC site indicate that groundwater transport in structured media may behave as a system of parallel flow tubes. These tubes are preferred flowpaths that enable contaminant transport parallel to bedding planes (strike) over distances of 1000s of meters. A significant flux of groundwater is focused within an interval defined by the interface between the competent bedrock and overlying highly-weathered saprolite, commonly referred to as the"transition zone." Characteristics of this transition zone are dense fractures and the relative absence of weathering products (e.g. clays)results in a significantly higher permeability compared to both the overlying clay-saprolite and underlying bedrock. Several stratabound low seismic velocity zones located below the transition zone were identified during geophysics studies and were also determined to be fractured high permeability preferred contaminant transport pathways during subsequent drilling activities. XANES analysis of precipitates collected from these deeper flow zones indicate 95% or more of the U deposited is U(VI). Linear combination fitting of the EXAFS data shows that precipitates are ~51±5% U(VI)-carbonate-like phase (e.g., liebigite) and ~49±5% U(VI) associated with an iron oxide phase; inclusion of a third component in the fit suggests that up to 15% of the U(VI) may be associated with a phosphate phase or OH- phase (e.g.,schoepite). Although precipitates with similar U(VI)-carbonate and/or phosphate associations were identified in the transition zone pathways,there were also U(VI) complexes adsorbed to mineral surfaces that would tend to be more readily mobilized. Groundwater in the different flow tubes has been determined to consist of different water quality types that vary with the solid phase encountered (e.g., clays, carbonates, clastics) as contaminants migrate along the flow paths. This lateral and vertical variability in geochemistry, particularly pH, has a significant impact on microbiological community composition and activity. Ribosomal RNA gene analyses coupled with physiological and genomic analyses suggest that bacteria from the genus Rhodanobacter(a diverse population of denitrifiers that are moderately acid tolerant) have a high relative abundance in the acidic source zone at the ORIFRC site.Watershed-scale analysis across different flow paths/tubes revealed strong negative correlation between pH and the absolute and relative abundance of Rhodanobacter. Recent studies also confirmed that the ORIFRC site hosts a diverse fungal community, with significant differences observed between acidic (pH <5) and circumneutral (>5) wells. The lack of nitrous oxide reduction capability in fungi, and the detection of denitrification potential in slurry microcosms suggest that fungi may have aheretofore under appreciated role in biogeochemical transformations, with implications forsite remediation and greenhouse gas emissions. Further research is needed to determine if these organisms can influence U(VI) mobility either directly through immobilization or indirectly through the depletion of nitrate.In conclusion, additional studies are required to quantify the processes (e.g., solid phase reactions, recharge, diffusion, microbial interactions) that are occurring along the groundwater flow tubes identified at the ORIFRC so predictive models can be parameterized and used to assess long-term contaminant fate and transport and remedial options.

Landfill cap models under simulated climate change precipitation::Impacts of cracks and root growth

Desiccation crack formation is a key process that needs to be understood in assessment of landfill cap performance under anticipated future climate change scenarios. The objectives of this study were to examine: (a) desiccation cracks and impacts that roots may have on their formation and resealing, and (b) their impacts on hydraulic conductivity under anticipated climate change precipitation scenarios. Visual observations, image analysis of thin sections and hydraulic conductivity tests were carried out on cores collected from two large-scale laboratory trial landfill cap models (∼80 × 80 × 90 cm) during a year of four simulated seasonal precipitation events. Extensive root growth in the topsoil increased percolation of water into the subsurface, and after droughts, roots grew deep into low-permeability layers through major cracks which impeded their resealing. At the end of 1 year, larger cracks had lost resealing ability and one single, large, vertical crack made the climate change precipitation model cap inefficient. Even though the normal precipitation model had developed desiccation cracks, its integrity was preserved better than the climate change precipitation model.

Controls on stone temperatures and the benefits of interdisciplinary exchange

Data derived from a series of field and laboratory studies of the influence of albedo and thermal conductivity on stone temperatures are reported. They indicate the complexity of surface/subsurface temperature response characteristics of different stone types exposed to the same conditions and highlight the influence of albedo and thermal conductivity on micro-environmental conditions at the rock/air interface – conditions which have significant implications for the nature and rate of weathering activity and which may, over time, affect any surface treatments applied to stone surfaces. Although the studies reviewed were carried out within the subject area of geomorphology, the data reported and the implications for stone weathering arising from them, may be of some relevance to the conservation science perspective on deterioration of contemporary, historical and archaeological stonework.

Geophysical and hydrogeological characterisation of the impacts of on-site wastewater treatment discharge to groundwater in a poorly productive bedrock acquifer

Contaminants discharging from on-site wastewater treatment systems (OSWTSs) can impact groundwater quality, threatening human health and surface water ecosystems. Risk of negative impacts becomes elevated in areas of extreme vulnerability with high water tables, where thin unsaturated intervals limit vadose zone attenuation. A combined geophysical/hydrogeological investigation into the effects of an OSWTS, located over a poorly productive aquifer (PPA) with thin subsoil cover, aimed to characterise effluent impacts on groundwater. Groundwater, sampled from piezometers down-gradient of the OSWTS percolation area displayed spatially erratic, yet temporally consistent, contaminant distributions. Electrical resistivity tomography identified an area of gross groundwater contamination close to the percolation area and, when combined with seismic refraction and water quality data, indicated that infiltrating effluent reaching the water table discharged to a deeper more permeable zone of weathered shale resting on more competent bedrock. Subsurface structure, defined by geophysics, indicated that elevated chemical and microbiological contaminant levels encountered in groundwater samples collected from piezometers, down-gradient of sampling points with lower contaminant levels, corresponded to those locations where piezometers were screened close to the weathered shale/competent rock interface; those immediately up-gradient were too shallow to intercept this interval, and thus the more impacted zone of the contaminant plume. Intermittent occurrence of faecal indicator bacteria more than 100 m down gradient of the percolation area suggested relatively short travel times. Study findings highlight the utility of geophysics as part of multidisciplinary investigations for OSWTS contaminant plume characterisation, while also demonstrating the capacity of effluent discharging to PPAs to impact groundwater quality at distance. Comparable geophysical responses observed in similar settings across Ireland suggest the phenomena observed in this study are more widespread than previously suspected.

Mechanistic Study of 1,3-Butadiene Formation in Acetylene Hydrogenation over the Pd-Based Catalysts Using Density Functional Calculations

Green oil, which leads to the deactivation of the catalysts used for the selective hydrogenation of acetylene, has long been observed but its formation mechanism is not fully understood. In this work, the formation of 1,3-butadiene, known to be the precursor of green oil, on both Pd(111) and Pd(211) surfaces is examined using density functional theory calculations. The pathways containing C-2 + C-2 coupling reactions as well as the corresponding hydrogenation reactions are studied in detail. Three pathways for 1,3-butadiene production, namely coupling plus hydrogenation and further hydrogenation, hydrogenation plus coupling plus hydrogenation, and a two step hydrogenation followed by coupling, are determined. By comparing the effective barriers, we identify the favored pathway on both surfaces. A general understanding toward the deactivation process of the industrial catalysts is also provided. In addition, the effects of the formation of subsurface carbon atoms as well as the Ag alloying on the 1,3-butadiene formation on Pd-based catalysts are also investigated and compared with experimental results.

Selective Hydrogenation of Acetylene over Pd-Boron Catalysts: A Density Functional Theory Study

Boron-modified Pd catalysts have shown excellent performance for the selective hydrogenation of alkynes experimentally. In the current work, we investigated the hydrogenation of acetylene on boron-modified Pd(111) and Pd(211) surfaces, utilizing density functional theory calculations. The activity of acetylene hydrogenation has been studied by estimating the effective barrier of the whole process. The selectivity of ethylene formation is investigated from a comparison between the desorption and the hydrogenation of ethylene as well as comparison between the ethylene and the 1,3-butadiene formation. Formation of subsurface carbon and hydrogen on both boron-modified Pd(111) and Pd(211) surfaces has also been evaluated, since these have been reported to affect both the activity and the selectivity of acetylene hydrogenation to produce ethylene on Pd surfaces. Our results provide some important insights into the Pd B catalysts for selective hydrogenation of acetylene and also for more complex hydrogenation systems, such as stereoselective hydrogenation of longer chain alkynes and selective hydrogenation of vegetable oil.

Integrating geophysical data and upscaling techniques to support regional groundwater flow modelling: A practical example of the Lagan Valley, Northern Ireland

When studying heterogeneous aquifer systems, especially at regional scale, a degree of generalization is anticipated. This can be due to sparse sampling regimes, complex depositional environments or lack of accessibility to measure the subsurface. This can lead to an inaccurate conceptualization which can be detrimental when applied to groundwater flow models. It is important that numerical models are based on observed and accurate geological information and do not rely on the distribution of artificial aquifer properties. This can still be problematic as data will be modelled at a different scale to which it was collected. It is proposed here that integrating geophysics and upscaling techniques can assist in a more realistic and deterministic groundwater flow model. In this study, the sedimentary aquifer of the Lagan Valley in Northern Ireland is chosen due to intruding sub-vertical dolerite dykes. These dykes are of a lower permeability than the sandstone aquifer. The use of airborne magnetics allows the delineation of heterogeneities, confirmed by field analysis. Permeability measured at the field scale is then upscaled to different levels using a correlation with the geophysical data, creating equivalent parameters that can be directly imported into numerical groundwater flow models. These parameters include directional equivalent permeabilities and anisotropy. Several stages of upscaling are modelled in finite element. Initial modelling is providing promising results, especially at the intermediate scale, suggesting an accurate distribution of aquifer properties. This deterministic based methodology is being expanded to include stochastic methods of obtaining heterogeneity location based on airborne geophysical data. This is through the Direct Sample method of Multiple-Point Statistics (MPS). This method uses the magnetics as a training image to computationally determine a probabilistic occurrence of heterogeneity. There is also a need to apply the method to alternate geological contexts where the heterogeneity is of a higher permeability than the host rock.

Combining multi-scale geophysical techniques for robust hydro-structural characterisation in catchments underlain by hard rock in post-glacial regions

Accurate conceptual models of groundwater systems are essential for correct interpretation of monitoring data in catchment studies. In surface-water dominated hard rock regions, modern ground and surface water monitoring programmes often have very high resolution chemical, meteorological and hydrological observations but lack an equivalent emphasis on the subsurface environment, the properties of which exert a strong control on flow pathways and interactions with surface waters. The reasons for this disparity are the complexity of the system and the difficulty in accurately characterising the subsurface, except locally at outcrops or in boreholes. This is particularly the case in maritime north-western Europe, where a legacy of glacial activity, combined with large areas underlain by heterogeneous igneous and metamorphic bedrock, make the structure and weathering of bedrock difficult to map or model. Traditional approaches which seek to extrapolate information from borehole to field-scale are of limited application in these environments due to the high degree of spatial heterogeneity. Here we apply an integrative and multi-scale approach, optimising and combining standard geophysical techniques to generate a three-dimensional geological conceptual model of the subsurface in a catchment in NE Ireland. Available airborne LiDAR, electromagnetic and magnetic data sets were analysed for the region. At field-scale surface geophysical methods, including electrical resistivity tomography, seismic refraction, ground penetrating radar and magnetic surveys, were used and combined with field mapping of outcrops and borehole testing. The study demonstrates how combined interpretation of multiple methods at a range of scales produces robust three-dimensional conceptual models and a stronger basis for interpreting groundwater and surface water monitoring data.

A '3-body' abrasion wear study of bioceramics for total hip joint replacements

The current study focuses on the effect of the material type and the lubricant on the abrasive wear behaviour of two important commercially available ceramic on ceramic prosthetic systems, namely, Biolox(R) forte and Bioloxl(R) delta (CeramTec AG, Germany). A standard microabrasion wear apparatus was used to produce '3-body' abrasive wear scars with three different lubricants: ultrapure water, 25 vol% new-born calf serum solution and 1 wt% carboxymethyl cellulose sodium salt (CMC-Na) solution. 1 mu m alumina particles were used as the abrasive. The morphology of the wear scar was examined in detail using Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). Subsurface damage accumulation was investigated by Focused Ion Beam (FIB) cross-sectional milling and Transmission Electron Microscopy (TEM). The effect of the lubricant on the '3-body' abrasive wear mechanisms is discussed and the effect of material properties compared. (C) 2009 Elsevier B.V. All rights reserved.

Linking watershed terrain and hydrology to soil chemical properties, microbial communities and impacts on soil organic C in a humid mid-latitude forested watershed

Understanding the response of humid mid-latitude forests to changes in precipitation, temperature, nutrient cycling, and disturbance is critical to improving our predictive understanding of changes in the surface-subsurface energy balance due to climate change. Mechanistic understanding of the effects of long-term and transient moisture conditions are needed to quantify
linkages between changing redox conditions, microbial activity, and soil mineral and nutrient interactions on C cycling and greenhouse gas releases. To illuminate relationships between the soil chemistry, microbial communities and organic C we established transects across hydraulic and topographic gradients in a small watershed with transient moisture conditions. Valley bottoms tend to be more frequently saturated than ridge tops and side slopes which generally are only saturated when shallow storm flow zones are active. Fifty shallow (~36”) soil cores were collected during timeframes representative of low CO2, soil winter conditions and high CO2, soil summer conditions. Cores were subdivided into 240 samples based on pedology and analyses of the geochemical (moisture content, metals, pH, Fe species, N, C, CEC, AEC) and microbial (16S rRNA gene
amplification with Illumina MiSeq sequencing) characteristics were conducted and correlated to watershed terrain and hydrology. To associate microbial metabolic activity with greenhouse gas emissions we installed 17 soil gas probes, collected gas samples for 16 months and analyzed them for CO2 and other fixed and greenhouse gasses. Parallel to the experimental efforts our data is being used to support hydrobiogeochemical process modeling by coupling the Community Land Model (CLM) with a subsurface process model (PFLOTRAN) to simulate processes and interactions from the molecular to watershed scales. Including above ground processes (biogeophysics, hydrology, and vegetation dynamics), CLM provides mechanistic water, energy, and organic matter inputs to the surface/subsurface models, in which coupled biogeochemical reaction
networks are used to improve the representation of below-ground processes. Preliminary results suggest that inclusion of above ground processes from CLM greatly improves the prediction of moisture response and water cycle at the watershed scale.