Dynamical instability in surface permeability characteristics of building sandstones in response to salt accumulation over time

This paper explores how the surface permeability of sandstone blocks changes over time in response to repeated salt weathering cycles. Surface permeability controls the amount of moisture and dissolved salt that can penetrate in and facilitate decay. Connected pores permit the movement of moisture (and hence soluble salts) into the stone interior, and where areas are more or less permeable soluble salts may migrate along preferred pathways at differential rates. Previous research has shown that salts can accumulate in the near-surface zone and lead to partial pore blocking which influences subsequent moisture ingress and causes rapid salt accumulation in the near-surface zone.

Two parallel salt weathering simulations were carried out on blocks of Peakmoor Sandstone of different volumes. Blocks were removed from simulations after 2, 5, 10, 20 and 60 cycles. Permeability measurements were taken for these blocks at a resolution of 20 mm, providing a grid of 100 permeability values for each surface. The geostatistical technique of ordinary kriging was applied to the data to produce a smoothed interpolation of permeability for these surfaces, and hence improve understanding of the evolution of permeability over time in response to repeated salt weathering cycles.

Results illustrate the different responses of the sandstone blocks of different volumes to repeated salt weathering cycles. In both cases, after an initial subtle decline in the permeability (reflecting pore blocking), the permeability starts to increase — reflected in a rise in mean, maximum and minimum values. However, between 10 and 20 cycles, there is a jump in the mean and range permeability of the group A block surfaces coinciding with the onset of meaningful debris release. After 60 cycles, the range of permeability in the group A block surface had increased markedly, suggesting the development of a secondary permeability. The concept of dynamic instability and divergent behaviour is applied at the scale of a single block surface, with initial small-scale differences across a surface having larger scale consequences as weathering progresses.

After cycle 10, group B blocks show a much smaller increase in mean permeability, and the range stays relatively steady — this may be explained by the capillary conditions set up by the smaller volume of the stone, allowing salts to migrate to the ‘back’ of the blocks and effectively relieving stress at the ‘front’ face.

Wear paths produced by individual hip-replacement patients— A large-scale, long-term follow-up study

Wear particle accumulation is one of the main contributors to osteolysis and implant failure in hip replacements. Altered kinematics produce significant differences in wear rates of hip replacements in simulator studies due to varying degrees of multidirectional motion. Gait analysis data from 153 hip-replacement patients 10-years post-operation were used to model two- and three-dimensional wear paths for each patient. Wear paths were quantified in two dimensions using aspect ratios and in three dimensions using the surface areas of the wear paths, with wear-path surface area correlating poorly with aspect ratio. The average aspect ratio of the patients wear paths was 3.97 (standard deviation ¼ 1.38), ranging from 2.13 to 10.86. Sixty percent of patients displayed aspect ratios between 2.50 and 3.99. However, 13% of patients displayed wear paths with aspect ratios 45.5, which indicates reduced multidirectional motion. The majority of total hip replacement (THR) patients display gait kinematics which produce multidirectional wear paths, but a significant minority display more linear paths.

Influence of preparation conditions on the characteristics of activated carbons produced in laboratory and pilot scale systems

The central theme of this investigation is to evaluate the feasibility of using bituminous coal as a precursor material for the production of chars and activated carbons using physical and chemical activation processes. The chemical activation process was accomplished by impregnating the raw materials with different dehydrating agents in different ratios and concentrations, prior to heat treatment (ZnCl2, KCl, KOH, NaOH and Fe2(SO4)3·xH2O). Steam activation of the precursor material was adopted for the preparation of activated carbon using physical activation technology. Different types of bituminous coal; namely, contaminated Columbian (contaminated with pet. coke), pure Columbian, Venezuelan and New Zealand bituminous coal were used in the production processes. BET surface area, micropore area, pore size distribution and total pore volume of the chars and activated carbons were determined from N2 adsorption/desorption isotherm, measured at 77 K. Charring conditions, charring temperature of 800 °C and charring time of 4 h, proved to be the optimum conditions for preparing chars. Contaminated Columbian were found to be the best precursor material for the production of char with reasonable physical characteristics (surface area = 138.1 m2 g-1 and total pore volume of 8.656 × 10-0.2 cm3 g-1). An improvement in the physical characteristics of the activated carbons was obtained upon the treatment of coal with dehydrating agents. Contaminated Columbian treated with 10 wt% ZnCl2 displayed the highest surface area and total pore volume (surface area = 231.5 m2 g-1 and total pore volume = 0.1227 cm3 g-1) with well-developed microporisity (micropore area = 92.3 m2 g-1). Venezuelan bituminous coal using the steam activation process was successful in producing activated carbon with superior physical characteristics (surface area = 863.50 m2 g-1, total pore volume = 0.469 cm3 g-1 and micropore surface area = 783.58 m2 g-1).

The broad-scale distribution of five jellyfish species across a temperate coastal environment

Jellyfish (medusae) are sometimes the most noticeable and abundant members of coastal planktonic communities, yet ironically, this high conspicuousness is not reflected in our overall understanding of their spatial distributions across large expanses of water. Here, we set out to elucidate the spatial (and temporal) patterns for five jellyfish species (Phylum Cnidaria, Orders Rhizostomeae and Semaeostomeae) across the Irish & Celtic Seas, an extensive shelf-sea area at Europe's northwesterly margin encompassing several thousand square kilometers. Data were gathered using two independent methods: (1) surface-counts of jellyfish from ships of opportunity, and (2) regular shoreline surveys for stranding events over three consecutive years. Jellyfish species displayed distinct species-specific distributions, with an apparent segregation of some species. Furthermore, a different species composition was noticeable between the northern and southern parts of the study area. Most importantly, our data suggests that jellyfish distributions broadly reflect the major hydrographic regimes (and associated physical discontinuities) of the study area, with mixed water masses possibly acting as a trophic barrier or non-favourable environment for the successful growth and reproduction of jellyfish species.

Determining the Sun's influence on Lateglacial and Holocene climates: a focus on climate response to centennial-scale solar forcing at 2800 cal. BP

The influence of solar variability on the climate of the Lateglacial and Holocene periods has been the subject of increasing discussion during the last decade. In the Mid-Holocene, several studies have identified cold/wet events that occur at ca 2800 cal. BP and a link with a reduction in solar activity, inferred from the C-14 record, has been postulated. We present results from a multi-proxy study of peat humification, plant macrofossils and testate amoebae from a raised bog at Glen West, northwest Ireland, that indicate that dry bog surface conditions were experienced in the north of Ireland at the time of the solar anomaly starting at 2800 cal. BP. With the aid of C-14 wiggle-matching and tephrochronology, an abrupt shift to wetter conditions is dated to ca 2700 cal. BP, coinciding with a C-14 maximum but clearly post-dating the 2800 cal. BP event identified elsewhere in Europe. We explore the significance of this apparent lag in the Irish record, considering the possible role of the ocean in generating spatial and temporal complexities in the climate patterns of the North Atlantic region. We conclude that these complexities are likely to give rise to time-transgressive climate responses around the North Atlantic that will only be recognised by more critical chronological approaches.

Limitations of instantaneous water quality sampling in surface-water catchments: Comparison with near-continuous phosphorus time-series data.

The validity of load estimates from intermittent, instantaneous grab sampling is dependent on adequate spatial coverage by monitoring networks and a sampling frequency that re?ects the variability in the system under study. Catchments with a ?ashy hydrology due to surface runoff pose a particular challenge as intense short duration rainfall events may account for a signi?cant portion of the total diffuse transfer of pollution from soil to water in any hydrological year. This can also be exacerbated by the presence of strong background pollution signals from point sources during low flows. In this paper, a range of sampling methodologies and load estimation techniques are applied to phosphorus data from such a surface water dominated river system, instrumented at three sub-catchments (ranging from 3 to 5 km2 in area) with near-continuous monitoring stations. Systematic and Monte Carlo approaches were applied to simulate grab sampling using multiple strategies and to calculate an estimated load, Le based on established load estimation methods. Comparison with the actual load, Lt, revealed signi?cant average underestimation, of up to 60%, and high variability for all feasible sampling approaches. Further analysis of the time series provides an insight into these observations; revealing peak frequencies and power-law scaling in the distributions of P concentration, discharge and load associated with surface runoff and background transfers. Results indicate that only near-continuous monitoring that re?ects the rapid temporal changes in these river systems is adequate for comparative monitoring and evaluation purposes. While the implications of this analysis may be more tenable to small scale ?ashy systems, this represents an appropriate scale in terms of evaluating catchment mitigation strategies such as agri-environmental policies for managing diffuse P transfers in complex landscapes.

The control of porosity at nano scale in resorcinol formaldehyde carbon aerogels

Organic aerogels were synthesized by sol–gel polymerization of resorcinol (R) with formaldehyde (F) catalyzed by sodium carbonate (C) followed by vacuum drying. The influence of the resorcinol/sodium carbonate ratio (R/C) on the porous structure of the resultant aerogels was investigated. The nitrogen adsorption–desorption measurements show that the aerogels possess a well developed porous structure and mesoporosity was found to increase with increasing the R/C ratio. Carbon aerogels were obtained by carbonization of RF aerogels. The carbonization temperature impacts the microstructure of the aerogels by pore transformations during carbonization probably due to the formation of micropores and shrinkage of the gel structure. The results showed that a temperature of 1073 Kis more effective in the development of the pore structure of the gel. Activated carbon aerogels were obtained from the CO2 activation of carbon aerogels. Activation results in an increase in the number of both micropores and mesopores, indicative of pore creation in the structure of the carbon. Activation at higher temperatures results in a higher degree of burn off and increases the pore volume and the surface area remarkably without change of the basic porous structure, pore size, and pore size distribution.

Near-surface temperature cycling of stone and its implications for scales of surface deterioration

Many previous studies into internal temperature gradients within stone have assumed smooth, exponential increases and decreases in sub-surface temperatures in response, for example, to diurnal patterns of heating and cooling and these have been used to explain phenomena such as large-scale contour scaling. This high-resolution experimental study, in which a porous limestone block was subjected to alternate surface heating and cooling using an infrared lamp, demonstrates that internal temperature gradients in response to short-term environmental cycles (measured in minutes) can in fact be complex and inconsistent. Results confirm the significance of very steep temperature/stress gradients within the outer 10 mm or less of exposed stone. Below this the data indicate complex patterns of temperature reversals, the amplitudes of which are attenuated with depth and which are influenced in their intensity and location by variations in the relative duration of heating and cooling phases. It is suggested that the reversals might represent ‘interference patterns’ between incoming and outgoing thermal waves, but whatever their origin they are potentially important because they occur within the zone in which many stone decay processes, especially 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. In particular, the reversals occur at a scale that is commensurate with decay by multiple flaking and could indicate an underlying control on this previously little-researched pattern of weathering. In the context of this publication, however, the main lesson to be learned from this study is that differing scales of behaviour require different scales of enquiry.

Plasma surface dynamics and smoothing in the relativistic few-cycle regime

Efficient production of coherent harmonic radiation from solid targets relies critically on the formation of smooth, short density scalelength plasmas. Recent experimental results (Dromey et al 2009 Nat. Phys. 5 146) suggest, however, that the target roughness on the scale of the emitted harmonic wavelength does not result in diffuse reflection-in apparent contradiction to the Rayleigh criterion for coherent reflection. In this paper we show, for the first time, using analytic theory and 2D PIC simulations, that the interaction of relativistically strong laser pulses with corrugated target surfaces results in a highly effective smoothing of the interaction surface and consequently the generation of highly collimated and temporally confined XUV pulses from rough targets, in excellent agreement with experimental observations.

Micron-scale fast electron filaments and recirculation determined from rear-side optical emission in high-intensity laser-solid interactions

The transport of relativistic electrons generated in the interaction of petawatt class lasers with solid targets has been studied through measurements of the second harmonic optical emission from their rear surface. The high degree of polarization of the emission indicates that it is predominantly optical transition radiation (TR). A halo that surrounds the main region of emission is also polarized and is attributed to the effect of electron recirculation. The variation of the polarization state and intensity of radiation with the angle of observation indicates that the emission of TR is highly directional and provides evidence for the presence of mu m-size filaments. A brief discussion on the possible causes of such a fine electron beam structure is given.

Pathways for delivery of surface water nutrients to receptors

Diffuse contaminants can make their way into rivers via a number of different pathways, including overland flow, interflow, and shallow and deep groundwater. Identification of the key pathway(s) delivering contaminants to a receptor is important for implementing effective water management strategies. The ‘Pathways Project’, funded by the Irish Environmental Protection Agency, is developing a catchment management tool that will enable practitioners to identify the critical source areas for diffuse contaminants, and the key pathways of interest in assessing contaminant problems on a catchment and sub-catchment scale.
One of the aims of the project is to quantify the flow and contaminant loadings being delivered to the stream via each of the main pathways. Chemical separation of stream event hydrographs is being used to supplement more traditional physical hydrograph separation methods. Distinct, stable chemical signatures are derived for each of the pathway end members, and the proportion of flow from each during a rainfall event can be determined using a simple mass balance approach.
Event sampling was carried out in a test catchment underlain by poorly permeable soils and bedrock, which is predominantly used for grazing with a number of one-off rural residential houses. Results show that artificial field drainage, which includes subterranean land drains and collector drains around the perimeters of the 1 to 10 ha fields, plays an important role in the delivery of flow and nutrients to the streams in these types of hydrogeological settings.
Nitrate infiltrates with recharge and is delivered to the stream primarily via the artificial drains and the shallow groundwater pathway. Longitudinal stream profiles show that the nitrate load input is relatively uniform over the 8 km length of the stream at high flows, suggesting widespread diffuse contaminant input. In contrast, phosphorus is adsorbed in the clay-rich soil and is transported mainly via the overland flow pathway and the artificial drains. Longitudinal stream profiles for phosphorus suggest a pattern of more discrete points of phosphorus inputs, which may be related to point sources of contamination.
These techniques have application elsewhere within a toolkit of methods for determining the key pathways delivering contaminants to surface water receptors.

Micro-scale biopitting by endolithic lichen and their role in meso-scale solution basin development on limestone

Data are reported demonstrating the potential role of microscale morphologies, induced by endolithic lichen communities, specifically Verrucaria baldensis, in the initiation and development of mesoscale solution basin formation on limestone in the Burren, Co. Clare. A biophysical model is proposed outlining the different microscale stages leading to solution basin initiation with a progression from initial lichen colonisation and growth, associated biopitting followed by biopit coalescence to form biotroughs, their subsequent enlargement and eventual incipient solution basin formation. This model provides one explanation for solution basin development as this end state may also be achieved through simple solutional means without biological input. The complexity of interactions at the rock / lichen interface are identified with emphasis on the spatial and temporal variability of these underlining the point that, as with macro-topographies at the landscape scale, rock surface micro-topographies also reflect historical weathering legacies.

Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.

Stochastic and deterministic processes interact in the assembly of desert microbial communities on a global scale

Extreme arid regions in the worlds' major deserts are typified by quartz pavement terrain. Cryptic hypolithic communities colonize the ventral surface of quartz rocks and this habitat is characterized by a relative lack of environmental and trophic complexity. Combined with readily identifiable major environmental stressors this provides a tractable model system for determining the relative role of stochastic and deterministic drivers in community assembly. Through analyzing an original, worldwide data set of 16S rRNA-gene defined bacterial communities from the most extreme deserts on the Earth, we show that functional assemblages within the communities were subject to different assembly influences. Null models applied to the photosynthetic assemblage revealed that stochastic processes exerted most effect on the assemblage, although the level of community dissimilarity varied between continents in a manner not always consistent with neutral models. The heterotrophic assemblages displayed signatures of niche processes across four continents, whereas in other cases they conformed to neutral predictions. Importantly, for continents where neutrality was either rejected or accepted, assembly drivers differed between the two functional groups. This study demonstrates that multi-trophic microbial systems may not be fully described by a single set of niche or neutral assembly rules and that stochasticity is likely a major determinant of such systems, with significant variation in the influence of these determinants on a global scale.