The importance of solid-phase distribution on the oral bioaccessibility of Ni and Cr in soils overlying Palaeogene basalt lavas, Northern Ireland

Potentially toxic elements (PTEs) including nickel and chromium are often present in soils overlying basalt at concentrations above regulatory guidance values due to the presence of these elements in underlying geology. Oral bioaccessibility testing allows the risk posed by PTEs to human health to be assessed; however, bioaccessibility is controlled by factors including mineralogy, particle size, solid-phase speciation and encapsulation. X-ray diffraction was used to characterise the mineralogy of 12 soil samples overlying Palaeogene basalt lavas in Northern Ireland, and non-specific sequential extraction coupled with chemometric analysis was used to determine the distribution of elements amongst soil components in 3 of these samples. The data obtained were related to total concentration and oral bioaccessible concentration to determine whether a relationship exists between the overall concentrations of PTEs, their bioaccessibility and the soils mineralogy and geochemistry. Gastric phase bioaccessible fraction (BAF %) ranged from 0.4 to 5.4 % for chromium in soils overlying basalt and bioaccessible and total chromium concentrations are positively correlated. In contrast, the range of gastric phase BAF for nickel was greater (1.4–43.8 %), while no significant correlation was observed between bioaccessible and total nickel concentrations. However, nickel BAF was inversely correlated with total concentration. Solid-phase fractionation information showed that bioaccessible nickel was associated with calcium carbonate, aluminium oxide, iron oxide and clay-related components, while bioaccessible chromium was associated with clay-related components. This suggests that weathering significantly affects nickel bioaccessibility, but does not have the same effect on the bioaccessibility of chromium.

An experimental and numerical investigation into the seismic performance of a multi-storey concentrically braced plan irregular structure

In this investigation, the seismic torsional response of a multi-storey concentrically braced frame (CBF) plan irregular structure is evaluated numerically and experimentally through a series of hybrid tests. CBF structures have become popular in seismic design because they are one of the most efficient types of steel structures to resist earthquake loading. However, their response under plan irregular conditions has received little focus mostly in part
due to their complex behaviour under seismic loading conditions. The majority of research on the seismic response of plan irregular structures is based purely on numerical investigations. This paper provides much needed experimental investigation of the seismic response of a CBF plan irregular structure with the aim of characterising the response of this class of structure. The effectiveness of the Eurocode 8 torsional effects provision as a method of designing for
low levels of mass eccentricity is evaluated. Results indicate that some of the observations made by purely numerical models are valid in that; torsionally stiff structures perform well and the stiff side of the structure is subjected to a greater ductility demand compared to the flexible side of the structure. The Eurocode 8 torsional effects provision is shown to be adequate in terms of ductility and interstorey drift however the structure performs poorly
in terms of floor rotation. Importantly, stiffness eccentricity occurs when the provision is applied to the structure when no mass eccentricity exists and results in a significant increase in floor rotations.

The lateritic profile of Balkouin, Burkina Faso: geochemistry, mineralogy and genesis

This study reports on the geochemical and mineralogical characterization of a lateritic profile cropping out in the Balkouin area, Central Burkina Faso, aimed at obtaining a better understanding of the processes responsible for the formation of the laterite itself and the constraints to its development. The lateritic profile rests on a Paleoproterozoic basement mostly composed of granodioritic rocks related to the Eburnean magmatic cycle passing upwards to saprolite and consists of four main composite horizons (bottom to top): kaolinite and clay-rich horizons, mottled laterite and iron-rich duricrust. In order to achieve such a goal, a multi-disciplinary analytical approach was adopted, which includes inductively coupled plasma (ICP) atomic emission and mass spectrometries (ICP-AES and ICP-MS respectively), X-ray powder diffraction (XRPD), scanning electron microscopy with energy dispersive spectrometry (SEM-EDS) and micro-Raman spectroscopy.

The geochemical data, and particularly the immobile elements distribution and REE patterns, show that the Balkouin laterite is the product of an in situ lateritization process that involved a strong depletion of the more soluble elements (K, Mg, Ca, Na, Rb, Sr and Ba) and an enrichment in Fe; Si was also removed, particularly in the uppermost horizons. All along the profile the change in composition is coupled with important changes in mineralogy. In particular, the saprolite is characterized by occurrence of abundant albitic plagioclase, quartz and nontronite; kaolinite is apparently absent. The transition to the overlying lateritic profile marks the breakdown of plagioclase and nontronite, thus allowing kaolinite to become one of the major components upwards, together with goethite and quartz. The upper part of the profile is strongly enriched in hematite (+ kaolinite). Ti oxides (at least in part as anatase) and apatite are typical accessory phases, while free aluminum hydroxides are notably absent. Mass change calculations emphasize the extent of the mass loss, which exceeds 50 wt% (and often 70 wt%) for almost all horizons; only Fe was significantly concentrated in the residual system.

The geochemical and mineralogical features suggest that the lateritic profile is the product of a continuous process that gradually developed from the bedrock upwards, in agreement with the Schellmann classic genetic model. The laterite formation must have occurred at low pH (? 4.5) and high Eh (? 0.4) values, i.e., under acidic and oxidizing environments, which allowed strongly selective leaching conditions. The lack of gibbsite and bohemite is in agreement with the compositional data: the occurrence of quartz (± amorphous silica) all along the profile was an inhibiting factor for the formation of free aluminum hydroxides.

Spatial statistics to estimate peat thickness using airborne radiometric data

Soil carbon stores are a major component of the annual returns required by EU governments to the Intergovernmental Panel on Climate Change. Peat has a high proportion of soil carbon due to the relatively high carbon density of peat and organic-rich soils. For this reason it has become increasingly important to measure and model soil carbon stores and changes in peat stocks to facilitate the management of carbon changes over time. The approach investigated in this research evaluates the use of airborne geophysical (radiometric) data to estimate peat thickness using the attenuation of bedrock geology radioactivity by superficial peat cover. Remotely sensed radiometric data are validated with ground peat depth measurements combined with non-invasive geophysical surveys. Two field-based case studies exemplify and validate the results. Variography and kriging are used to predict peat thickness from point measurements of peat depth and airborne radiometric data and provide an estimate of uncertainty in the predictions. Cokriging, by assessing the degree of spatial correlation between recent remote sensed geophysical monitoring and previous peat depth models, is used to examine changes in peat stocks over time. The significance of the coregionalisation is that the spatial cross correlation between the remote and ground based data can be used to update the model of peat depth. The result is that by integrating remotely sensed data with ground geophysics, the need is reduced for extensive ground-based monitoring and invasive peat depth measurements. The overall goal is to provide robust estimates of peat thickness to improve estimates of carbon stocks. The implications from the research have a broader significance that promotes a reduction in the need for damaging onsite peat thickness measurement and an increase in the use of remote sensed data for carbon stock estimations.

Rapid magmatic processes accompany arc-continent collision: the Western Bismarck arc, Papua New Guinea

New U-Th-Ra, major and trace element, and Sr-Nd-Pb isotope data are presented for young lavas from the New Britain and Western Bismarck arcs in Papua New Guinea. New Britain is an oceanic arc, whereas the latter is the site of an arc-continent collision. Building on a recent study of the Manus Basin, contrasts between the two arcs are used to evaluate the processes and timescales of magma generation accompanying arc-continent collision and possible slab detachment. All three suites share many attributes characteristic of arc lavas that can be ascribed to the addition of a regionally uniform subduction component derived from the subducting altered oceanic crust and sediment followed by dynamic melting of the modified mantle. However, the Western Bismarck arc lavas diverge from the Pb isotope mixing array formed by the New Britain and the Manus Basin lavas toward elevated Pb-208/Pb-204. We interpret this to reflect a second and subsequent addition of sediment melt at crustal depth during collision. U-238 and Ra-226 excesses are preserved in all of the lavas and are greatest in the Western Bismarck arc. High-Mg andesites with high Sr/Y ratios in the westernmost arc are attributed to recent shallow mantle flux melting at the slab edge. Data for two historical rhyolites are also presented. Although these rhyolites formed in quite different tectonic settings and display different geochemical and isotopic compositions, both formed from mafic parents within millennia.

Integrating petrography, mineralogy and hydrochemistry to constrain the influence and distribution of groundwater contributions to baseflow in poorly productive aquifers: Insights from Gortinlieve catchment, Co. Donegal, NW Ireland

Identifying groundwater contributions to baseflowforms an essential part of surfacewater body characterisation. The Gortinlieve catchment (5 km2) comprises a headwater stream network of the Carrigans River, itself a tributary of the River Foyle, NW Ireland. The bedrock comprises poorly productive metasediments that are characterised by fracture porosity. We present the findings of a multi-disciplinary study that integrates new hydrochemical and mineralogical investigations with existing hydraulic, geophysical and structural data to identify the scales of groundwater flow and the nature of groundwater/bedrock interaction (chemical denudation). At the catchment scale, the development of deep weathering profiles is controlled by NE-SW regional scale fracture zones associated with mountain building during the Grampian orogeny. In-situ chemical denudation of mineral phases is controlled by micro- to meso-scale fractures related to Alpine compression during Palaeocene to Oligocene times. The alteration of primary muscovite, chlorite (clinochlore) and albite along the surfaces of these small-scale fractures has resulted in the precipitation of illite, montmorillonite and illite/montmorillonite clay admixtures. The interconnected but discontinuous nature of these small-scale structures highlights the role of larger scale faults and fissures in the supply and transportation of weathering solutions to/from the sites of mineral weathering. The dissolution of primarily mineral phases releases the major ions Mg, Ca and HCO3 that are shown to subsequently formthe chemical makeup of groundwaters. Borehole groundwater and stream baseflow hydrochemical data are used to constrain the depths of groundwater flow pathways influencing the chemistry of surface waters throughout the stream profile. The results show that it is predominantly the lower part of the catchment, which receives inputs from catchment/regional scale groundwater flow, that is found to contribute to the maintenance of annual baseflow levels. This study identifies the importance
of deep groundwater in maintaining annual baseflow levels in poorly productive bedrock systems.

Wetting of compacted clays under laterally restrained conditions: Initial state, overburden pressure and mineralogy

Compacted clay fills are generally placed at the optimum value of water content and, immediately after placement, they are unsaturated. Wetting might subsequently occur due, for example, to rainfall infiltration, which can cause volumetric deformation of the fill (either swell or collapse) with associated loss of shear strength and structural integrity. If swelling takes place under partially restrained deformation, due for example to the presence of a buried rigid structure or a retaining wall, additional stresses will develop in the soil and these can be detrimental to the stability of walling elements and other building assets. Factors such as dry density, overburden pressure, compaction water content and type of clay are known to influence the development of stresses. This paper investigates these factors by means of an advanced stress path testing programme performed on four different clays with different mineralogy, index properties and geological histories. Specimens of kaolin clay, London Clay, Belfast Clay and Ampthill Clay were prepared at different initial states and subjected to ‘controlled’ wetting, whereby the suction was reduced gradually to zero under laterally restrainedconditions (i.e. K0 conditions). The results showed that the magnitude of the increase in horizontal stresses (and therefore the increase of K0) is influenced by the overburden pressure, compaction water content, dry density at the time of compaction and mineralogy.

MarcoPolo-R near earth asteroid sample return mission

MarcoPolo-R is a sample return mission to a primitive Near-Earth Asteroid (NEA) proposed in collaboration with NASA. It will rendezvous with a primitive NEA, scientifically characterize it at multiple scales,and return a unique sample to Earth unaltered by the atmospheric entry process or terrestrial weathering. MarcoPolo-R will return bulk samples (up to 2 kg) from an organic-rich binary asteroid to Earth for laboratory analyses, allowing us to: explore the origin of planetary materials and initial stages of habitable planet formation; identify and characterize the organics and volatiles in a primitive asteroid; understand the unique geomorphology, dynamics and evolution of a binaryNEA. This project is based on the previous Marco Polo mission study,which was selected for the Assessment Phase of the first round of Cosmic Vision. Its scientific rationale was highly ranked by ESA committees andit was not selected only because the estimated cost was higher than theallotted amount for an M class mission. The cost of Marco Polo-R will be reduced to within the ESA medium mission budget by collaboration withAPL (John Hopkins University) and JPL in the NASA program for coordination with ESA's Cosmic Vision Call. The baseline target is a binary asteroid (175706) 1996 FG3, which offers a very efficient operational and technical mission profile. A binary target also providesenhanced science return. The choice of this target will allow newinvestigations to be performed more easily than at a single object, andalso enables investigations of the fascinating geology and geophysics ofasteroids that are impossible at a single object. Several launch windows have been identified in the time-span 2020-2024. A number of otherpossible primitive single targets of high scientific interest have beenidentified covering a wide range of possible launch dates. The baselinemission scenario of Marco Polo-R to 1996 FG3 is as follows: a singleprimary spacecraft provided by ESA, carrying the Earth Re-entry Capsule, sample acquisition and transfer system provided by NASA, will be launched by a Soyuz-Fregat rocket from Kourou into GTO and using two space segment stages. Two similar missions with two launch windows, in 2021 and 2022 and for both sample return in 2029 (with mission durationof 7 and 8 years), have been defined. Earlier or later launches, in 2020 or 2024, also offer good opportunities. All manoeuvres are carried out by a chemical propulsion system. MarcoPolo-R takes advantage of three industrial studies completed as part of the previous Marco Polo mission (see ESA/SRE (2009)3, Marco Polo Yellow Book) and of the expertise of the consortium led by Dr. A.F. Cheng (PI of the NASA NEAR Shoemaker mission) of the JHU-APL, including JPL, NASA ARC, NASA LaRC, and MIT.