[en] This paper describes the detrital mineralogy, early diagenetic reactions and authigenic mineral precipitates for freshwater contaminated sediments deposited in an urban water body (the Salford Quays of the Manchester Ship Canal, Greater Manchester, UK). These sediments contain a mix of natural and anthropogenic detrital grains. Detrital grains are dominated by quartz and clay grains, whilst anthropogenic grains are dominated by metal-rich glass grains, concentrated at a depth of 12-17cm in the sediment as a result of historical inputs. Sediment porewaters contain significant concentrations of Fe, Mn, Zn and phosphate. Bacterial Fe(III) and Mn(IV) reduction are hypothesised to supply Fe²⁺ and Mn²⁺ to porewaters, with phosphate released from Fe oxide reduction or organic matter oxidation. Petrographic observations indicate that the metal-rich glass grains are undergoing chemical dissolution during early diagenesis, supplying Fe and Zn to porewaters. The most abundant authigenic mineral in the sediments is vivianite (Fe₃(PO₄)₂.8H₂O), containing a significant level of redlingite (Mn₃²⁺(PO₄)₂.8H₂O), with minor framboidal pyrite (FeS₂). Electron microprobe analysis shows the vivianite to contain Zn, Cu and Pb, suggesting that vivianite acts as a long-term sink for these metals in this sediment. This implies that authigenic vivianite in freshwater sediments may act as a long-term sink for metals, in a similar manner to sulphides in marine sediments. This study highlights that the nature of detrital and diagenetic mineralogy, in addition to porewater and sediment chemistry, needs to be considered in assessing contaminated sediments

[en] Road-deposited sediment (RDS) is an accumulation of particulates upon street surfaces in urban centres. It is commonly highly contaminated and has major potential impacts upon surface water quality and human health, as well as becoming a waste material upon street sweeping. Although significant research has been undertaken upon the fine fraction within these systems, there is a lack of detailed, high-resolution grain-specific mineralogical and chemical data for the coarser fractions, which contain the bulk of the contamination by mass. The study reported here utilizes backscatter electron microscopic, electron microprobe and Raman spectroscopic analysis to provide novel data on RDS material from Manchester, UK, with significant implications for the improved understanding of source discrimination and contaminant metal speciation. The RDS samples studied are highly heterogeneous and the abundant nature of anthropogenic grains is particularly apparent. The RDS material has been found to be composed of a number of grain types: (i) silicate and alumino-silicate grains derived from a wide range of sources; (ii) iron oxide grains derived from the corrosion of galvanized steel; (iii) iron-rich glass grains derived as slag material from metal and waste processing activities and (iv) spherical Fe oxide and Fe-rich glass grains derived from high temperature combustion processes. Elemental metallic grains (Fe, Cu, Pb) are also present in minor amounts. Electron microprobe analysis shows that the Fe oxide and Fe-rich glass grains act as the major hosts for contaminant metal elements within these sediments. The recognition of Fe oxides being an important host for metals is consistent with previous inferences made from bulk chemical sequential analysis. However, the presence of glass slag phases as major hosts of metals is not recognised in these sequential extraction schemes, leading to erroneous inferences and inputs into risk assessments. It is clear that high resolution grain-specific chemical analysis, as reported here, is the key to fully understanding these urban contaminated sediment systems.

[en] Highlights: • A novel upscaling method is proposed to quantify pores from the nm-to mm-scale. • Three advanced 3D imaging techniques are applied across five distinct scales. • A two-step analysis prior to upscaling ensures the images are representative. • Four types of pores are recognized at nanoscale and then all upscaled to mm-scale. • Upscaled porosity differs by less than 10% compared to measured helium porosity. -- Abstract: Microstructures and pore systems in shales are key to understanding the role of shale in many energy applications. This study proposes a novel multi-stage upscaling procedure to comprehensively investigate the heterogeneous and complex microstructures and pore systems in a laminated and microfractured shale, utilising 3D multi-scale imaging data. Five imaging techniques were used for characterisation from sub-nanoscale to macroscale (core-scale), spanning four orders of magnitude. Image data collected using X-ray tomography, Focused Ion Beam, and Electron Tomography techniques range in voxel size from 0.6 nm to 13 μm. Prior to upscaling, a novel two-step analysis was performed to ensure sub-samples were representative. Following this, a three-step procedure, based on homogenising descriptors and computed volume coefficients, was used to upscale the quantified microstructure and pore system. At the highest resolution (nanoscale), four distinct pore types were identified. At the sub-micron scale equations were derived for three pore-associated phases. At the microscale, the volume coefficients were recalculated to upscale the pore system to the millimetre- scale. The accuracy of the upscaling methodology was verified, predicting the total porosity within 7.2% discrepancy. The results provide a unique perspective to understand heterogeneous rock types, breaking though prior scale limitations in the pore system.

[en] Atmospheric deposition of trace metals and metalloids from anthropogenic sources has led to the contamination of many European peatlands. To assess the fate and behaviour of previously deposited arsenic and lead, we constructed catchment-scale mass budgets for a degraded peatland in Northern England. Our results show a large net export of both lead and arsenic via runoff (282 ± 21.3 gPb ha^-1 y^-1 and 60.4 ± 10.5 gAs ha^-1 y^-1), but contrasting controls on this release. Suspended particulates account for the majority of lead export, whereas the aqueous phase dominates arsenic export. Lead release is driven by geomorphological processes and is a primary effect of erosion. Arsenic release is driven by the formation of a redox-dynamic zone in the peat associated with water table drawdown, a secondary effect of gully erosion. Degradation of peatland environments by natural and anthropogenic processes has the potential to release the accumulated pool of legacy contaminants to surface waters. - Highlights: → The fluvial outputs of arsenic and lead in the degraded peatland are an order-of-magnitude greater than atmospheric inputs. → The particulate phase dominates fluvial lead export, whereas the aqueous phase dominates fluvial arsenic export. → Lead export is a primary effect of peat erosion, whereas arsenic export is a secondary effect of peat erosion. - Degraded peatlands can be significant sources of previously deposited arsenic and lead

[en] The sediments in the Salford Quays, a heavily-modified urban water body, contain high levels of organic matter, Fe, Zn and nutrients as a result of past contaminant inputs. Vivianite [Fe₃(PO₄)_2.8H₂O] has been observed to have precipitated within these sediments during early diagenesis as a result of the release of Fe and P to porewaters. These mineral grains are small (<100 μm) and micron-scale analysis techniques (SEM, electron microprobe, μ-EXAFS, μ-XANES and Raman) have been applied in this study to obtain information upon the structure of this vivianite and the nature of Zn uptake in the mineral. Petrographic observations, and elemental, X-ray diffraction and Raman spectroscopic analysis confirms the presence of vivianite. EXAFS model fitting of the FeK-edge spectra for individual vivianite grains produces Fe-O and Fe-P co-ordination numbers and bond lengths consistent with previous structural studies of vivianite (4O atoms at 1.99-2.05 A; 2P atoms at 3.17-3.25 A). One analysed grain displays evidence of a significant Fe³⁺ component, which is interpreted to have resulted from oxidation during sample handling and/or analysis. EXAFS modelling of the Zn K-edge data, together with linear combination XANES fitting of model compounds, indicates that Zn may be incorporated into the crystal structure of vivianite (4O atoms at 1.97 A; 2P atoms at 3.17 A). Low levels of Zn sulphate or Zn-sorbed goethite are also indicated from linear combination XANES fitting and to a limited extent, the EXAFS fitting, the origin of which may either be an oxidation artifact or the inclusion of Zn sulphate into the vivianite grains during precipitation. This study confirms that early diagenetic vivianite may act as a sink for Zn, and potentially other contaminants (e.g. As) during its formation and, therefore, forms an important component of metal cycling in contaminated sediments and waters. Furthermore, for the case of Zn, the EXAFS fits for Zn phosphate suggest this uptake is structural and not via surface adsorption

[en] Highlights: • In-situ synchrotron imaging is demonstrated to investigate fracturing in shales. • 3D images were recorded during stepped loading and used to perform digital volume correlation. • The deformation zones were quantitatively resolved. • Composition, texture and orientation influence fracture initiation and propagation. The feasibility and advantages of synchrotron imaging have been demonstrated to effectively characterise fracture initiation and propagation in shales during indentation tests. These include 1) fast (minute-scale) and high-resolution (μm-scale) imaging of fracture initiation, 2) concurrent spatial and temporal information (4D) about fracture development, 3) quantification and modelling of shale deformation prior to fracture. Imaging experiments were performed on four shale samples with different laminations and compositions in different orientations, representative of three key variables in shale microstructure. Fracture initiation and propagation were successfully captured in 3D over time, and strain maps were generated using digital volume correlation (DVC). Subsequently, post-experimental fracture geometries were characterised at nano-scale using complementary SEM imaging. Characterisation results highlight the influence of microstructural and anisotropy variations on the mechanical properties of shales. The fractures tend to kink at the interface of two different textures at both macroscale and microscale due to deformation incompatibility. The average composition appears to provide the major control on hardness and fracture initiation load; while the material texture and the orientation of the indentation to bedding combine to control the fracture propagation direction and geometry. This improved understanding of fracture development in shales is potentially significant in the clean energy applications.