Quantitative micro‐X‐ray fluorescence scanning spectroscopy of wet sediment based on the X‐ray absorption and emission theories: Its application to freshwater lake sedimentary sequences

Micro‐X‐ray fluorescence scanning spectroscopy of marine and lake sedimentary sequences can provide detailed palaeoenvironmental records through element intensity proxy data. However, problems with the effects of interstitial pore water on the micro‐X‐ray fluorescence intensities have been pointed out. This is because the X‐ray fluorescence intensities are measured directly at the surfaces of split wet sediment core samples. This study developed a new method for correcting X‐ray fluorescence data to compensate for the effects of pore water using a scanning X‐ray analytical microscope. This involved simultaneous use of micro‐X‐ray fluorescence scanning spectroscopy and an X‐ray transmission detector. To evaluate the interstitial pore water content from the X‐ray transmission intensities, a fine‐grained sediment core retrieved from Lake Baikal (VER99‐G12) was used to prepare resin‐embedded samples with smooth surfaces and uniform thickness. Simple linear regression between the linear absorption coefficients of the samples and their porosity, based on the Lambert–Beer law, enabled calculation of the interstitial pore spaces and their resin content with high reproducibility. The X‐ray fluorescence intensities of resin‐embedded samples were reduced compared with those of dry sediment samples because of: (i) the X‐ray fluorescence absorption of resin within sediment; and (ii) the sediment dilution effects by resin. An improved micro‐X‐ray fluorescence correction equation based on X‐ray fluorescence emission theory considers the instrument's sensitivity to each element, which provides a reasonable explanation of these two effects. The resin‐corrected X‐ray fluorescence intensity was then successfully converted to elemental concentrations using simple linear regression between the data from micro‐X‐ray fluorescence scanning spectroscopy and from the conventional analyzer. In particular, the calculated concentration of SiO₂ over the depth of the core, reflecting diatom/biogenic silica concentration, was significantly changed by the calibrations, from a progressively decreasing trend to an increasing trend towards the top of the core.     

Textural evolution of perovskite in the Afrikanda alkaline–ultramafic complex,Kola Peninsula,Russia

Perovskite is a common accessory mineral in a variety of mafic and ultramafic rocks, but perovskite deposits are rare and studies of perovskite ore deposits are correspondingly scarce. Perovskite is a key rock-forming mineral and reaches exceptionally high concentrations in olivinites, diverse clinopyroxenites and silicocarbonatites in the Afrikanda alkaline–ultramafic complex (Kola Peninsula, NW Russia). Across these lithologies, we classify perovskite into three types (T1–T3) based on crystal morphology, inclusion abundance, composition, and zonation. Perovskite in olivinites and some clinopyroxenites is represented by fine-grained, equigranular, monomineralic clusters and networks (T1). In contrast, perovskite in other clinopyroxenites and some silicocarbonatites has fine- to coarse-grained interlocked (T2) and massive (T3) textures. Electron backscatter diffraction reveals that some T1 and T2 perovskite grains in the olivinites and clinopyroxenites are composed of multiple subgrains and may represent stages of crystal rotation, coalescence and amalgamation. We propose that in the olivinites and clinopyroxenites, these processes result in the transformation of clusters and networks of fine-grained perovskite crystals (T1) to mosaics of more coarse-grained (T2) and massive perovskite (T3). This interpretation suggests that sub-solidus processes can lead to the development of coarse-grained and massive perovskite. A combination of characteristic features identified in the Afrikanda perovskite (equigranular crystal mosaics, interlocked irregular-shaped grains, and massive zones) is observed in other oxide ore deposits, particularly in layered intrusions of chromitites and intrusion-hosted magnetite deposits and suggests that the same amalgamation processes may be responsible for some of the coarse-grained and massive textures observed in oxide deposits worldwide.     

A County‐Level Risk Assessment of the Deep Water Horizon Oil Spill in the Gulf of Mexico

This paper undertakes a risk assessment of coastal counties in the Gulf of Mexico impacted by the 2010 Deep Water Horizon oil spill. The study evaluates hazard risk from the perspective of community resilience, social capital, and access to resources. The proposed hazard risk location model re‐specifies risk as a function of hazard, exposure, and coping ability. The model employs an autoregressive function and a threshold analysis to develop a place‐based risk assessment. The results indicate that spatial variation in risk levels coincides with locational differences in social capital across the study area. Geographical proximity to the spill, population density, and unemployment rate are also key factors in determining overall risk. Furthermore, temporal variation in risk levels is determined by exposure to previous hazard events and changes in the business cycle.     

Dissolved and total organic and inorganic carbon in some British rivers

Rivers transport both organic and inorganic carbon from their sources to the sea. Results of ~800 organic and inorganic analyses from various British rivers of contrasting size and land use are presented here: (1) the headwater River Tern, a rural river of 852 km² catchment; (2) the Ouseburn, a small urban 55 km² catchment; (3) the River Tyne, a larger river system of ~3000 km² catchment; (4) a spatial survey from 205 sample sites on ~60 rivers from SW England. We found that, with the exception of peat-rich headwaters, DIC concentration is always greater than DOC. DIC is primarily in the form HCO₃ ⁻ , with DIC concentrations highest in highly urbanised catchments, typically greater than those observed in catchments with carbonate bedrock, demonstrating a significant and previously unrecognised anthropogenic inorganic carbon input to urban rivers.     

High frequency measurements of dissolved inorganic and organic nutrients using instrumented moorings in the southern and central North Sea

The aim of this study was to investigate the cycling of dissolved inorganic and organic nutrients using moored instrumented buoys (SmartBuoys) during the spring bloom in the North Sea. The instrumentation on the buoys enabled high frequency measurements of water-column integrated irradiance and in situ chlorophyll to be made, and also preserved water sample collection which were used for dissolved inorganic and organic nutrient analyses. The SmartBuoys were located in the year-round well-mixed plume zone associated with the River Thames and in the summer stratified central North Sea. These site locations allowed comparison of nutrient concentrations and cycling, and spring bloom development at two contrasting sites. The spring bloom was expected to be initiated at both stations due to increasing insolation and decreasing suspended load leading to higher water-column integrated irradiance. Due to differences in suspended load between the sites, the spring bloom started ∼2 months earlier in the central North Sea. The spring bloom in the Thames plume also resulted in higher maximum phytoplankton biomass due to the higher pre-bloom nutrient concentrations associated with riverine input. The use of SmartBuoys is also shown to allow the cycling of dissolved organic nutrients to be examined over the critical, and often undersampled, spring bloom period. Dissolved Organic Nitrogen (DON) clearly increased during the spring bloom in the central North Sea compared to winter concentrations. DON also increased in the Thames plume although showing greater winter variability related to higher riverine and sedimentary dissolved organic matter input at this shallow (∼18 m) coastal site. DON increase during the spring bloom was therefore related to primary production at both sites probably due to active release by phytoplankton. At both stations DON decreased to pre-bloom concentrations as the bloom declined suggesting the released DON was bioavailable and removed due to heterotrophic uptake and production. The preserved nutrient samples from the central North Sea site were also suitable for Dissolved Organic Phosphorus (DOP) analysis due to their low suspended load with similar trends and cycling to DON, albeit at lower concentrations. This suggested similar processes controlling both DON and DOP. The variable timing of short term events such as the spring bloom makes sampling away from coastal regions difficult without the use of autonomous technology. This study demonstrates for the first time the applicability of using preserved samples from automated buoys for the measurement of dissolved organic nutrients.     

Plutonium diffusivity in compacted bentonite

Measurements on plutonium diffusivity in water-saturated compacted bentonite were carried out. Representative specimens of sodium bentonite were taken from the Tsukinuno and Kuroishi mines situated in northeast Japan. Tsukinuno bentonite was divided into three types: raw type, purified Na-type, and H-type which was prepared by treating Na-type bentonite with hydrochloric acid. Kuroishi bentonite contained chlorite as impurity. H-type bentonite was used as reference for the convenience of profile measurement in bentonite, since plutonium diffusivity in H-type bentonite was considered to be larger than that in Na-type bentonite because of low pH and low swelling pressure of H-type bentonite.

Sampled bentonite was compacted into pellets of 20 mm in diameter and 20 mm in height. Bulk densities of these specimens were 1200–1800 kg/m³ for purified Na-type and H-type bentonite and 1600 kg/m³ for raw type bentonite.

Plutonium profiles obtained in H-type bentonite can be explained by diffusion equation with constant concentration source. Diffusivity ranges from 10^-13 to 10¹² m²/s for H-type and Kuroishi impure sodium bentonite. Diffusivity in both raw type and purified Tsukinuno bentonite was was estimated to less than 10^-14 M²/s. Diffusivity in H-type bentonite showed a tendency to decrease with increasing density. Influence of in bentonite was also studied. Quartz content up to 50% or hematite content up to 1% did not influence diffusivity significantly in H-type bentonite.

The chemical species of plutonium in pore water of Na-type and H-type were estimated Pu(OH)₃^-; and PuO₂^- , respectively.