Kalle Kirsimäe

Phosphorus removal using Ca-rich hydrated oil shale ash as filter material--the effect of different phosphorus loadings and wastewater compositions.

We studied the phosphorus (P) binding capacity of Ca-rich alkaline filter material - hydrated oil shale ash (i.e. hydrated ash) in two onsite pilot-scale experiments (with subsurface flow filters) in Estonia: one using pre-treated municipal wastewater with total phosphorus (TP) concentration of 0.13-17.0 mg L(-1) over a period of 6 months, another using pre-treated landfill leachate (median TP 3.4 mg L(-1)) for a total of 12 months. The results show efficient P removal (median removal of phosphates 99%) in horizontal flow (HF) filters at both sites regardless of variable concentrations of several inhibitors. The P removal efficiency of the hydrated ash increases with increasing P loading, suggesting direct precipitation of Ca-phosphate phases rather than an adsorption mechanism. Changes in the composition of the hydrated ash suggest a significant increase in P concentration in all filters (e.g. from 489.5 mg kg(-1) in initial ash to 664.9 mg kg(-1) in the HF filter after one year in operation), whereas almost all TP was removed from the inflow leachate (R(2) = 0.99). Efficiency was high throughout the experiments (median outflow from HF hydrated ash filters 0.05-0.50 mg L(-1)), and P accumulation did not show any signs of saturation.

Electrospun nanofibers as a potential controlled-release solid dispersion system for poorly water-soluble drugs.

Electrospinning was introduced as a novel technique for preparing controlled-release (CR) amorphous solid dispersions (SD) and polymeric nanofibers of a poorly water-soluble drug. Piroxicam (PRX) was used as a low-dose poorly-soluble drug and hydroxypropyl methylcellulose (HPMC) as an amorphous-state stabilising carrier polymer in nanofibers. Raman spectroscopy, X-ray powder diffraction (XPRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) were used in the physical characterisation of the CR-SD nanofibers. Special attention was paid on the effects of a polymer and solvent system on the solid-state properties and physical stability of nanofibers. The average dry diameter of the electrospun CR-SD nanofibers ranged from 400 to 600 nm (SEM). PRX existed in amorphous form in the nanofibers immediately after fabrication and after a short-term (3-month) aging at low temperature (6-8 °C/0% RH) and ambient room temperature (22 °C/0% RH). At higher temperature and humidity (30 °C/85% RH), however, amorphous PRX in the nanofibers tended to slowly recrystallise to PRX form III. The electrospun CR-SD nanofibers exhibited a short lag-time, the absence of initial burst release and zero-order linear CR dissolution kinetics. In conclusion, electrospinning can be used to fabricate supersaturating CR-SD nanofibers of PRX and HPMC, and to stabilise the amorphous state of PRX.

ALTERED VOLCANIC ASH AS AN INDICATOR OF MARINE ENVIRONMENT, REFLECTING pH AND SEDIMENTATION RATE – EXAMPLE FROM THE ORDOVICIAN KINNEKULLE BED OF BALTOSCANDIA

The composition of altered volcanic ash of the Late Ordovician Kinnekulle bed was studied in geological sections of the Baltic Paleobasin. The composition of altered ash varies with paleosea depth from northern Estonia to Lithuania. The ash bed in shallow shelf limestones contains an association of illite-smectite (I-S) and K-feldspar, with the K2O content ranging from 7.5 to 15.3%. The limestone in the transition zone between shallow- and deep-shelf environments contains I-S-dominated ash with K2O content from 6.0 to 7.5%. In the deep-shelf marlstone and shale, the volcanic ash bed consists of I-S and kaolinite with a K2O content ranging from 4.1 to 6.0%. This shows that authigenic silicates from volcanic ash were formed during the early sedimentary-diagenetic processes. The composition of the altered volcanic ash can be used as a paleoenvironmental indicator showing the pH of the seawater or porewater in sediments as well as the sedimentation rate.

Composition, diagenetic transformation and alkalinity potential of oil shale ash sediments

Oil shale is a primary fuel in the Estonian energy sector. After combustion 45-48% of the oil shale is left over as ash, producing about 5-7 Mt of ash, which is deposited on ash plateaus annually almost without any reuse. This study focuses on oil shale ash plateau sediment mineralogy, its hydration and diagenetic transformations, a study that has not been addressed. Oil shale ash wastes are considered as the biggest pollution sources in Estonia and thus determining the composition and properties of oil shale ash sediment are important to assess its environmental implications and also its possible reusability. A study of fresh ash and drillcore samples from ash plateau sediment was conducted by X-ray diffractometry and scanning electron microscopy. The oil shale is highly calcareous, and the ash that remains after combustion is derived from the decomposition of carbonate minerals. It is rich in lime and anhydrite that are unstable phases under hydrous conditions. These processes and the diagenetic alteration of other phases determine the composition of the plateau sediment. Dominant phases in the ash are hydration and associated transformation products: calcite, ettringite, portlandite and hydrocalumite. The prevailing mineral phases (portlandite, ettringite) cause highly alkaline leachates, pH 12-13. Neutralization of these leachates under natural conditions, by rainwater leaching/neutralization and slow transformation (e.g. carbonation) of the aforementioned unstable phases into more stable forms, takes, at best, hundreds or even hundreds of thousands of years.

MINERALOGICAL AND Rb-Sr ISOTOPE STUDIES OF LOW-TEMPERATURE DIAGENESIS OF LOWER CAMBRIAN CLAYS OF THE BALTIC PALEOBASIN OF NORTH ESTONIA

X-ray diffraction (XRD), Rb-Sr isotope analysis, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), and Fourier transform infrared (FTIR) methods were used to study diagenetic illite and illite-smectite (I-S) in Lower Cambrian unlithified clays of shallow depth of burial in the northern part of the intercratonic Baltic paleosedimentary basin of the East-European Platform. The studies focused on the <0.06-µm size fraction of the clay. This fraction consists of a highly illitic illite-smectite (I-S) and a poorly crystalline illite (PCI), with some traces of Fe-rich chlorite also present. Rb-Sr isotopic data for the <0.06-µm size fractions suggest that the illitic I-S and PCI have different formation ages. No precise isotopic ages were derived directly owing to the composite illite mineralogy and retention of radiogenic Sr. This retention occurred because of imperfect isotopic homog-enization at low water/rock ratios. The age of burial diagenesis is proposed to coincide with the time of maximum burial depth, which was achieved during the Middle to Late Devonian and continued until Permian-Triassic erosion. Because of the shallow depth of burial (<2 km), diagenesis was probably a low-temperature (<50°C) transformation process. The resident time of 100–150 million years at maximum burial had a major influence in the process.

Soluplus Graft Copolymer: Potential Novel Carrier Polymer in Electrospinning of Nanofibrous Drug Delivery Systems for Wound Therapy

Electrospinning is an effective method in preparing polymeric nanofibrous drug delivery systems (DDSs) for topical wound healing and skin burn therapy applications. The aim of the present study was to investigate a new synthetic graft copolymer (Soluplus) as a hydrophilic carrier polymer in electrospinning of nanofibrous DDSs. Soluplus (polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft copolymer (PCL-PVAc-PEG)) was applied in the nonwoven nanomats loaded with piroxicam (PRX) as a poorly water-soluble drug. Raman spectroscopy, X-ray powder diffraction, differential scanning calorimetry, and scanning electron microscopy (SEM) were used in the physical characterization of nanofibrous DDSs. According to the SEM results, the drug-loaded PCL-PVAc-PEG nanofibers were circular in cross-section with an average diameter ranging from 500 nm up to 2 µm. Electrospinning stabilized the amorphous state of PRX. In addition, consistent and sustained-release profile was achieved with the present nanofibrous DDSs at the physiologically relevant temperature and pH applicable in wound healing therapy. In conclusion, electrospinning can be used to prepare nanofibrous DDSs of PCL-PVAc-PEG graft copolymer (Soluplus) and to stabilize the amorphous state of a poorly water-soluble PRX. The use of this synthetic graft copolymer can open new options to formulate nanofibrous DDSs for wound healing.

Solid-state properties of softwood lignin and cellulose isolated by a new acid precipitation method.

Solid-state and powder properties of softwood lignin and cellulose prepared by a new catalytic oxidation and acid precipitation method were characterized and compared with the commercial softwood and hardwood lignin and cellulose products. Catalytic pre-treated softwood lignin (CPSL) and cellulose (CPSC) were isolated from pine wood (Pinus sylvestris). CPSL with nearly micronized-scale particle size showed excellent powder flow and densification behavior due to the round shape and electrically minimum charged surface characteristics of particles. CPSL and the reference lignin studied were amorphous solids while CPSC exhibited a typical crystal lattice for cellulose I. In conclusion, physicochemical material properties of lignin and cellulose can be modified for biomedical and pharmaceutical applications with the present catalytic oxidation and acid precipitation method.

The mid-Ordovician Osmussaar breccia in Estonia linked to the disruption of the L-chondrite parent body in the asteroid belt

The Middle Ordovician (466 Ma) Osmussaar breccia, situated along the northwestern coast of Estonia, is rich in angular chromite grains of extraterrestrial origin (>13 grains kg(-1)) and shocked quartz. The angularity of the chromite grains implies that they have not been transported or reworked to any large extent, connoting that the brecciation is the result of a contemporary impactor, either as a direct consequence of the impact or as a result of an earthquake triggered by the impact, and thus is not, as previously suggested, redeposited material from the nearby similar to 70 m.y. older Neugrund impact structure. The chemical composition of the chromite indicates that the impactor was an ordinary chondrite of L-type, which concurs well with the hypothesis that the influx of large bodies to Earth increased during this period due to the breakup of the L-chondrite parent body. This in turn gives support to the recent suggestion that abundant coeval mega-breccias worldwide are impact triggered. The presence of extraterrestrial chromite also strengthens the theory that physical pieces of a large celestial body can survive upon impact with Earth. (Less)

ILLITIZATION OF EARLY PALEOZOIC K-BENTONITES IN THE BALTIC BASIN: DECOUPLING OF BURIAL- AND FLUID-DRIVEN PROCESSES

The mineralogical characteristics of Ordovician and Silurian K-bentonites in the Baltic Basin were investigated in order to understand better the diagenetic development of these sediments and to link illitization with the tectonothermal evolution of the Basin. The driving mechanisms of illitization in the Baltic Basin are still not fully understood. The organic material thermal alteration indices are in conflict with the illite content in mixed-layer minerals. The clay fraction of the bentonites is mainly characterized by mixed-layered illite-smectite and kaolinite except in the Upper Ordovician Katian K-bentonites where mixed-layer chlorite-smectite (corrensite) occurs. The variation in expandability plus other geological data suggest that the illitization of Ordovician and Silurian K-bentonites in the Baltic Basin was controlled by a combination of burial and fluid driven processes. The illitization in the south and southwest sectors of the basin was effected mainly by burial processes. The influence of the burial process decreases with decreasing maximum burial towards the central part of the basin. The advanced illitization of the shallowburied succession in the north and northwest sectors of the basin was enhanced by the prolonged flushing of K-rich fluids in relation to the latest phase of development of the Scandinavian Caledonides ≈420–400 Ma.

The Osmussaar Breccia in Northwestern Estonia — Evidence of a ~475 Ma Earthquake or an Impact?

The Osmussaar Breccia occurs in beds of the ~475 Ma basal Middle Ordovician (Arenig and Llanvirn series) siliclastic-carbonate rocks of northwestern Estonia. The Breccia consists of fragmented and slightly displaced (sandy) limestones, which are penetrated by veins and bodies of strongly cemented, breccia-like, lime-rich sandstone injections. The rocks above (horizontally-bedded, hard limestone) and below (weakly cemented silt and sandstone) are undisturbed and do not contain the sediment intrusions. Osmussaar Breccia is found over an area of more than 5000 km2 and is distributed in a west- east oriented elliptical half-circle centred approximately at Osmussaar Island (59°18′ N; 23°28′ E). The thickness of the brecciated unit ranges from 1-1.5 m on Osmussaar to a few (tens of) cm at ~70 km east of the island. Arenitic sandstone of the sediment injections contains quartz grains with planar deformation features (PDF). Several hypotheses concerning the origin of the Osmussaar event have been proposed: catastrophic earthquake, regional tectonic movements, tectonic movements occurring simultaneously with coastal processes, and an impact event. The latter hypothesis was suggested in connection with the discovery of the nearby-situated Neugrund impact structure. However, the sediment intrusions are stratigraphically ~60 Ma younger than the impact structure. Osmussaar Breccia does not correspond to any known impact structure of this age in Baltoscandia. Also, results of a seabed geophysical survey in the Baltic Sea for the search of a possible undiscovered feature did not identify any large structure in the area of the Osmussaar Breccia. Consequently, we suggest that a devastating ~475 Ma earthquake with an epicentre close to Osmussaar split the sea floor. It initiated underwater mud-flows eroding the primary Neugrund crater ejecta and/or crater rim walls, thus reworking the impact materials into the sedimentary injections, which is suggested by rounded morphology of the shocked quartz grains found in breccia matrix.