In-depth characterization of exhaust particles performed on-board a modern cruise ship applying a scrubber.

To comply with environmental regulations, ship operators may adopt exhaust after-treatment devices such as scrubbers or selective catalytic reduction (SCR). Beyond gaseous emission control, these technologies impact the exhaust particles emitted from marine engines to the atmosphere. This study characterizes comprehensively the chemical composition and physical properties of exhaust aerosol particles upstream and downstream a hybrid scrubber operating in open loop mode on-board a modern cruise ship. The study considers two engines, one equipped with SCR and both with scrubber, during engine load conditions of 75 % and 40 %, and the influence of marine gas oil (MGO) use in addition to heavy fuel oil (HFO). At least 4 different particle types were observed in the exhaust based on transmission electron microscopy (TEM) studies both upstream and downstream scrubber, and both scrubber and SCR affected the particle number size distribution (PSD). The geometric mean diameter (GMD) of the particles increased over scrubber both due to removal of nucleation mode particles and particle growth in the scrubber. The scrubber effectively decreased particle number (PN) and, also, non-volatile particles, but the effect depended on particle size and no significant decrease was observed in number of particles above 50 nm, typically comprising black carbon (BC) and in the case of HFO combustion, also asymmetrical metal containing particles. In addition to PN, concentrations of PAH compounds were reduced in the scrubber. The results may be further utilized when including the exhaust aerosol characteristics from ships applying scrubbers to emission inventories, as well as climate and air quality models.

Magnetic domain wall dynamics studied by in-situ Lorentz microscopy with aid of custom-made Hall-effect sensor holder.

We built a custom-made holder with a Hall-effect sensor to measure the single point magnetic flux density inside a transmission electron microscope (TEM, JEM-F200, JEOL). The measurement point is at the same place as the sample inside the TEM. We utilized information collected with the Hall-effect sensor holder to study magnetic domain wall (DW) dynamics by in-situ Lorentz microscopy. We generated an external magnetic field to the sample using the objective lens (OL) of the TEM. Based on our measurements with the Hall-effect sensor holder, the OL has nearly linear response, and when it is switched off, the strength of the magnetic field in the sample region is very close to 0 mT. A ferritic-pearlitic sample studied has globular and lamellar cementite (Fe3C) carbides in the ferrite matrix. Based on the in-situ Lorentz microscopy experiments, DWs in the ferritic matrix perpendicular to the lamellar carbides start to move first at ∼10 mT. At 160 mT, DWs inside the globular carbide start to disappear, and the saturation occurs at ∼210 mT. At 288 mT, the DWs parallel to the lamellar carbides still exist. Thus, these lamellar carbides are very strong pinning sites for DWs. We also run dynamical micromagnetic simulations to reproduce the DW disappearance in the globular carbide. As in the in-situ experiments, the DWs stay stable until the external field reaches the magnitude of 160 mT, and the DWs disappear before the field is 214 mT. In general, the micromagnetic simulations supported very well the interpretation of the experimental findings.

Influence of the photodeposition sequence on the photocatalytic activity of plasmonic Ag-Au/TiO2 nanocomposites.

Bimetallic Ag-Au/TiO2 nanocomposites were synthesized by sequential photodeposition in order to investigate the effect of surface plasmon resonance (SPR) properties on photocatalytic activity for solar water splitting and methylene blue (MB) degradation. The photodeposition times were optimized for monometallic Ag/TiO2 and Au/TiO2 nanocomposites to yield maximum SPR absorption in the visible range. It was found that the photocatalytic activity of bimetallic Ag-Au/TiO2 nanocomposites outperformed monometallic nanocomposites only when Au was photodeposited first on TiO2, which was attributed to Au-core-Ag-shell nanoparticle morphology. In contrast, reversing the photodeposition order resulted in Ag-Au alloy nanoparticle morphology, which was mediated by the galvanic replacement reaction during the second photodeposition. Alloying was not beneficial to the photocatalytic activity. These results demonstrate alloying during sequential photodeposition providing new insights for the synthesis of TiO2-based photocatalysts with plasmon-enhanced absorption in the visible range.

Self-assembled cellulose nanofiber-carbon nanotube nanocomposite films with anisotropic conductivity.

In this study, a nanocellulose-based material showing anisotopic conductivity is introduced. The material has up to 1000 times higher conductivity along the dry-line boundary direction than along the radial direction. In addition to the material itself, the method to produce the material is novel and is based on the alignment of cationic cellulose nanofibers (c-CNFs) along the dry-line boundary of an evaporating droplet composed of c-CNFs in two forms and conductive multi-walled carbon nanotubes (MWCNTs). On the one hand, c-CNFs are used as a dispersant of MWCNTs, and on the other hand they are used as an additional suspension element to create the desired anisotropy. When the suspended c-CNF is left out, and the nanocomposite film is manufactured using the high energy sonicated c-CNF/MWCNT dispersion only, conductive anisotropy is not present but evenly conducting nanocomposite films are obtained. Therefore, we suggest that suspending additional c-CNFs in the c-CNF/MWCNT dispersion results in nanocomposite films with anisotropic conductivity. This is a new way to obtain nanocomposite films with substantial anisotropic conductivity.

Interface Engineering of TiO2 Photoelectrode Coatings Grown by Atomic Layer Deposition on Silicon.

Titanium dioxide (TiO2) can protect photoelectrochemical (PEC) devices from corrosion, but the fabrication of high-quality TiO2 coatings providing long-term stability has remained challenging. Here, we compare the influence of Si wafer cleaning and postdeposition annealing temperature on the performance of TiO2/n+-Si photoanodes grown by atomic layer deposition (ALD) using tetrakis(dimethylamido)titanium (TDMAT) and H2O as precursors at a growth temperature of 100 °C. We show that removal of native Si oxide before ALD does not improve the TiO2 coating performance under alkaline PEC water splitting conditions if excessive postdeposition annealing is needed to induce crystallization. The as-deposited TiO2 coatings were amorphous and subject to photocorrosion. However, the TiO2 coatings were found to be stable over a time period of 10 h after heat treatment at 400 °C that induced crystallization of amorphous TiO2 into anatase TiO2. No interfacial Si oxide formed during the ALD growth, but during the heat treatment, the thickness of interfacial Si oxide increased to 1.8 nm for all of the samples. Increasing the ALD growth temperature to 150 °C enabled crystallization at 300 °C, which resulted in reduced growth of interfacial Si oxide followed by a 70 mV improvement in the photocurrent onset potential.

Vanadia-Zirconia and Vanadia-Hafnia Catalysts for Utilization of Volatile Organic Compound Emissions.

Utilization is a sustainable and interesting alternative for the destructive treatment of volatile organic compounds due to avoided CO2 emission. This work concentrates on the development of active and sulfur-tolerant catalysts for the utilization of contaminated methanol. Impregnated and sol-gel prepared vanadia-zirconia and vanadia-hafnia catalysts were thoroughly characterized by N2 sorption, analytical (S)TEM, elemental analysis, XRD and Raman spectroscopy, and their performances were evaluated in formaldehyde production from methanol and methanethiol mixture. The results showed higher activity of the sol-gel prepared catalysts due to formation of mono- and polymeric vanadia species. Unfortunately, the most active vanadia sites were deactivated more easily than the metal-mixed oxide HfV2O7 and ZrV2O7 phases, as well as crystalline V2O5 observed in the impregnated catalysts. Metal-mixed oxide phases were formed in impregnated catalysts through formation of defects in HfO2 and ZrO2 structure during calcination at 600 °C, which was evidenced by Raman spectroscopy. The sol-gel prepared vanadia-zirconia and vanadia-hafnia catalysts were able to produce formaldehyde from contaminated methanol with high selectivity at temperature around 400 °C, while impregnated catalysts required 50-100 °C higher temperatures.

Cellulose Mesh with Charged Nanocellulose Coatings as a Promising Carrier of Skin and Stem Cells for Regenerative Applications.

Engineering artificial skin constructs is an ongoing challenge. An ideal material for hosting skin cells is still to be discovered. A promising candidate is low-cost cellulose, which is commonly fabricated in the form of a mesh and is applied as a wound dressing. Unfortunately, the structure and the topography of current cellulose meshes are not optimal for cell growth. To enhance the surface structure and the physicochemical properties of a commercially available mesh, we coated the mesh with wood-derived cellulose nanofibrils (CNFs). Three different types of mesh coatings are proposed in this study as a skin cell carrier: positively charged cationic cellulose nanofibrils (cCNFs), negatively charged anionic cellulose nanofibrils (aCNFs), and a combination of these two materials (c+aCNFs). These cell carriers were seeded with normal human dermal fibroblasts (NHDFs) or with human adipose-derived stem cells (ADSCs) to investigate cell adhesion, spreading, morphology, and proliferation. The negatively charged aCNF coating significantly improved the proliferation of both cell types. The positively charged cCNF coating significantly enhanced the adhesion of ADSCs only. The number of NHDFs was similar on the cCNF coatings and on the noncoated pristine cellulose mesh. However, the three-dimensional (3D) structure of the cCNF coating promoted cell survival. The c+aCNF construct proved to combine benefits from both types of CNFs, which means that the c+aCNF cell carrier is a promising candidate for further application in skin tissue engineering.

Physical Characteristics of Particle Emissions from a Medium Speed Ship Engine Fueled with Natural Gas and Low-Sulfur Liquid Fuels.

Particle emissions from marine traffic affect significantly air quality in coastal areas and the climate. The particle emissions were studied from a 1.4 MW marine engine operating on low-sulfur fuels natural gas (NG; dual-fuel with diesel pilot), marine gas oil (MGO) and marine diesel oil (MDO). The emitted particles were characterized with respect to particle number (PN) emission factors, PN size distribution down to nanometer scale (1.2-414 nm), volatility, electric charge, morphology, and elemental composition. The size distribution of fresh exhaust particles was bimodal for all the fuels, the nucleation mode highly dominating the soot mode. Total PN emission factors were 2.7 × 1015-7.1 × 1015 #/kWh, the emission being the lowest with NG and the highest with MDO. Liquid fuel combustion generated 4-12 times higher soot mode particle emissions than the NG combustion, and the harbor-area-typical lower engine load (40%) caused higher total PN emissions than the higher load (85%). Nonvolatile particles consisted of nanosized fuel, and spherical lubricating oil core mode particles contained, e.g., calcium as well as agglomerated soot mode particles. Our results indicate the PN emissions from marine engines may remain relatively high regardless of fuel sulfur limits, mostly due to the nanosized particle emissions.

Carbon coated TiO2 nanoparticles prepared by pulsed laser ablation in liquid, gaseous and supercritical CO2.

We report on the synthesis of TiO2 nanoparticles using nanosecond pulse laser ablation of titanium in liquid, gaseous and supercritical CO2. The produced particles were observed to be mainly anatase-TiO2 with some rutile-TiO2. In addition, the particles were covered by a carbon layer. Raman and x-ray diffraction data suggested that the rutile content increases with CO2 pressure. The nanoparticle size decreased and size distribution became narrower with the increase in CO2 pressure and temperature, however the variation trend was different for CO2 pressure compared to temperature. Pulsed laser ablation in pressurized CO2 is demonstrated as a single step method for making anatase-TiO2/carbon nanoparticles throughout the pressure and temperature ranges 5-40 MPa and 30 °C-50 °C, respectively.

Development and application of implementation tools for rehabilitation guidelines.

OBJECTIVE: To describe a project to develop guideline implementation tools (GItools) for rehabilitation guidelines, and a collaboration between a guideline producer and a healthcare organization to implement guidelines into care pathways. DESIGN: Descriptive case study. METHODS: A national guideline organization in Finland launched a 3-year project in 2015 to implement rehabilitation recommendations. Usability of the GItools was evaluated and improved, based on literature, workshops and surveys. An implementation plan guided the production of the GItools. An implementation plan was developed to integrate the shoulder disorders guideline into a care pathway at Päijät-Häme district rehabilitation unit. The implementation plan was produced in 3 facilitated workshops, which included brainstorming, snowballing, prioritizing and short lectures. RESULTS: Twenty implementation plans and 119 different GItools for 22 guidelines were developed. The GItools, in particular patient material, were perceived as useful for the facilitation of guideline implementation. Four seminars and 14 sessions of continuous medical education were arranged. A plan was developed and executed for the implementation of the shoulder disorders guideline. CONCLUSION: It is feasible for a guideline producer to systematically include GItools into rehabilitation guidelines. This implementation project was an example of a successful collaboration between a guideline producer and a healthcare organization.

Incorporating evidence-based rehabilitation into clinical practice guidelines.

OBJECTIVE: Rehabilitation is often neglected in clinical practice guidelines, even when there is evidence for its effectiveness. The Current Rehabilitation development project, documented in this article, aimed to develop processes and structures to incorporate evidence and good practice on rehabilitation and functional capacity into the Finnish national Current Care Guidelines. DESIGN: Descriptive assessment. METHODS: The 3-year Current Rehabilitation development project was launched in 2012. It began with an assessment of existing rehabilitation evidence on the Current Care Guideline database and a query to Finnish rehabilitation experts. The project group developed and compiled tools for Current Care editors and guideline panels. The editorial team continued to monitor changes in rehabilitation evidence in the guidelines. RESULTS: During the years 2012-2014, a total of 54 guidelines were published, and rehabilitation was incorporated into 31 of them. The number of rehabilitation-related evidence summaries increased from 49 to 164. During the next 3 years an additional 41 guidelines were published. Rehabilitation was incorporated to 24 of them, and the number of rehabilitation-related evidence summaries increased from 78 to 136. CONCLUSION: The level of evidence criteria used for rehabilitative interventions were the same as for symptomatic or curative interventions. Evidence showing the effectiveness of rehabilitation increased substantially during the project.

The effect of inferior turbinate surgery on ciliated epithelium: A randomized, blinded study.

OBJECTIVES/HYPOTHESIS: The aim of this study was to evaluate statistically the effects of radiofrequency ablation, diode laser, and microdebrider-assisted inferior turbinoplasty techniques on ciliated epithelium and mucociliary function. STUDY DESIGN: Prospective randomized study. METHODS: A total of 66 consecutively randomized adult patients with enlarged inferior turbinates underwent either a radiofrequency ablation, diode laser, or microdebrider-assisted inferior turbinoplasty procedure. Assessments were conducted prior to surgery and 3 months subsequent to the surgery. The effect on ciliated epithelium was evaluated using a score based on the blinded grading of the preoperative and postoperative scanning electron microscopy images of mucosal samples. The effect on mucociliary function, in turn, was evaluated using saccharin transit time measurement. RESULTS: The score of the number of cilia increased statistically significantly in the radiofrequency ablation (P = .03) and microdebrider-assisted inferior turbinoplasty (P = .04) groups, but not in the diode laser group. The score of the squamous metaplasia increased statistically significantly in the diode laser group (P = .002), but not in the other two groups. There were no significant changes found between the preoperative and postoperative saccharin transit time values in any of the treatment groups. CONCLUSIONS: Radiofrequency ablation and microdebrider-assisted inferior turbinoplasty are more mucosal preserving techniques than the diode laser, which was found to increase the amount of squamous metaplasia at the 3-month follow-up. The number of cilia seemed to even increase after radiofrequency ablation and microdebrider-assisted inferior turbinoplasty procedures, but not after diode laser. Nevertheless, the mucociliary transport was equally preserved in all three groups. LEVEL OF EVIDENCE: 1b Laryngoscope, 129:18-24, 2019.

Synthesis of ZnO nanowires with supercritical carbon dioxide and post heat treatment.

Zinc oxide (ZnO) nanowires are used in applications such as gas sensors and solar cells. This work presents a novel synthesis route for ZnO nanowires using supercritical carbon dioxide (scCO2) and post heat treatment. The method used scCO2 and a precursor solution as reactants to form nanowires on a galvanized surface. After the scCO2 treatment, the substrate was heat-treated. The surfaces were characterized with SEM, TEM, EDS, FTIR, XRD and optical spectroscopy. The FTIR results showed that the surface structure had changed from zinc hydroxycarbonate to ZnO during the heat treatment. The nanowires were slightly bent due to the heat treatment according to the SEM images. The presence of ZnO was further confirmed with XRD. The bandgap of the structure was determined by reflectance measurements and showed a value of 3.23 eV. The synthesis method presented in this study offers a unique approach into the formation of ZnO nanowires in a facile, rapid and environmentally friendly process.

Nutrient management via struvite precipitation and recovery from various agroindustrial wastewaters: Process feasibility and struvite quality.

Improving environmental protection and finding sustainable and renewable resources of nutrients are core issues in circular bioeconomy. Thus, this study evaluated the efficiency of recovering struvite, MgNH4PO4·6H2O, from different agro-industrial wastewaters (four highly loaded reject waters of anaerobically co-digested agro-industrial waste and a raw swine slurry) and assessed the quality of recovered struvite crystals and their reusability as fertilizer. The efficiency of crystallization (Ec 40-80%) and amount of struvite in the precipitate (Pp 55-94%) highly varied due to the characteristics of influent wastewaters, particularly to the content of competing elements, such as alkaline and heavy metals and total solids (TS). In particular, Ec (94, 75, 61%) and Pp (76, 66, 48%) decreased at increasing TS (0.57, 0.73, 0.99%), demonstrating the hindering effect of solid content on struvite recovery and quality. According to X-ray diffraction analysis, the structure of all isolated samples corresponded to crystalline, orthorhombic struvite, which exhibited high purity (32-48 g/kgd N, 114-132 g/kgd P, and 99-116 g/kgd Mg) containing only a few foreign elements, whose amount depended on the characteristics of the influent wastewater. All struvite contained other plant macronutrients (K, Ca) and many micronutrients (Fe, Na, Cu, Mn, Co, Zn) that further enhance its agronomic value. Therefore, this study showed that struvite can be successfully recovered from a wide range of highly loaded agroindustrial wastewaters, and that the quality of the recovered struvite could be suitable for reuse in agriculture.

Fabrication of ultrathin multilayered superomniphobic nanocoatings by liquid flame spray, atomic layer deposition, and silanization.

Superomniphobic, i.e. liquid-repellent, surfaces have been an interesting area of research during recent years due to their various potential applications. However, producing such surfaces, especially on hard and resilient substrates like stainless steel, still remains challenging. We present a stepwise fabrication process of a multilayered nanocoating on a stainless steel substrate, consisting of a nanoparticle layer, a nanofilm, and a layer of silane molecules. Liquid flame spray was used to deposit a TiO2 nanoparticle layer as the bottom layer for producing a suitable surface structure. The interstitial Al2O3 nanofilm, fabricated by atomic layer deposition (ALD), stabilized the nanoparticle layer, and the topmost fluorosilane layer lowered the surface energy of the coating for enhanced omniphobicity. The coating was characterized with field emission scanning electron microscopy, focused ion beam scanning electron microscopy, x-ray photoelectron spectroscopy, contact angle (CA) and sliding angle (SA) measurements, and microscratch testing. The widely recognized requirements for superrepellency, i.e. CA > 150° and SA < 10°, were achieved for deioinized water, diiodomethane, and ethylene glycol. The mechanical stability of the coating could be varied by tuning the thickness of the ALD layer at the expense of repellency. To our knowledge, this is the thinnest superomniphobic coating reported so far, with the average thickness of about 70 nm.

Aligned Poly(ε-caprolactone) Nanofibers Guide the Orientation and Migration of Human Pluripotent Stem Cell-Derived Neurons, Astrocytes, and Oligodendrocyte Precursor Cells In Vitro.

Stem cell transplantations for spinal cord injury (SCI) have been studied extensively for the past decade in order to replace the damaged tissue with human pluripotent stem cell (hPSC)-derived neural cells. Transplanted cells may, however, benefit from supporting and guiding structures or scaffolds in order to remain viable and integrate into the host tissue. Biomaterials can be used as supporting scaffolds, as they mimic the characteristics of the natural cellular environment. In this study, hPSC-derived neurons, astrocytes, and oligodendrocyte precursor cells (OPCs) are cultured on aligned poly(ε-caprolactone) nanofiber platforms, which guide cell orientation to resemble that of spinal cord in vivo. All cell types are shown to efficiently spread over the nanofiber platform and orient according to the fiber alignment. Human neurons and astrocytes require extracellular matrix molecule coating for the nanofibers, but OPCs grow on nanofibers without additional treatment. Furthermore, the nanofiber platform is combined with a 3D hydrogel scaffold with controlled thickness, and nanofiber-mediated orientation of hPSC-derived neurons is also demonstrated in a 3D environment. In this work, clinically relevant materials and substrates for nanofibers, fiber coatings, and hydrogel scaffolds are used and combined with cells suitable for developing functional cell grafts for SCI repair.

Pulsed Laser Ablation-Induced Green Synthesis of TiO2 Nanoparticles and Application of Novel Small Angle X-Ray Scattering Technique for Nanoparticle Size and Size Distribution Analysis.

This paper aims to introduce small angle X-ray scattering (SAXS) as a promising technique for measuring size and size distribution of TiO2 nanoparticles. In this manuscript, pulsed laser ablation in liquids (PLAL) has been demonstrated as a quick and simple technique for synthesizing TiO2 nanoparticles directly into deionized water as a suspension from titanium targets. Spherical TiO2 nanoparticles with diameters in the range 4-35 nm were observed with transmission electron microscopy (TEM). X-ray diffraction (XRD) showed highly crystalline nanoparticles that comprised of two main photoactive phases of TiO2: anatase and rutile. However, presence of minor amounts of brookite was also reported. The traditional methods for nanoparticle size and size distribution analysis such as electron microscopy-based methods are time-consuming. In this study, we have proposed and validated SAXS as a promising method for characterization of laser-ablated TiO2 nanoparticles for their size and size distribution by comparing SAXS- and TEM-measured nanoparticle size and size distribution. SAXS- and TEM-measured size distributions closely followed each other for each sample, and size distributions in both showed maxima at the same nanoparticle size. The SAXS-measured nanoparticle diameters were slightly larger than the respective diameters measured by TEM. This was because SAXS measures an agglomerate consisting of several particles as one big particle which slightly increased the mean diameter. TEM- and SAXS-measured mean diameters when plotted together showed similar trend in the variation in the size as the laser power was changed which along with extremely similar size distributions for TEM and SAXS validated the application of SAXS for size distribution measurement of the synthesized TiO2 nanoparticles.

Insight to Nanoparticle Size Analysis-Novel and Convenient Image Analysis Method Versus Conventional Techniques.

The aim of this paper is to introduce a new image analysis program "Nanoannotator" particularly developed for analyzing individual nanoparticles in transmission electron microscopy images. This paper describes the usefulness and efficiency of the program when analyzing nanoparticles, and at the same time, we compare it to more conventional nanoparticle analysis techniques. The techniques which we are concentrating here are transmission electron microscopy (TEM) linked with different image analysis methods and X-ray diffraction techniques. The developed program appeared as a good supplement to the field of particle analysis techniques, since the traditional image analysis programs suffer from the inability to separate the individual particles from agglomerates in the TEM images. The program is more efficient, and it offers more detailed morphological information of the particles than the manual technique. However, particle shapes that are very different from spherical proved to be problematic also for the novel program. When compared to X-ray techniques, the main advantage of the small-angle X-ray scattering (SAXS) method is the average data it provides from a very large amount of particles. However, the SAXS method does not provide any data about the shape or appearance of the sample.

Hydrothermal carbonization of pulp mill streams.

The progress of the conversion, the yield, the structure and the morphology of the produced carbonaceous materials as a function of time were systematically studied with pyrolysis-GC/FID and FESEM microscope. The conversion of galactoglucomannan, bleached kraft pulp and TEMPO oxidized cellulose nanofibrils followed the reaction route of glucose being slower though with fibrous material, higher molar mass and viscosity. The conversion of kraft lignin was minor following completely different reaction route. Carbonaceous particles of different shape and size were produced with yields between 23% and 73% after 4h with being higher for lignin than carbohydrates. According to the results, potential pulp mill streams represent lignocellulosic resources for generation of carbonaceous materials.

Coating of gold nanoparticles made by pulsed laser ablation in liquids with silica shells by simultaneous chemical synthesis.

Coating of gold nanoparticles with silica shells by the well known Stöber-method requires the use of additional coupling agents to seed the growth of the shell as gold does not form a native oxide. Here we report a novel single-step process to create the gold nanoparticles directly into a mixture of tetraethyl orthosilicate and a catalyst by means of pulsed laser ablation in liquids. We observe that good silica shells are achieved only when all of the reagents are present during the production of the nanoparticles. Experiments with two different laser wavelengths: 515 nm and 1030 nm, show that the formation of the shell is efficient only with the laser wavelength close to the plasmon resonance of the gold nanoparticles. We propose a model indicating that the shell formation is initiated by laser-induced heating of the particles.