Abstract: Multiplex detection of emerging pollutants is essential to improve quality control of water treatment plants, which requires portable systems capable of real-time monitoring. In this paper we describe a flexible, dual electrochemical sensing device that detects nonylphenol and paroxetine in tap water samples. The platform contains two voltammetric sensors, with different working electrodes that were either pretreated or functionalized. Each working electrode was judiciously tailored to cover the concentration range of interest for nonylphenol and paroxetine, and square wave voltammetry was used for detection. An electrochemical pretreatment with sulfuric acid on the printed electrode enabled a selective detection of nonylphenol in 1.0-10 x 10(-6) mol L-1 range with a limit of detection of 8.0 x 10(-7) mol L-1. Paroxetine was detected in the same range with a limit of detection of 6.7 x 10(-7) mol L-1 using the printed electrode coated with a layer of carbon spherical shells. Simultaneous detection of the two analytes was achieved in tap water samples within 1 min, with no fouling and no interference effects. The long-term monitoring capability of the dual sensor was demonstrated in phosphate buffer for 45 days. This performance is statistically equivalent to that of high-performance liquid chromatography (HPLC) for water analysis. The dual-sensor platform is generic and may be extended to other water pollutants and clinical biomarkers in real-time monitoring of the environment and health conditions.

Abstract: Solid state compounds which exhibit non-centrosymmetric crystal structures are of great interest due to the physical properties they can exhibit. The 'hybrid improper' mechanism – in which two non-polar distortion modes couple to, and stabilize, a further polar distortion mode, yielding an acentric crystal structure – offers opportunities to prepare a range of novel non-centrosymmetric solids, but examples of compounds exhibiting acentric crystal structures stabilized by this mechanism are still relatively rare. Here we describe a series of bismuth-containing layered perovskite oxide phases, RbBiNb2O7, LiBiNb2O7 and NaBiNb2O7, which have structural frameworks compatible with hybrid-improper ferroelectricity, but also contain Bi3+ cations which are often observed to stabilize acentric crystal structures due to their 6s(2) electronic configurations. Neutron powder diffraction analysis reveals that RbBiNb2O7 and LiBiNb2O7 adopt polar crystal structures (space groups I2cm and B2cm respectively), compatible with stabilization by a trilinear coupling of non-polar and polar modes. The Bi3+ cations present are observed to enhance the magnitude of the polar distortions of these phases, but are not the primary driver for the acentric structure, as evidenced by the observation that replacing the Bi3+ cations with Nd3+ cations does not change the structural symmetry of the compounds. In contrast the non-centrosymmetric, but non-polar structure of NaBiNb2O7 (space group P2(1)2(1)2(1)) differs significantly from the centrosymmetric structure of NaNdNb2O7, which is attributed to a second-order Jahn-Teller distortion associated with the presence of the Bi3+ cations.

Abstract: The Stark effect is one of the most efficient mechanisms to manipulate many-body states in nanostructured systems. In mono- and few-layer transition metal dichalcogenides, it has been successfully induced by optical and electric field means. Here, we tune the optical emission energies and dissociate excitonic states in MoSe2 monolayers employing the 220 MHz in-plane piezoelectric field carried by surface acoustic waves. We transfer the monolayers to high dielectric constant piezoelectric substrates, where the neutral exciton binding energy is reduced, allowing us to efficiently quench (above 90%) and red-shift the excitonic optical emissions. A model for the acoustically induced Stark effect yields neutral exciton and trion in-plane polarizabilities of 530 and 630 x 10(-5) meV/(kV/cm)(2), respectively, which are considerably larger than those reported for monolayers encapsulated in hexagonal boron nitride. Large in-plane polarizabilities are an attractive ingredient to manipulate and modulate multiexciton interactions in two-dimensional semiconductor nanostructures for optoelectronic applications.

Abstract: The interaction between dislocations and nano-precipitates during deformation directly influences hardening response of precipitation-strengthening metals such as Al-Mg-Si alloys. However, how coherent and semi-coherent nano-precipitates accommodate external deformation applied to an Al alloy remains to be elucidated. In-situ tensile experiments in a transmission electron microscope (TEM) were conducted to study the dynamic process of dislocations cutting through coherent needle-like beta '' precipitates with diameters of 3 similar to 8 nm. Comprehensive investigations using in-situ, ex-situ TEM and atom probe tomography uncovered that beta '' precipitates were firstly sheared into small fragments, and then the rotation of the fragments, via sliding along precipitate/matrix interfaces, destroyed their initially coherent interface with the Al matrix. In contrast, semi-coherent beta' precipitates with sizes similar to beta '' were more difficult to be fragmented and accumulation of dislocations at the interface increased interface misfit between beta' and the Al matrix. Consequently, beta' precipitates could basically maintain their needle-like shape after the tensile deformation. This research gains new insights into the interaction between nano-precipitates and dislocations. (C) 2021 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Abstract: Scanning electron microscopy coupled with microanalysis (SEM-EDX) is an important analytical tool for the morphological and chemical characterization of different types of materials. In many applications, SEM-EDX elemental maps are usually used and processed as images, thus flattening and reducing the spectroscopic information contained in EDX hyperspectral data cubes. The exploitation of the full hyperspectral dataset could be indeed very useful for the study of complex matrices like soil. In order to maximize the information attainable by SEM-EDX data cubes analysis, the software package “Datamuncher Gamma” was implemented and applied to study soil aggregates. By using this approach, different phases (silicates, aluminosilicates, Ca-carbonates, Ca-phosphates, organic matter, iron oxides) inside soil aggregates were successfully identified and segmented. The advantages of this method over the common ROI imaging approach are presented. Finally, this method was used to compare different aggregates in a Cr-polluted soil and understand their possible pedological history. The present method can be used for the analysis of every type of SEM-EDX data cubes, allowing its application to different types of samples and fields of study.

Abstract: Meeting rooms are reserved 30% of working hours but only used for 20% of that time. By implementing a strategy where the available capacity is leased to the wider market rather than just the building users, there is a positive impact on the economic, environmental, and social factors of the building and its surroundings. This study uses the building 'The Globe' in The Hague as a case study, and then projects the results to the entire city. In case of The Globe, implementing a lease out strategy achieves a reduction of 36% of the annual rent of the meeting rooms to the building's tenant. The owner benefits from a revenue increase of 12.5%, with the same operational expenses (except the reservation system), leading to a proportional higher valuation of the building. Annual energy consumption may be lowered by 6.2%. This study contributes to the literature by considering the total benefits that could be obtained by more efficient use of office space that is currently underused. The application of technology generates added value for economic, environmental, and social factors. These factors are important in real estate as they (among others) have a direct link to the Environmental, Social and Governance (ESG) analysis that investors make before proceeding with an investment.

Abstract: The approaching end-of life phase of early installed PV modules gave rise to a variety of potential end-of-life strategies, ranging from basic generic waste management strategies to advanced case-specific recycling options. However, no comprehensive assessment on the full range of technological possibilities is available and only limited attention was given to the material recovery rates of these different technologies in light of circular economy. In addition, current material recovery rates are indifferent towards the material value and the value of their secondary applications. Based on an extensive literature review, ten end-of-life scenarios with potential learning effects are identified and their material flows are quantified using a combined material and substance flow analysis. Subsequently, material recovery rates from a mass, economic value and embodied energy perspective are calculated, incorporating the differences in secondary applications. The differences in the mass-based recovery rates of the seven end-of-life scenarios that did not have landfill or municipal waste incineration as the main destination were minimal, as 73-79% of the mass was recovered for the best-case learning scenario. For the economic value recovery rate (9-66%) and the embodied energy recovery rate (18-45%), more profound differences were found. The collection rate was identified as most crucial parameter for all end-of-life scenarios, learning scenarios and recycling indicators. The mass-based recovery rate might favor end-of-life scenarios that lead to dissipation of valuable materials in non-functional secondary applications. Additional targets are required to avoid cascading of valuable materials and to avoid the economic cost and environmental burden of virgin materials.

Abstract: Electron microscopy is an excellent tool which provides resolution down to the atomic scale with up to pm precision in locating atoms. The characterization of materials in these length scales is of utmost importance to answer questions in biology, chemistry and material science. The successful implementation of aberration-corrected microscopes made atomic resolution imaging relatively easy, this could give the impression that the development of novel electron microscopy techniques would stagnate and only the application of these instruments as giant magnifying tools would continue. This is of course not true and a multitude of problems still exist in electron microscopy. Two of such issues are discussed below. One of the biggest problems in electron microscopy is the presence of beam damage which occurs due the fact that the highly energetic incoming electrons have sufficient kinetic energy to change the structure of the material. The amount of damage induced depends on the dose, hence minimizing this dose during an experiment is beneficial. This minimizing of the total dose comes at the expense of more noise due to the counting nature of the electrons. For this reason, the implementation of four dimensional scanning transmission electron microscopy (4D STEM) experiments has reduced the total dose needed per acquisition. However, the current cameras used to measure the diffraction patterns are still two orders of magnitude slower than to the conventional STEM methods. Improving the acquisition speed would make the 4D STEM technique more feasible and is of utmost importance for the beam sensitive materials since less dose is used during the acquisition. In TEM there is not only the possibility to perform imaging experiments but also spectroscopic measurements. There are two frequently used methods: electron energy-loss spectroscopy (EELS) and energy dispersive x-ray spectroscopy (EDX). EELS measures the energy-loss spectrum of the incoming electron which gives information on the available excitations in the material providing elemental sensitivity. In EDX, the characteristic x-rays, arising from the decay of an atom which is initially excited due to the incoming electrons, are detected providing similar elemental analysis. Both methods are able to provide comparable elemental information where in certain circumstances one outperforms the other. However, both methods have a detection limit of approximately 100-1000 ppm which is not sufficient for some materials. In this thesis, two novel techniques which can make significant progress for the two problems discussed above.

Abstract: Scaling down the size of transistors has been a trend for several decades which has led to improved transistor performance, increased transistor density and hence the overall computation power of IC chips. The trend slowed in recent years due to reliability and power consumption issues at the nanoscale. Hence strain is introduced into transistor channels that has beneficial effects on improving the mobility of charge carriers, providing an alternative pathway for enhancing transistor performance. Therefore, monitoring strain is vital for the semiconductor industry. With the recent trend of decreasing device dimensions (FinFETS ~ 10-20nm) and strain modulation being used throughout, industry needs a reliable and fast method as quality control or defect characterisation. Such a universal strain measurement method does not exist, and one relies on a combination of quantitative in-line methods and complex off-line approaches. In this thesis, I investigated TEM and Raman spectroscopy-based methodologies for strain measurement. In terms of TEM methodologies, advancements are made for the STEM moiré imaging, targeting strain spatial resolution enhancement. I introduce advanced quadrature demodulation and phase stepping interferometry applied to STEM moiré that greatly enhances the spatial resolution while providing enhanced field of view and sensitivity for strain measurement. We introduce ways to reduce scan distortions in strain maps using an alternative scan strategy called “Block scanning” and the non-linear regression applied for strain extraction. Prospects for 3D strain analysis using high-resolution tomography is also investigated which gives direct access for the full second order strain tensors calculation. Finally, we compare strain measurements from TEM techniques with inline techniques like Raman spectroscopy. Raman stress measurement involves sensitive identification of the TO and LO phonon peaks. Raman spectrum of strained Ge transistor channel consists of strongly overlapping peaks within the spectral resolution of the spectrometer. Hence, the process of deconvolution of the two peaks is rather challenging. Hence, we explore new polarisation geometries like radially polarised incoming light which was shown to ease the deconvolution problem resulting in improved precision for Raman stress–strain measurements.

Abstract: In the biogeochemical flows on Earth, the reactive nitrogen (Nr) level has three times surpassed the safe boundary. The severe transgression of this boundary goes against sustainable planetary development. The modern food production process excessively relies on synthetic Nr fertilizers from the Haber– Bosch process. However, the massive loss of valuable nitrogen resources (i.e., 78-89%) from agriculture has been causing severe nitrogen cascade. Besides, the domestic wastewater in some local areas is discharged without proper treatment, making it a nonnegligible source of Nr pollution for local water bodies. Anthropogenic activities keep pumping out Nr pollution via point-source and non-point-source (NPS) emissions. Compared to the NPS emissions, point sources give visible and identified waste streams. It is vital to intervene the nitrogen cascade from point sources and facilitate humanity back to the safe Nr boundary. The collected and collectible Nr streams from food production, waste management, and recycling secondary raw materials can be used as waste-based fertilizers for agricultural cultivation. Besides the well-investigated recovery of inorganic Nr, organic Nr accounts for a massive Nr proportion on the Earth. Proper handling and treatment make these useful organic fertilizers for soil-based cultivation. However, these organic Nr fertilizers cannot directly apply to fertigation or hydroponic cultivation systems, and further biological conversion via nitrogen mineralization and nitrification to nitrate is essential. Besides the direct Nr cycling, the indirect Nr cycling ‘over the atmosphere’ should also be considered. In this way, the nitrogen cycle can be completed via converting the waste Nr back to nitrogen gas (i.e., Nr removal) and then synthesizing into Nr again. The municipal wastewater treatment plants receive a vast amount of low-strength Nr wastewater (mainly as ammonium) daily. Compared to the conventional nitrification/denitrification process, partial nitritation/anammox (PN/A) is considered a resource- and cost-effective technology for wastewater with a low COD/N ratio. Moreover, the novel autotrophic denitratation/anammox process could be a good Nr removal process for wastewater containing both ammonium and nitrate. This Ph.D. thesis aimed to develop Nr recovery, conversion, and removal bioreactor strategies for different types of waste streams and biomass. Nr recovery was investigated on high-strength Nr waste streams for fertigation or hydroponic applications in Chapters 2 and 3. On the other hand, Nr removal was studied on the medium- to low-strength Nr waste streams in Chapters 4 and 5. In Chapter 2, a novel mineralization and nitrification system was proposed, producing nutrient solutions from solid organic fertilizers for hydroponic systems. Batch tests showed that aerobic incubation at 35°C could realize the NO₃⁻-N production efficiency above 90% from a novel microbial fertilizer. Subsequently, in the stirred tank bioreactor test, NO₃⁻-N production efficiency stabilized in a range of 44-51% under the influent loading rate of 400 mg TN L⁻¹ d⁻¹ at a 5-day HRT. Using Ca(OH)₂ and Mg(OH)₂ as pH control reagents generated the nutrient solutions with different P, Ca, and Mg nutrient levels. After modeling the nutrient balancing process, the proportion of organic-sourced NO₃⁻-N in the Hoagland nutrient solution (HNS) of Ca(OH)₂ scenario was 92.7%, while only 37.4% in the Mg(OH)₂ scenario. Compared to commercial scenarios, the total costs of the organic-sourced HNS can be cost-competitive for hydroponic cultivation. In Chapter 3, the Nr recovery as nitrate (NO₃⁻-N) from diluted human urine (around 670 mg N L⁻¹) was explored in a trickling filter (TF) for the first time. A novel concept of in-situ integrating the TF system into hydroponic systems was proposed as meaningful progress towards sustainable agriculture. The difference between synthetic and real urine in nitrification efficiency was found to be negligible. The full nitrification of alkalinized real urine was realized in the pH-controlled TF by calcium hydroxide (Ca(OH)₂) at around pH 6. The TF could handle different urine collection batches and maintain relatively stable nitrification performance, with NO₃⁻-N production efficiency and rate of 88±3% and 136±4 mg N L⁻¹ d⁻¹, respectively. The optimal HLR to realize this nitrification performance was 2 m³ m⁻² h⁻¹, with energy consumption of 1.8 kWh electricity kg⁻¹ NO₃⁻-N production. Ca(OH)₂, as a cheap base, its triple advantages on urine alkalinization, full nitrification, and macronutrient supplementation were successfully demonstrated in our proposed concept. In Chapter 4, towards more sustainable wastewater treatment, the feasibility of one-stage partial nitritation/anammox (PN/A) was investigated in three parallel packed-bed trickling filters (TFs), with three types of carrier materials of different specific surface areas. Synthetic wastewater containing 100-250 mg NH₄⁺-N L⁻¹ was tested to mimic medium-strength household waste streams after carbon removal. Interestingly, the cheap carrier based on expanded clay achieved similar rates as commercially used plastic carrier materials. The top passive ventilation combined with an optimum hydraulic loading rate of 1.8 m³ m⁻² h⁻¹ could reach approximately 60% total nitrogen (TN) removal at a rate of 300 mg N L⁻¹ d⁻¹. A relatively low NO₃⁻-N production (13%) via PN/A was achieved in TFs. Most of the TN removal took place in the top compartment, where anammox activity was the highest. Energy consumption estimation (0.78 kWh electricity g⁻¹ N removed) suggested that the proposed process could be a suitable low-cost alternative for nitrogen removal. In Chapter 5, coupling sulfur-driven denitratation (SDN) with anammox was proposed to treat the wastewater containing both NO₃⁻-N and NH₄⁺-N, like the secondary effluents of mainstream PN/A processes. To explore the feasibility of sufficient and stable NO₂⁻-N accumulation via SDN in the long term, the effects of pH setpoints, residual NO₃⁻-N level, and biomass-specific NO₃⁻-N loading rate (BSNLR) were investigated. Alternating the pH setpoints between 7.0 and 8.5 could temporarily stimulate the NO₂⁻-N accumulation. Both the residual NO₃⁻-N and BSNLR showed highly positive correlations with the NO₂⁻-N accumulation efficiency. Under the control of pH 8.5, 1.0±0.8 mg NO₃⁻-N L⁻¹ and 150±42 mg NO₃⁻-N g⁻¹ VSS d⁻¹, SDN could produce 6.4±1.0 mg NO₂⁻-N L⁻¹ in the short term. Thiobacillus members may play a crucial role in managing the NO₂⁻-N accumulation, but the reduction of abundance and possible adaptation significantly impaired the efficacy of control strategies in the long run. Overall, novel technologies have been proposed to sustainably convert Nr in waste streams and biomass. The decision for Nr recovery versus removal and synthesis should be based on specific cases with the best environmental, economic, and human-health sustainability. In the future, the Nr management concepts should be further improved to make the nitrogen cycle more sustainable with higher resource use efficiency and less Nr emissions to the environment. Although the thesis is mainly focused on limited types of Nr waste streams, it pointed out the direction of sustainable Nr management and could facilitate the Nr back to the safe boundary in the long run.

Abstract: Some volatile organic compounds (VOCs), generated and accumulated in exhibition cases, are capable of inducing degradation in historical artifacts. In this context, it is of special importance to distinguish between VOCs emitted by the construction materials and/or the historical objects, with the ultimate goal of proposing an appropriate mitigation strategy. To pursue this goal, a comprehensive analysis based on solid phase microextraction (SPME) coupled to gas chromatography-mass spectrometry (GC-MS) has been optimized. The sampling setup used in this study does not require any modification of the exhibition design, and the testing remained nearly invisible and unobtrusive to museum visitors. This methodology has been applied to an issue encountered at the National Museum of the American Indian (Smithsonian Institution), where an unpleasant smell was detected in airtight exhibition cases already on display containing sensitive historical objects. The analysis of the volatiles emitted by construction materials allowed for identification of characteristic markers emitted by each material, and the ability to identify their overall contribution in the exhibition case. Via this method, SPME-GC-MS confirmed via the detection of some specific markers that the unpleasant smell was released by one of the construction materials and had accumulated in the exhibition case. In addition, due to the measurements taken in different positions around the exhibition cases, results were useful to point out the range of efficiency of the sorbent material placed in some of the exhibition cases as a first attempt of mitigation technique. (C) 2020 Elsevier Masson SAS. All rights reserved.

Abstract: Two mass spectrometry (MS) methods, solid-phase microextraction gas chromatography (SPME–GC–MS) and direct analysis in real time (DART-MS), have been explored to investigate widespread efflorescence observed on exhibited objects at the Smithsonian’s National Museum of the American Indian in New York (NMAI-NY). Both methods show great potential, in terms of speed of analysis and level of information, for identifying the organic component of the efflorescence as 2,2,6,6-tetramethyl-4-piperidinol (TMP-ol) emitted by the structural adhesive (Terostat MS 937) used for exhibit case construction. The utility of DART-MS was proven by detecting the presence of TMP-ol in construction materials in a fraction of the time and effort required for SPME–GC–MS analysis. In parallel, an unobtrusive SPME sampling strategy was used to detect volatile organic compounds (VOCs) accumulated in the exhibition cases. This sampling technique can be performed by collections and conservation staff at the museum and shipped to an off-site laboratory for analysis. This broadens the accessibility of MS techniques to museums without access to instrumentation or in-house analysis capabilities.

Abstract: This study investigates the complex mixture of volatile organic compounds (VOCs) released by and accumulated within a collection of historic medicinal, pharmaceutical, and cosmetic artifacts housed at the National Museum of American History (Smithsonian Institution). In recent years, staff have become concerned, both for the safety of the objects and for personnel working in the collection, about strong unremediated odors accumulating within several storage cabinets. Museum staff also wondered if non-odorous off-gassing might need remediation. Solid-phase microextraction combined with gas chromatography–mass spectrometry analysis (SPME–GC–MS) was used to identify VOCs present in the storage room housing the collection. Over 160 compounds were detected and identified overall. Among these, 49 appeared to be directly related to ingredients used in the manufacture of many collection items. The results of the study suggest that SPME–GC–MS can be a strong tool for the rapid screening of multicomponent museum collections exhibiting off-gassing problems, before the pursuit of other more tedious analytical approaches. Additionally, the study reveals valuable insight into the characteristic volatile emission of historic medicinal, pharmaceutical, and cosmetic artifacts, increasing understanding of, and decision-making for, similar collections of objects. Eventually, it is hoped that this information can be used to inform mitigation strategies for the capture and reduction of VOCs in collections storage areas.

Abstract: The current work, designed for the photoelectrochemical detection of DNA, evaluates light-responsive DNA probes carrying molecular photosensitizers generating singlet oxygen (1O2). We take advantage of their chromophore’s ability to produce 1O2 upon photoexcitation and subsequent photocurrent response. Type I, fluorescent and type II photosensitizers were studied using diode lasers at 406 nm blue, 532 nm green and 659 nm red lasers in the presensce and absence of a redox reporter, hydroquinone (HQ). Only type II photosensitizers (producing 1O2) resulted in a noticeable photocurrent in 1–4 nA range upon illumination, in particular, dissolved DNA probes labeled with chlorin e6 and erythrosine were found to give a well-detectable photocurrent response in the presence of HQ. Whereas, Type I photosensitizers and fluorescent chromophores generate negligible photocurrents (<0.15 nA). The analytical performance of the sensing system was evaluated using a magnetic beads-based DNA assay on disposable electrode platforms, with a focus to enhance the sensitivity and robustness of the technique in detecting complementary DNA targets. Amplified photocurrent responses in the range of 70–100 nA were obtained and detection limits of 17 pM and 10 pM were achieved using magnetic beads-captured chlorin e6 and erythrosine labeled DNA probes respectively. The presented novel photoelectrochemical detection can further be optimized and employed in applications for which enzymatic amplification such as polymerase chain reaction (PCR) is not applicable owing to their limitations and as an effective alternative to colorimetric detection when rapid detection of specific nucleic acid targets is required.

Abstract: Due to the high water- and nutrient-use efficiency, hydroponic cultivation is increasingly vital in progressing to environment-friendly food production. To further alleviate the environmental impacts of synthetic fertilizer production, the use of recovered nutrients should be encouraged in horticulture and agriculture at large. Solid organic fertilizers can largely contribute to this, yet their physical and chemical nature impedes application in hydroponics. This study proposes a bioreactor for mineralization and nitrification followed by a supplementation step for limiting macronutrients to produce nitrate-based solutions from solid fertilizers, here based on a novel microbial fertilizer. Batch tests showed that aerobic conversions at 35 °C could realize a nitrate (NO₃−-N) production efficiency above 90% and a maximum rate of 59 mg N L−1 d−1. In the subsequent bioreactor test, nitrate production efficiencies were lower (44–51%), yet rates were higher (175–212 mg N L−1 d−1). Calcium and magnesium hydroxide were compared to control the bioreactor pH at 6.0 ± 0.2, while also providing macronutrients for plant production. A mass balance estimation to mimic the Hoagland nutrient solution showed that 92.7% of the NO₃−-N in the Ca(OH)₂ scenario could be organically sourced, while this was only 37.4% in the Mg(OH)₂ scenario. Besides, carbon dioxide (CO₂) generated in the bioreactor can be used for greenhouse carbon fertilization to save operational expenditure (OPEX). An estimation of the total OPEX showed that the production of a nutrient solution from solid organic fertilizers can be cost competitive compared to using commercially available liquid inorganic fertilizer solutions.