3D Nanofabrication inside rapid prototyped microfluidic channels showcased by wet-spinning of single micrometre fibres

Microfluidics is an established multidisciplinary research domain with widespread applications in the fields of medicine, biotechnology and engineering. Conventional production methods of microfluidic chips have been limited to planar structures, preventing the exploitation of truly three-dimensional architectures for applications such as multi-phase droplet preparation or wet-phase fibre spinning. Here the challenge of nanofabrication inside a microfluidic chip is tackled for the showcase of a spider-inspired spinneret. Multiphoton lithography, an additive manufacturing method, was used to produce free-form microfluidic masters, subsequently replicated by soft lithography. Into the resulting microfluidic device, a threedimensional spider-inspired spinneret was directly fabricated in-chip via multiphoton lithography. Applying this unprecedented fabrication strategy, the to date smallest printed spinneret nozzle is produced. This spinneret resides tightly sealed, connecting it to the macroscopic world. Its functionality is demonstrated by wet-spinning of single-digit micron fibres through a polyacrylonitrile coagulation process induced by a water sheath layer. The methodology developed here demonstrates fabrication strategies to interface complex architectures into classical microfluidic platforms. Using multiphoton lithography for in-chip fabrication adopts a high spatial resolution technology for improving geometry and thus flow control inside microfluidic chips. The showcased fabrication methodology is generic and will be applicable to multiple challenges in fluid control and beyond

Global CO2 Emissions From Dry Inland Waters Share Common Drivers Across Ecosystems

Many inland waters exhibit complete or partial desiccation, or have vanished due to global change, exposing sediments to the atmosphere. Yet, data on carbon dioxide (CO2) emissions from these sediments are too scarce to upscale emissions for global estimates or to understand their fundamental drivers. Here, we present the results of a global survey covering 196 dry inland waters across diverse ecosystem types and climate zones. We show that their CO2 emissions share fundamental drivers and constitute a substantial fraction of the carbon cycled by inland waters. CO2 emissions were consistent across ecosystem types and climate zones, with local characteristics explaining much of the variability. Accounting for such emissions increases global estimates of carbon emissions from inland waters by 6% (~0.12 Pg C y−1). Our results indicate that emissions from dry inland waters represent a significant and likely increasing component of the inland waters carbon cycle

Global CO2 emissions from dry inland waters share common drivers across ecosystems

Many inland waters exhibit complete or partial desiccation, or have vanished due to global change, exposing sediments to the atmosphere. Yet, data on carbon dioxide (CO2) emissions from these sediments are too scarce to upscale emissions for global estimates or to understand their fundamental drivers. Here, we present the results of a global survey covering 196 dry inland waters across diverse ecosystem types and climate zones. We show that their CO2 emissions share fundamental drivers and constitute a substantial fraction of the carbon cycled by inland waters. CO2 emissions were consistent across ecosystem types and climate zones, with local characteristics explaining much of the variability. Accounting for such emissions increases global estimates of carbon emissions from inland waters by 6% (~0.12 Pg C y−1). Our results indicate that emissions from dry inland waters represent a significant and likely increasing component of the inland waters carbon cycle

Workshop on membrane fouling and monitoring: a summary

Gathering for a workshop hosted by Robert Field at Oxford University, some of the world's leading experts in membrane fouling presented and discussed recent research progress in this area. The delegates paid particular attention to the key issue of biofouling because of its importance in water treatment and its inherent complexity compared to the mechanics of inorganic particulate fouling. It was remarked that the characterisation and understanding of the extracellular polymeric substances (EPS) in biofilms, and the transparent exopolymers (TEP) involved in their development is still a particularly difficult task, which was a subject present during the entire workshop. Furthermore, advances in characterisation of fouling layers and biofilms utilising ultrasonic time-domain reflectometry (UTDR) and confocal laser scanning microscopy (CLSM) were presented, along with a cautionary perspective on interpretation of data from small sample areas. While membrane fouling reduction is traditionally tackled with a prevention and removal strategy, an alternative biofilm management approach was put forward. Although a lot of physical and chemical techniques were presented, delegates also stressed the importance of microbiology for getting the whole picture and the need for a range of carefully selected analytical techniques to do so. This paper summarises the proceedings and discussion at this workshop in September 2012

Direct Observation of Deformation in Microgel Filtration

Colloidal filtration processes using porous membranes suffer from productivity loss due to colloidal matter retention and continuous build-up by the retained matter. Especially during filtration of soft matter, the deformation of the individual colloids that make up the filter cake may be significant; however, this deformation and its impact remain unresolved so far. Yet, understanding the deformation on the single colloid level as well as on the ensemble level is important to be able to deconvolute filter cake properties from resistance increase of the membrane either by simultaneous internal adsorption or blocking of pores. Here, we report on the compression of a filter cake by filtrating soft microgels in a microfluidic channel in front of a model membrane. To study the single colloid deformation amorphous and crystalline domains were built up in front of the membrane and visualized on-line using confocal fluorescence microscopy while adjusting the degree of permeation, i.e., the transmembrane flux. Results show locally pronounced asymmetric deformation in amorphous domains, while the microgels in colloidal crystals approached regular polyeder shape. Increasing the flux beyond the maximum colloid deformation results in non-isochoric microgel behavior. The presented methodology enables a realistic description of complex colloidal matter deposits during filtration

Microfluidic colloid filtration

Filtration of natural and colloidal matter is an essential process in today’s water treatment processes. The colloidal matter is retained with the help of micro- and nanoporous synthetic membranes. Colloids are retained in a “cake layer” – often coined fouling layer. Membrane fouling is the most substantial problem in membrane filtration: colloidal and natural matter build-up leads to an increasing resistance and thus decreasing water transport rate through the membrane. Theoretical models exist to describe macroscopically the hydrodynamic resistance of such transport and rejection phenomena; however, visualization of the various phenomena occurring during colloid retention is extremely demanding. Here we present a microfluidics based methodology to follow filter cake build up as well as transport phenomena occuring inside of the fouling layer. The microfluidic colloidal filtration methodology enables the study of complex colloidal jamming, crystallization and melting processes as well as translocation at the single particle level

Magnetically Actuable Complex-Shaped Microgels for Spatio-Temporal Flow Control

Complex-shaped microgels are promising building blocks for soft metamaterials. Their active and remote orientational control provides significant potential in architecting them in time and space. This work describes the use of magnetically actuable microgels of complex shape for spatio-temporal flow control and showcases the concept for microfluidic impellers. First, the fabrication of complex-shaped magnetically actuable poly(ethylene glycol) diacrylate based microgels via stop-flow lithography is presented. The microgels comprise a pre-programmed magnetic moment set by pre-aligned maghemite nanospindles during the fabrication step. This feature allows the microgels to be positioned in a static magnetic field and rotate under application of a rotating external field. The dependence of the magnetic field rotation rate and strength, maghemite content, and microgel shape on the magnetic response of the microgels is comprehensively quantified. Finally, the magnetic complex-shaped microgels are integrated as actuable impellers in a microfluidic chip. The microgels are positioned in space by polymerizing them around fixed poly(dimethylsiloxane) (PDMS) pillars. Free rotation around the PDMS pillar is achieved due to the oxygen inhibition layer at the chip and pillar surface. The versatility of the fabrication methodology is showcased by the investigation of in-chip mixing in a microfluidic device consisting of soft responsive impellers

Soft Temperature-Responsive Microgels of Complex Shape in Stop-Flow Lithography

Stop-flow lithography (SFL) has emerged as a facile high-throughput fabrication method for μm-sized anisometric particles; yet, the fabrication of soft, anisometric microgels has not frequently been addressed in the literature. Furthermore, and to the best of the authors' knowledge, no soft, complex-shaped microgels with temperature-responsive behavior have been fabricated with this technology before. However, such microgels have tremendous potential as building blocks and actuating elements in rapidly developing fields, such as tissue engineering and additive manufacturing of soft polymeric building blocks, bio-hybrid materials, or soft micro-robotics. Given their great potential, we prove in this work that SFL is a viable method for the fabrication of soft, temperature-responsive, and complex-shaped microgels. The microgels, fabricated in this work, consist of poly(N-isopropylacrylamide) (pNIPAm), which is crosslinked with N,N'-methylenebis(acrylamide). The results confirm that the shape of the pNIPAm microgels is determined by the transparency mask, used in SFL. Furthermore, it is shown that, in order to realize stable microgels, a minimum threshold of crosslinker concentration of 2 wt% is required. Above this threshold, the stiffness of pNIPAm microgels can be deliberately altered by adjusting the concentration of the crosslinker. The fabricated pNIPAm microgels show the targeted temperature-responsive behavior. Within this context, temperature-dependent reversible swelling is confirmed, even for fractal-like geometries, such as micro snowflakes. Thus, these microgels provide the targeted unique combination of softness, shape complexity, and temperature responsiveness and increase the freedom of design for actuated building blocks

PEDOT:PSS-CNT Composite Particles Overcome Contact Resistances in Slurry Electrodes for Flow-Electrode Capacitive Deionization

Activated carbon (AC) particles constitute the current material of choice concerning the preparation of flow electrodes for flow-electrode capacitive deionization (FCDI). They are inexpensive, mass-producible, highly conductive, and exhibit a large specific surface area for ion adsorption. However, despite recent advances concerning the modification of AC slurries, their density, and hydrophobicity still constitute major challenges regarding particle aggregation, sedimentation, and pumpability, restricting their particle load to approximately 25 wt.%. Since the particle volume fraction directly correlates to the chance of particle contact, which dictates the charge transfer and hence the degree of flow electrode utilization, the development of AC-based slurries seems to stagnate. This study addresses these challenges by investigating poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS)-based suspensions as an alternative to conventional carbon-based flow electrodes. The corresponding conductive hydrogel particles feature softness, internal porosity, low density, hydrophilicity, and a mass-specific salt adsorption capacity that exceeds AC by up to ten times. FCDI experiments can reveal that, contrary to AC, the inherent properties of PEDOT:PSS-based particles simplify the slurry preparation process and enable flow electrode circulation at significantly higher particle volume fractions. These results suggest that PEDOT:PSS-based hydrogel particles are a promising candidate to overcome the percolation and contact-related challenges of state-of-the-art AC slurries

Applying the core-satellite species concept: Characteristics of rare and common riverine dissolved organic matter

Peer reviewed: TrueAcknowledgements: We thank the WHONDRS consortium for facilitating generation of data used in this manuscript, including study design, crowdsourced sample collection, sample analysis, and public data publishing. We also thank the organizers and participants of the virtual crowdsourced workshop (Borton et al., 2022) where the initial scientific questions and hypotheses were developed.IntroductionDissolved organic matter (DOM) composition varies over space and time, with a multitude of factors driving the presence or absence of each compound found in the complex DOM mixture. Compounds ubiquitously present across a wide range of river systems (hereafter termed core compounds) may differ in chemical composition and reactivity from compounds present in only a few settings (hereafter termed satellite compounds). Here, we investigated the spatial patterns in DOM molecular formulae presence (occupancy) in surface water and sediments across 97 river corridors at a continental scale using the “Worldwide Hydrobiogeochemical Observation Network for Dynamic River Systems—WHONDRS” research consortium.MethodsWe used a novel data-driven approach to identify core and satellite compounds and compared their molecular properties identified with Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS).ResultsWe found that core compounds clustered around intermediate hydrogen/carbon and oxygen/carbon ratios across both sediment and surface water samples, whereas the satellite compounds varied widely in their elemental composition. Within surface water samples, core compounds were dominated by lignin-like formulae, whereas protein-like formulae dominated the core pool in sediment samples. In contrast, satellite molecular formulae were more evenly distributed between compound classes in both sediment and water molecules. Core compounds found in both sediment and water exhibited lower molecular mass, lower oxidation state, and a higher degree of aromaticity, and were inferred to be more persistent than global satellite compounds. Higher putative biochemical transformations were found in core than satellite compounds, suggesting that the core pool was more processed.DiscussionThe observed differences in chemical properties of core and satellite compounds point to potential differences in their sources and contribution to DOM processing in river corridors. Overall, our work points to the potential of data-driven approaches separating rare and common compounds to reduce some of the complexity inherent in studying riverine DOM.</jats:sec