Search results for: carbo-iron colloids

Authors: Jiancheng Zheng

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When metals are released into water from mining activities, they undergo changes chemically, physically and biologically and then may become more mobile and transportable along the waterway from their original sites. Natural colloids, including both organic and inorganic entities, are naturally occurring in any aquatic environment with sizes in the nanometer range. Natural colloids in a water system play an important role, quite often a key role, in binding and transporting compounds. When assessing and evaluating metals in natural waters, their sources, mobility, fate, and distribution patterns in the system are the major concerns from the point of view of assessing environmental contamination and pollution during resource development. There are a few ways to quantify colloids and accordingly study how metals distribute on different sizes of colloids. Current research results show that the presence of colloids can enhance the transport of some heavy metals in water, while heavy metals may also have an influence on the transport of colloids when cations in the water system change colloids and/or the ion strength of the water system changes. Therefore, studies into the relationship between different sizes of colloids and different metals in a water system are necessary and needed as natural colloids in water systems are complex mixtures of both organic and inorganic as well as biological materials. Their stability could be sensitive to changes in their shapes, phases, hardness and functionalities due to coagulation and deposition et al. and chemical, physical, and biological reactions. Because metal contaminants’ adsorption on surfaces of colloids is closely related to colloid properties, it is desired to fraction water samples as soon as possible after a sample is taken in the natural environment in order to avoid changes to water samples during transportation and storage. For this reason, this study carried out groundwater sample processing in the field, using Prep/Scale tangential flow filtration systems with 3-level cartridges (1 kDa, 10 kDa and 100 kDa). Groundwater samples from seven sites at Fort MacMurray, Alberta, Canada, were fractionated during the 2015 field sampling season. All samples were processed within 3 hours after samples were taken. Preliminary results show that although the distribution pattern of metals on colloids may vary with different samples taken from different sites, some elements often tend to larger colloids (such as Fe and Re), some to finer colloids (such as Sb and Zn), while some of them mainly in the dissolved form (such as Mo and Be). This information is useful to evaluate and project the fate and mobility of different metals in the groundwaters and possibly in environmental water systems.

Keywords: metal, colloid, groundwater, mobility, fractionation, sorption

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Authors: Emmanuelle Maria, Pierre Crançon, Gaëtane Lespes

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Colloids are ubiquitous in the environment and are known to play a major role in enhancing the transport of trace elements, thus being an important vector for contaminants dispersion. Colloids study and characterization are necessary to improve our understanding of the fate of pollutants in the environment. However, in stream water and groundwater, colloids are often very poorly concentrated. It is therefore necessary to pre-concentrate colloids in order to get enough material for analysis, while preserving their initial structure. Many techniques are used to extract and/or pre-concentrate the colloidal phase from bulk aqueous phase, but yet there is neither reference method nor estimation of the impact of these different techniques on the colloids structure, as well as the bias introduced by the separation method. In the present work, we have tested and compared several methods of colloidal phase extraction/pre-concentration, and their impact on colloids properties, particularly their size distribution and their elementary composition. Ultrafiltration methods (frontal, tangential and centrifugal) have been considered since they are widely used for the extraction of colloids in natural waters. To compare these methods, a ‘synthetic groundwater’ was used as a reference. The size distribution (obtained by Field-Flow Fractionation (FFF)) and the chemical composition of the colloidal phase (obtained by Inductively Coupled Plasma Mass Spectrometry (ICPMS) and Total Organic Carbon analysis (TOC)) were chosen as comparison factors. In this way, it is possible to estimate the pre-concentration impact on the colloidal phase preservation. It appears that some of these methods preserve in a more efficient manner the colloidal phase composition while others are easier/faster to use. The choice of the extraction/pre-concentration method is therefore a compromise between efficiency (including speed and ease of use) and impact on the structural and chemical composition of the colloidal phase. In perspective, the use of these methods should enhance the consideration of colloidal phase in the transport of pollutants in environmental assessment studies and forensics.

Keywords: chemical composition, colloids, extraction, preconcentration methods, size distribution

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Authors: Feixiong Chen, Naoufel Haddour, Marie Frenea-Robin, Yves MéRieux, Yann Chevolot, Virginie Monnier

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Neonatal thrombopenia occurs when the mother generates antibodies against her baby’s platelet antigens. It is particularly critical for newborns because it can cause coagulation troubles leading to intracranial hemorrhage. In this case, diagnosis must be done quickly to make platelets transfusion immediately after birth. Before transfusion, platelet antigens must be tested carefully to avoid rejection. The majority of thrombopenia (95 %) are caused by antibodies directed against Human Platelet Antigen 1a (HPA-1a) or 5b (HPA-5b). The common method for antigen platelets detection is polymerase chain reaction allowing for identification of gene sequence. However, it is expensive, time-consuming and requires significant blood volume which is not suitable for newborns. We propose to develop a point-of-care device based on double functionalized magnetic colloids with 1) antibodies specific to antigen platelets and 2) highly sensitive electroactive molecules in order to be detected by an electrochemical microsensor. These magnetic colloids will be used first to isolate platelets from other blood components, then to capture specifically platelets bearing HPA-1a and HPA-5b antigens and finally to attract them close to sensor working electrode for improved electrochemical signal. The expected advantages are an assay time lower than 20 min starting from blood volume smaller than 100 µL. Our functionalization procedure based on amine dendrimers and NHS-ester modification of initial carboxyl colloids will be presented. Functionalization efficiency was evaluated by colorimetric titration of surface chemical groups, zeta potential measurements, infrared spectroscopy, fluorescence scanning and cyclic voltammetry. Our results showed that electroactive molecules and antibodies can be immobilized successfully onto magnetic colloids. Application of a magnetic field onto working electrode increased the detected electrochemical signal. Magnetic colloids were able to capture specific purified antigens extracted from platelets.

Keywords: Magnetic Nanoparticles , Electroactive Molecules, Antibody, Platelet

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Authors: Emmanuelle Maria, Pierre Crançon, Gaëtane Lespes

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The knowledge of uranium migration processes within underground environments is a major issue in the environmental risk assessment associated with nuclear activities. This process is identified as strongly controlled by adsorption mechanisms, thus leading to strongly delayed migration paths. Colloidal ligands are likely to significantly increase the mobility of uranium in natural environments. The ability of colloids to mobilize and transport uranium depends on their origin, their nature, their structure, their stability and their reactivity with uranium. Thus, the colloidal mobilization and transport properties are often described as site-specific. In this work, the colloidal phases of two leachates obtained from two different horizons of the same podzolic soil were characterized with a speciation approach. For this purpose, a multi-technique strategy was used, based on Field-Flow Fractionation coupled to Ultraviolet, Multi-Angle Light Scattering and Inductively Coupled Plasma Mass Spectrometry (AF4-UV-MALS-ICPMS), Transmission Electron Microscopy (TEM), Electrospray Ionization Orbitrap Mass Spectrometry (ESI-Orbitrap), and Time-Resolved Laser Fluorescence Spectroscopy (TRLFS-EEM). Thus, elemental composition, size distribution, microscopic structure, colloidal stability and possible organic and/or inorganic content of colloids were determined, as well as their association with uranium. The leachates exhibit differences in their physical and chemical characteristics, mainly in the nature of organic matter constituents. The multi-technique investigation strategy used provides original data about colloidal phase structure and composition, offering a new vision of the way the uranium can be mobilized and transported in the considered soil. This information is a real significant contribution opening the way to our understanding and predicting of the colloidal transport.

Keywords: colloids, migration, multi-technique, speciation, transport, uranium

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Authors: Omkar Gaonkar, Indumathi Nambi, Suresh G. Kumar

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The functional and morphological aspects of soil structure determine the soil quality. The dispersion of colloidal soil particles, especially the clay fraction and rupture of soil aggregates, both of which play an important role in soil structure development, lead to degradation of soil quality. The main objective of this work was to determine the effect of the behaviour of soil colloids on the agricultural soil structure and quality. The effect of commercial humic acid and soil natural organic matter on the electrical and structural properties of the soil colloids was also studied. Agricultural soil, belonging to the sandy loam texture class from northern part of India was considered in this study. In order to understand the changes in the soil quality in the presence and absence of humic acids, the soil fabric and structure was analyzed by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) Spectroscopy and Scanning Electron Microscopy (SEM). Electrical properties of natural soil colloids in aqueous suspensions were assessed by zeta potential measurements at varying pH values with and without the presence of humic acids. The influence of natural organic matter was analyzed by oxidizing the natural soil organic matter with hydrogen peroxide. The zeta potential of the soil colloids was found to be negative in the pH range studied. The results indicated that hydrogen peroxide treatment leads to deflocculation of colloidal soil particles. In addition, the humic acids undergoes effective adsorption onto the soil surface imparting more negative zeta potential to the colloidal soil particles. The soil hydrophilicity decreased in the presence of humic acids which was confirmed by surface free energy determination. Thus, it can be concluded that the presence of humic acids altered the soil fabric and structure, thereby affecting the soil quality. This study assumes significance in understanding soil aggregation and the interactions at soil solid-liquid interface.

Keywords: humic acids, natural organic matter, zeta potential, soil quality

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Authors: Pierre Bauduin, Coralie Pasquier, Alban Jonchere, Luc Girard, Olivier Diat

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Ionic species, such as polyoxometalates (POMs) or (metal-) boron clusters, are at the frontier between ions and (charged-)colloids due to their nm size. We show here that the large size and low charge density of POMs, compared to classical ions, are responsible for a peculiar behavior called “super-chaotropy”. This property refers to the strong propensity of nano-ions to adsorb at neutral polar interfaces, via non-specific interactions. It has strong effects on phase transitions in soft matter and can, for example, stabilize colloidal systems such as surfactant foams. A simple way for evaluating and classifying nano-ions, such as POMs, according to their super-chaotropy is proposed here. The super-chaotropic behavior of nano-ions opens many opportunities in separation science, catalysis, and for the design of nanostructured hybrid materials.

Keywords: colloids, foams, surfactant, salt effect, colloidal stability, nano-ions

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Authors: Zemmouri Hassiba, Lounici Hakim, Mameri Nabil

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Dried crushed seeds of Moringa oleifera contain an effective soluble protein; a natural cationic polyelectrolyte which causes coagulation. The present study aims to investigate the performance of Moringa oleifera seed extract as natural coagulant in clarification of secondary wastewater treatment highly charged in colloidal. A series of Jar tests was undertaken using raw wastewater providing from secondary decanter of Reghaia municipal wastewater treatment plant (MWWTP) located in East of Algiers, Algeria. Coagulation flocculation performance of Moringa oleifera was evaluated through supernatant residual turbidity. Various influence parameters namely Moringa oleifera dosage and pH have been considered. Tests on Reghaia wastewater, having 129 NTU of initial turbidity, showed a removal of 69.45% of residual turbidity with only 1.5 mg/l of Moringa oleifera. This sufficient removal capability encourages the use of this bioflocculant for treatment of turbid waters. Based on this result, the coagulant seed extract of Moringa oleifera is better suited to clarify municipal wastewater by removing turbidity. Indeed, Moringa oleifera which is a natural resource available locally (South of Algeria) coupled to the non-toxicity, biocompatibility and biodegradability, may be a very interesting alternative to the conventional coagulants used so far.

Keywords: coagulation flocculation, colloids, moringa oleifera, secondary wastewater

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Authors: Sascha E. Oswald, Jan Busch

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The in-situ dechlorination of contamination by chlorinated solvents in groundwater via zero-valent iron (nZVI) is potentially an efficient and prompt remediation method. A key requirement is that nZVI has to be introduced in the subsurface in a way that substantial quantities of the contaminants are actually brought into direct contact with the nZVI in the aquifer. Thus it could be a more flexible and precise alternative to permeable reactive barrier techniques using granular iron. However, nZVI are often limited by fast agglomeration and sedimentation in colloidal suspensions, even more so in the aquifer sediments, which is a handicap for the application to treat source zones or contaminant plumes. Colloid-supported nZVI show promising characteristics to overcome these limitations and Carbo-Iron Colloids is a newly developed composite material aiming for that. The nZVI is built onto finely ground activated carbon of about a micrometer diameter acting as a carrier for it. The Carbo-Iron Colloids are often suspended with a polyanionic stabilizer, and carboxymethyl cellulose is one with good properties for that. We have investigated the transport behavior of Carbo-Iron Colloids (CIC) on different scales and for different conditions to assess its mobility in aquifer sediments as a key property for making its application feasible. The transport properties were tested in one-dimensional laboratory columns, a two-dimensional model aquifer and also an injection experiment in the field. Those experiments were accompanied by non-invasive tomographic investigations of the transport and filtration processes of CIC suspensions. The laboratory experiments showed that a larger part of the CIC can travel at least scales of meters for favorable but realistic conditions. Partly this is even similar to a dissolved tracer. For less favorable conditions this can be much smaller and in all cases a particular fraction of the CIC injected is retained mainly shortly after entering the porous medium. As field experiment a horizontal flow field was established, between two wells with a distance of 5 meters, in a confined, shallow aquifer at a contaminated site in North German lowlands. First a tracer test was performed and a basic model was set up to define the design of the CIC injection experiment. Then CIC suspension was introduced into the aquifer at the injection well while the second well was pumped and samples taken there to observe the breakthrough of CIC. This was based on direct visual inspection and total particle and iron concentrations of water samples analyzed in the laboratory later. It could be concluded that at least 12% of the CIC amount injected reached the extraction well in due course, some of it traveling distances larger than 10 meters in the non-uniform dipole flow field. This demonstrated that these CIC particles have a substantial mobility for reaching larger volumes of a contaminated aquifer and for interacting there by their reactivity with dissolved contaminants in the pore space. Therefore they seem suited well for groundwater remediation by in-situ formation of reactive barriers for chlorinated solvent plumes or even source removal.

Keywords: carbo-iron colloids, chlorinated solvents, in-situ remediation, particle transport, plume treatment

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Authors: Marine Reymond, Michael Descostes, Marie Muguet, Clemence Besancon, Martine Leermakers, Catherine Beaucaire, Sophie Billon, Patricia Patrier

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²²⁶Ra is one of the radionuclides resulting from the disintegration of ²³⁸U. Due to its half-life (1600 y) and its high specific activity (3.7 x 1010 Bq/g), ²²⁶Ra is found at the ultra-trace level in the natural environment (usually below 1 Bq/L, i.e. 10-13 mol/L). Because of its decay in ²²²Rn, a radioactive gas with a shorter half-life (3.8 days) which is difficult to control and dangerous for humans when inhaled, ²²⁶Ra is subject to a dedicated monitoring in surface waters especially in the context of uranium mining. In natural waters, radionuclides occur in dissolved, colloidal or particular forms. Due to the size of colloids, generally ranging between 1 nm and 1 µm and their high specific surface areas, the colloidal fraction could be involved in the transport of trace elements, including radionuclides in the environment. The colloidal fraction is not always easy to determine and few existing studies focus on ²²⁶Ra. In the present study, a complete multidisciplinary approach is proposed to assess the colloidal transport of ²²⁶Ra. It includes water sampling by conventional filtration (0.2µm) and the innovative Diffusive Gradient in Thin Films technique to measure the dissolved fraction (<10nm), from which the colloidal fraction could be estimated. Suspended matter in these waters were also sampled and characterized mineralogically by X-Ray Diffraction, infrared spectroscopy and scanning electron microscopy. All of these data, which were acquired on a rehabilitated former uranium mine, allowed to build a geochemical model using the geochemical calculation code PhreeqC to describe, as accurately as possible, the colloidal transport of ²²⁶Ra. Colloidal transport of ²²⁶Ra was found, for some of the sampling points, to account for up to 95% of the total ²²⁶Ra measured in water. Mineralogical characterization and associated geochemical modelling highlight the role of barite, a barium sulfate mineral well known to trap ²²⁶Ra into its structure. Barite was shown to be responsible for the colloidal ²²⁶Ra fraction despite the presence of kaolinite and ferrihydrite, which are also known to retain ²²⁶Ra by sorption.

Keywords: colloids, mining context, radium, transport

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Authors: Amr Saeb, Khalid Al-Rubeaan, Mohamed Abouelhoda, Manojkumar Selvaraju, Hamsa Tayeb

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Background: P. mirabilis is a common uropathogenic bacterium that can cause major complications in patients with long-standing indwelling catheters or patients with urinary tract anomalies. In addition, P. mirabilis is a common cause of chronic osteomyelitis in diabetic foot ulcer (DFU) patients. Methodology: P. mirabilis SCDR1 was isolated from a diabetic ulcer patient. We examined P. mirabilis SCDR1 levels of resistance against nano-silver colloids, the commercial nano-silver and silver containing bandages and commonly used antibiotics. We utilized next generation sequencing techniques (NGS), bioinformatics, phylogenetic analysis and pathogenomics in the identification and characterization of the infectious pathogen. Results: P. mirabilis SCDR1 is a multi-drug resistant isolate that also showed high levels of resistance against nano-silver colloids, nano-silver chitosan composite and the commercially available nano-silver and silver bandages. The P. mirabilis-SCDR1 genome size is 3,815,621 bp with G+C content of 38.44%. P. mirabilis-SCDR1 genome contains a total of 3,533 genes, 3,414 coding DNA sequence genes, 11, 10, 18 rRNAs (5S, 16S, and 23S), and 76 tRNAs. Our isolate contains all the required pathogenicity and virulence factors to establish a successful infection. P. mirabilis SCDR1 isolate is a potential virulent pathogen that despite its original isolation site, wound, it can establish kidney infection and its associated complications. P. mirabilis SCDR1 contains several mechanisms for antibiotics and metals resistance including, biofilm formation, swarming mobility, efflux systems, and enzymatic detoxification. Conclusion: P. mirabilis SCDR1 is the spontaneous nano-silver resistant bacterial strain. P. mirabilis SCDR1 strain contains all reported pathogenic and virulence factors characteristic for the species. In addition, it possesses several mechanisms that may lead to the observed nano-silver resistance.

Keywords: Proteus mirabilis, multi-drug resistance, silver nanoparticles, resistance, next generation sequencing techniques, genome analysis, bioinformatics, phylogeny, pathogenomics, diabetic foot ulcer, xenobiotics, multidrug resistance efflux, biofilm formation, swarming mobility, resistome, glutathione S-transferase, copper/silver efflux system, altruism

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Authors: Zita Šereš, Dragana Šoronja Simović, Ljubica Dokić, Lidietta Giorno, Biljana Pajin, Cecilia Hodur, Nikola Maravić

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Membrane technology is convenient for separation of suspended solids, colloids and high molecular weight materials that are present. The idea is that the waste stream from edible oil industry, after the separation of oil by using skimmers is subjected to microfiltration and the obtained permeate can be used again in the production process. The wastewater from edible oil industry was used for the microfiltration. For the microfiltration of this effluent a tubular membrane was used with a pore size of 200 nm at transmembrane pressure in range up to 3 bar and in range of flow rate up to 300 L/h. Box–Behnken design was selected for the experimental work and the responses considered were permeate flux and chemical oxygen demand (COD) reduction. The reduction of the permeate COD was in the range 40-60% according to the feed. The highest permeate flux achieved during the process of microfiltration was 160 L/m²h.

Keywords: ceramic membrane, edible oil, microfiltration, wastewater

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Authors: T. Bielewicz, S. Dogan, C. Klinke

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Two-dimensional, solution-processable semiconductor materials are interesting for low-cost electronic applications [1]. We demonstrate the synthesis of lead sulfide nanosheets and how their size, shape and height can be tuned by varying concentrations of pre-cursors, ligands and by varying the reaction temperature. Especially, the charge carrier confinement in the nanosheets’ height adjustable from 2 to 20 nm has a decisive impact on their electronic properties. This is demonstrated by their use as conduction channel in a field effect transistor [2]. Recently we also showed that especially thin nanosheets show a high carrier multiplication (CM) efficiency [3] which could make them, through the confinement induced band gap and high photoconductivity, very attractive for application in photovoltaic devices. We are already able to manufacture photovoltaic devices out of single nanosheets which show promising results.

Keywords: physical sciences, chemistry, materials, chemistry, colloids, physics, condensed-matter physics, semiconductors, two-dimensional materials

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Authors: Tan Yong Sheng Edgar, Yeong Wai Yee

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Age-related macular degeneration (AMD) is one of the leading cause of blindness. It can cause severe visual loss due to damaged retinal pigment epithelium (RPE). RPE is an important component of the retinal tissue. It functions as a transducing boundary for visual perception making it an essential factor for sight. The RPE also functions as a metabolically complex and functional cell layer that is responsible for the local homeostasis and maintenance of the extra photoreceptor environment. Thus one of the suggested method of treating such diseases would be regenerating these RPE cells. As such, we intend to grow these cells using a synthetic scaffold to provide a stable environment that reduces the batch effects found in natural scaffolds. Stiffness of the scaffold will also be investigated to determine the optimal Young’s modulus for cultivating these cells. The cells will be generated into a monolayer cell sheet and their functions such as formation of tight junctions and gene expression patterns will be assessed to evaluate the cell sheet quality compared to a native RPE tissue.

Keywords: RPE, scaffold, characterization, biomaterials, colloids and nanomedicine

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Authors: Heitor Oliveira, Gabriele De-Waal, Juergen Schmenger, Lynsey Godfrey, Tibor Kovacs

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Rheolaser MASTER™ makes use of multiple scattering of light, caused by scattering objects in a continuous medium (such as droplets and particles in colloids), to characterize the viscoelasticity of soft materials. It offers an alternative to conventional rheometers to characterize viscoelasticity of products such as hair cosmetics. Up to six simultaneous measurements at controlled temperature can be carried out simultaneously (10-15 min), and the method requires only minor sample preparation work. Conversely to conventional rheometer based methods, no mechanical stress is applied to the material during the measurements. Therefore, the properties of the exact same sample can be monitored over time, like in aging and stability studies. We determined the elastic index (EI) of water/emulsion mixtures (1 ≤ fat alcohols (FA) ≤ 5 wt%) and emulsion/gel-network mixtures (8 ≤ FA ≤ 17 wt%) and compared with the elastic/sorage mudulus (G’) for the respective samples using a TA conventional rheometer with flat plates geometry. As expected, it was found that log(EI) vs log(G’) presents a linear behavior. Moreover, log(EI) increased in a linear fashion with solids level in the entire range of compositions (1 ≤ FA ≤ 17 wt%), while rheometer measurements were limited to samples down to 4 wt% solids level. Alternatively, a concentric cilinder geometry would be required for more diluted samples (FA > 4 wt%) and rheometer results from different sample holder geometries are not comparable. The plot of the rheolaser output parameters solid-liquid balance (SLB) vs EI were suitable to monitor product aging processes. These data could quantitatively describe some observations such as formation of lumps over aging time. Moreover, this method allowed to identify that the different specifications of a key raw material (RM < 0.4 wt%) in the respective gel-network (GN) product has minor impact on product viscoelastic properties and it is not consumer perceivable after a short aging time. Broadening of a RM spec range typically has a positive impact on cost savings. Last but not least, the photon path length (λ*)—proportional to droplet size and inversely proportional to volume fraction of scattering objects, accordingly to the Mie theory—and the EI were suitable to characterize product destabilization processes (e.g., coalescence and creaming) and to predict product stability about eight times faster than our standard methods. Using these parameters we could successfully identify formulation and process parameters that resulted in unstable products. In conclusion, Rheolaser allows quick and reliable characterization of viscoelastic properties of hair cosmetics that are related to their performance and stability. It operates in a broad range of product compositions and has applications spanning from the formulation of our hair cosmetics to fast release criteria in our production sites. Last but not least, this powerful tool has positive impact on R&D development time—faster delivery of new products to the market—and consequently on cost savings.

Keywords: colloids, hair cosmetics, light scattering, performance and stability, soft materials, viscoelastic properties

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Authors: Zita Šereš, Ljubica Dokić, Nikola Maravić, Dragana Šoronja Simović, Cecilia Hodur, Ivana Nikolić, Biljana Pajin

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New environmental regulations and the increasing market preference for companies that respect the ecosystem had encouraged the industry to look after new treatments for its effluents. The sugar industry, one of the largest emitter of environmental pollutants, follows this tendency. Membrane technology is convenient for separation of suspended solids, colloids and high molecular weight materials that are present in a wastewater from the sugar industry. The idea is to microfilter the wastewater, where the permeate passes through the membrane and becomes available for recycle and re-use in the sugar manufacturing process. For microfiltration of this effluent a tubular ceramic membrane was used with a pore size of 200 nm at transmembrane pressure in range of 1 – 3 bars and in range of flow rate of 50 – 150 l/h. Kenics static mixer was used for permeate flux enhancement. Turbidity and suspended solids were removed and the permeate flux was continuously monitored during the microfiltration process. The flux achieved after 90 minutes of microfiltration was in a range of 50-70 L/m2h. The obtained turbidity decrease was in the range of 50-99% and the total amount of suspended solids was removed.

Keywords: ceramic membrane, microfiltration, permeate flux, sugar industry, wastewater

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Authors: Coline Bretz, Andrea Vaccaro, Dario Leumann

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The food, personal care, and cosmetic industries are seeing increased consumer demand for more sustainable and innovative ingredients. When developing new formulations incorporating such ingredients, stability is one of the first criteria that must be assessed, and it is thus of great importance to have a method that can detect instabilities early and quickly. Diffusing Wave Spectroscopy (DWS) is a light scattering technique that probes the motion,i.e., the mean square displacement (MSD), of colloids, such as nanoparticles in a suspension or droplets in emulsions. From the MSD, the rheological properties of the surrounding medium can be determined via the so-called microrheology approach. In the case of purely viscous media, it is also possible to obtain information about particle size. DWS can thus be used to monitor the size evolution of particles, droplets, or bubbles in aging dispersions, emulsions, or foams. In the context of early instability detection in emulsions, DWS offers considerable advantages, as the samples are measured in a contact-free manner, using only small quantities of samples loaded in a sealable cuvette. The sensitivity and rapidity of the technique are key to detecting and following the ageing of emulsions reliably. We present applications of DWS focused on the characterization of emulsions. In particular, we demonstrate the ability to record very subtle changes in the structural properties early on. We also discuss the various mechanisms at play in the destabilization of emulsions, such as coalescence or Ostwald ripening, and how to identify them through this technique.

Keywords: instrumentation, emulsions, stability, DWS

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Authors: Joshua Paul Steimel, Michael Pappas, Ethan Hall

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Particle-particle interactions are critical in determining the state of an active matter system. Unique and ubiquitous non-equilibrium behavior like swarming, vortexing, spiraling, and much more is governed by interactions between active units or particles. In hybrid active-passive matter systems, the attraction between spinning active units in a 2D monolayer of passive particles is controlled by the mechanical behavior of the passive monolayer. We demonstrate here that the range and dynamics of this attraction can be controlled by changing the composition of the passive monolayer by adding dopant passive particles. These dopant passive particles effectively pin the movement of dislocation motion in the passive media and reduce the probability of defect motion required to erode the bridge of passive particles between active spinners, thus reducing the range of attraction. Additionally, by adding an out of plane component to the magnetic moment and creating a top-like motion a short range repulsion emerges between the top-like particle. At inter-top distances less than four particle diameters apart, the tops repel but beyond that, distance attract up to 13 particle diameters apart. The tops were also able to locally and transiently anneal the passive monolayer. Thus we demonstrate that by tuning several parameters of the hybrid active matter system, one can observe very different emergent behavior.

Keywords: active matter, colloids, ferromagnetic, annealing

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Authors: Brayan Daniel Riascos Arteaga, Carlos Costa Perez

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Landfill leachate has an important fraction of humic substances, mainly humic acids (HAs), which often represent more than half value of COD, specially in liquids proceeded from composting processes of organic fraction of solid wastes. We propose in this article a new method of pH sensitive flocculation for COD and colour reduction in landfill leachate based on the chemical properties of HAs. Landfill leachate with a high content of humic acids can be efficiently treated by pH sensitive flocculation at pH 2.0, reducing COD value in 86.1% and colour in 84.7%. Mechanism of pH sensitive flocculation is based in protonation first of phenolic groups and later of carboxylic acid groups in the HAs molecules, resulting in a reduction of Zeta potential value. For pH over neutrality, carboxylic acid and phenolic groups are ionized and Zeta potential increases in absolute value, maintaining HAs in suspension as colloids and conducting flocculation to be obstructed. Ionized anionic groups (carboxylates) can interact electrostatically with cations abundant in leachate (site binding) aiding to maintain HAs in suspension. Simulation of this situation and ideal visualization of Zeta potential behavior is described in the paper and aggregation of molecules by H-bonds is proposed as the main step in separation of HAs from leachate and reduction of COD value in this complex liquid. CHNS analysis, FT-IR spectrometry and UV–VIS spectrophotometry show chemical elements content in the range of natural and commercial HAs, clear aromaticity and carboxylic acids and phenolic groups presence in the precipitate from landfill leachate

Keywords: landfill leachate, humic acids, COD, chemical treatment, flocculation

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Authors: Włodzimierz Przewodowski, Agnieszka Przewodowska

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Colloidal metal nanoparticles have drawn increasing attention in the field of phytopathology because of their unique properties and possibilities of applications. Their antibacterial activity, no induction of the development of pathogen resistance and the ability to penetrate most of biological barriers make them potentially useful in the fighting against dangerous pathogens. These properties are very important in the case of protection of strategic crops in the world, like potato - fourth crop in the world - which is host to numerous pathogenic microorganisms causing serious diseases, significantly affecting yield and causing the economic losses. One of the most important and difficult to reduce pathogen of potato plant is quarantine bacterium Clavibacter michiganensis ssp. sepedonicus (Cms) responsible for ring rot disease. Control and detection of these pathogens is very complicated. Application of healthy, certified seed material as well as hygiene in potato production and storage are the most efficient ways of preventing of ring rot disease. Currently used disinfectants and pesticides, have many disadvantages, such as toxicity, low efficiency, selectivity, corrosiveness, and the inability to eliminate the pathogens in potato tissue. In this situation, it becomes important to search for new formulations based on components harmful to health, yet efficient, stable during prolonged period of time and a with wide range of biocide activity. Such capabilities are offered by the latest generation of biocidal nanoparticles such as colloidal metals. Therefore the aim of the presented research was to develop newly antibacterial preparation based on colloidal metal nanoparticles and checking their influence on the Cms bacteria. Our preliminary results confirmed high efficacy of the nano-colloids in controlling the this selected pathogen.

Keywords: clavibacter michiganensis ssp. sepedonicus, colloidal metal nanoparticles, phytopathology, bacteria

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Authors: Pawel Albrycht, Monika Ksiezopolska-Gocalska, Robert Holyst

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Surface Enhanced Raman Spectroscopy (SERS) is a technique of growing importance not only in purely scientific research related to analytical chemistry. It finds more and more applications in broadly understood testing - medical, forensic, pharmaceutical, food - and everywhere works perfectly, on one condition that SERS substrates used for testing give adequate enhancement, repeatability, and homogeneity of SERS signal. This is a problem that has existed since the invention of this technique. Some laboratories use as SERS amplifiers colloids with silver or gold nanoparticles, others form rough silver or gold surfaces, but results are generally either weak or unrepeatable. Furthermore, these structures are very often highly specific - they amplify the signal only of a small group of compounds. It means that they work with some kinds of analytes but only with those which were used at a developer’s laboratory. When it comes to research on different compounds, completely new SERS 'substrates' are required. That underlay our decision to develop universal substrates for the SERS spectroscopy. Generally, each compound has different affinity for both silver and gold, which have the best SERS properties, and that's what depends on what signal we get in the SERS spectrum. Our task was to create the platform that gives a characteristic 'fingerprint' of the largest number of compounds with very high repeatability - even at the expense of the intensity of the enhancement factor (EF) (possibility to repeat research results is of the uttermost importance). As specified above SERS substrates are offered by SERSitive company. Applied method is based on cyclic potentiodynamic electrodeposition of silver or silver-gold nanoparticles on the conductive surface of ITO-coated glass at controlled temperature of the reaction solution. Silver nanoparticles are supplied in the form of silver nitrate (AgNO₃, 10 mM), gold nanoparticles are derived from tetrachloroauric acid (10 mM) while sodium sulfite (Na₂O₃, 5 mM) is used as a reductor. To limit and standardize the size of the SERS surface on which nanoparticles are deposited, photolithography is used. We secure the desired ITO-coated glass surface, and then etch the unprotected ITO layer which prevents nanoparticles from settling at these sites. On the prepared surface, we carry out the process described above, obtaining SERS surface with nanoparticles of sizes 50-400 nm. The SERSitive platforms present highly sensitivity (EF = 10⁵-10⁶), homogeneity and repeatability (70-80%).

Keywords: electrodeposition, nanoparticles, Raman spectroscopy, SERS, SERSitive, SERS platforms, SERS substrates

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Authors: M. Ghali, M. Elnimr, G. F. Ali, A. M. Eissa, H. Talaat

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CuIn₃Se₅ material is indexed as ordered vacancy compounds having excellent matching properties with CuInGaSe (CIGS) solar absorber layer. For example, the valence band offset of CuIn₃Se₅ with CIGS is nearly 0.3 eV, and the lattice mismatch is less than 1%, besides the absence of discontinuity in their conduction bands. Thus, CuIn₃Se₅ can work as a passivation layer for repelling holes from CIGS/CdS interface and hence to reduce the interface carriers recombination and consequently enhancing the efficiency of CIGS/CdS solar cells. Theoretically, it was reported earlier that an improvement in the efficiency of p-CIGS-based solar cell with a thin ~100 nm of n-CuIn₃Se₅ layer is expected. Recently, a reported experiment demonstrated significant improvement in the efficiency of Molecular Beam Epitaxy (MBE) grown CIGS solar cells from 13.4 to 14.5% via inserting a thin layer of MBE-grown Cu(In,Ga)₃Se₅ layer at the CdS/CIGS interface. It should be mentioned that CuIn₃Se₅ material in either bulk or thin film form, are usually fabricated by high vacuum physical vapor deposition techniques (e.g., three-source co-evaporation, RF sputtering, flash evaporation, and molecular beam epitaxy). In addition, achieving photosensitive films of n-CuIn₃Se₅ material is important for new hybrid organic/inorganic structures, where inorganic photo-absorber layer, with n-type conductivity, can form n–p junction with organic p-type material (e.g., conductive polymers). A detailed study of the physical properties of CuIn₃Se₅ is still necessary for better understanding of device operation and further improvement of solar cells performance. Here, we report on the low-cost synthesis of CuIn₃Se₅ material in nano-scale size, with an average diameter ~10nm, using simple solution-based colloidal chemistry. In contrast to traditionally grown bulk tetragonal CuIn₃Se₅ crystals using high Vacuum-based technology, our colloidal CuIn₃Se₅ nanocrystals show cubic crystal structure with a shape of nanoparticles and band gap ~1.33 eV. Ink-coated thin films prepared from these nanocrystals colloids; display n-type character, 1.26 eV band gap and strong photo-responsive behavior with incident white light. This suggests the potential use of colloidal CuIn₃Se₅ as an active layer in all-solution-processed thin film solar cells.

Keywords: nanocrystals, CuInSe, thin film, optical properties

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Authors: Jafar S. Noori, Jan Romano-deGea, Maria Dimaki, John Mortensen, Winnie E. Svendsen

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Pesticides have been intensively used in agriculture to control weeds, insects, fungi, and pest. One of the most commonly used pesticides is glyphosate. Glyphosate has the ability to attach to the soil colloids and degraded by the soil microorganisms. As glyphosate led to the appearance of resistant species, the pesticide was used more intensively. As a consequence of the heavy use of glyphosate, residues of this compound are increasingly observed in food and water. Recent studies reported a direct link between glyphosate and chronic effects such as teratogenic, tumorigenic and hepatorenal effects although the exposure was below the lowest regulatory limit. Today, pesticides are detected in water by complicated and costly manual procedures conducted by highly skilled personnel. It can take up to several days to get an answer regarding the pesticide content in water. An alternative to this demanding procedure is offered by electrochemical measuring techniques. Electrochemistry is an emerging technology that has the potential of identifying and quantifying several compounds in few minutes. It is currently not possible to detect glyphosate directly in water samples, and intensive research is underway to enable direct selective and quantitative detection of glyphosate in water. This study focuses on developing and modifying a sensor chip that has the ability to selectively measure glyphosate and minimize the signal interference from other compounds. The sensor is a silicon-based chip that is fabricated in a cleanroom facility with dimensions of 10×20 mm. The chip is comprised of a three-electrode configuration. The deposited electrodes consist of a 20 nm layer chromium and 200 nm gold. The working electrode is 4 mm in diameter. The working electrodes are modified by creating molecularly imprinted polymers (MIP) using electrodeposition technique that allows the chip to selectively measure glyphosate at low concentrations. The modification included using gold nanoparticles with a diameter of 10 nm functionalized with 4-aminothiophenol. This configuration allows the nanoparticles to bind to the working electrode surface and create the template for the glyphosate. The chip was modified using electrodeposition technique. An initial potential for the identification of glyphosate was estimated to be around -0.2 V. The developed sensor was used on 6 different concentrations and it was able to detect glyphosate down to 0.5 mgL⁻¹. This value is below the accepted pesticide limit of 0.7 mgL⁻¹ set by the US regulation. The current focus is to optimize the functionalizing procedure in order to achieve glyphosate detection at the EU regulatory limit of 0.1 µgL⁻¹. To the best of our knowledge, this is the first attempt to modify miniaturized sensor electrodes with functionalized nanoparticles for glyphosate detection.

Keywords: pesticides, glyphosate, rapid, detection, modified, sensor

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Authors: Sanjay K. Behera, Debasish Saha, Paramesh Gadige, Ranjini Bandyopadhyay

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The zero shear viscosity (η₀) of a suspension of hard sphere colloids characterized by a significant polydispersity (≈10%) increases with increase in volume fraction (ϕ) and shows a dramatic increase at ϕ=ϕg with the system entering a colloidal glassy state. Fragility which is the measure of the rapidity of approach of these suspensions towards the glassy state is sensitive to its size polydispersity and stiffness of the particles. Soft poly(N-isopropylacrylamide) (PNIPAM) particles deform in the presence of neighboring particles at volume fraction above the random close packing volume fraction of undeformed monodisperse spheres. Softness, therefore, enhances the packing efficiency of these particles. In this study PNIPAM particles of a nearly constant swelling ratio and with polydispersities varying over a wide range (7.4%-48.9%) are synthesized to study the effects of polydispersity on the dynamics of suspensions of soft PNIPAM colloidal particles. The size and polydispersity of these particles are characterized using dynamic light scattering (DLS) and scanning electron microscopy (SEM). As these particles are deformable, their packing in aqueous suspensions is quantified in terms of effective volume fraction (ϕeff). The zero shear viscosity (η₀) data of these colloidal suspensions, estimated from rheometric experiments as a function of the effective volume fraction ϕeff of the suspensions, increases with increase in ϕeff and shows a dramatic increase at ϕeff = ϕ₀. The data for η₀ as a function of ϕeff fits well to the Vogel-Fulcher-Tammann equation. It is observed that increasing polydispersity results in increasingly fragile supercooled liquid-like behavior, with the parameter ϕ₀, extracted from the fits to the VFT equation shifting towards higher ϕeff. The observed increase in fragility is attributed to the prevalence of dynamical heterogeneities (DHs) in these polydisperse suspensions, while the simultaneous shift in ϕ₀ is ascribed to the decoupling of the dynamics of the smallest and largest particles. Finally, it is observed that the intrinsic nonlinearity of these suspensions, estimated at the third harmonic near ϕ₀ in Fourier transform oscillatory rheological experiments, increases with increase in polydispersity. These results are in agreement with theoretical predictions and simulation results for polydisperse hard sphere colloidal glasses and clearly demonstrate that jammed suspensions of polydisperse colloidal particles can be effectively fluidized with increasing polydispersity. Suspensions of these particles are therefore excellent candidates for detailed experimental studies of the effects of polydispersity on the dynamics of glass formation.

Keywords: dynamical heterogeneity, effective volume fraction, fragility, intrinsic nonlinearity

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Authors: Ana M. Antolín, Sandra Contreras, Francesc Medina, Didier Tichit

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Introduction: High levels of nitrates (> 50 ppm NO3-) in drinking water are potentially risky to human health. In the recent years, the trend of nitrate concentration in groundwater is rising in the EU and other countries. Conventional catalytic nitrate reduction processes into N2 and H2O lead to some toxic intermediates and by-products, such as NO2-, NH4+, and NOx gases. Alternatively, photocatalytic nitrate removal using solar irradiation and heterogeneous catalysts is a very promising and ecofriendly technique. It has been scarcely performed and more research on highly efficient catalysts is still needed. In this work, different nanocatalysts supported on Aeroxide Titania P25 (P25) have been prepared varying: 0.5-4 % wt. Ag); Pt (2, 4 % wt.); Pt precursor (H2PtCl6/K2PtCl6); and impregnation order of both metals. Pt was chosen in order to increase the selectivity to N2 and decrease that to NO2-. Catalysts were characterized by nitrogen physisorption, X-Ray diffraction, UV-visible spectroscopy, TEM and X Ray-Photoelectron Spectroscopy. The aim was to determine the influence of the composition and the preparation method of the catalysts on the conversion and selectivity in the nitrate reduction, as well as going through an overall and better understanding of the process. Nanocatalysts synthesis: For the mono and bimetallic catalysts preparation, wise-drop wetness impregnation of the precursors (AgNO3, H2PtCl6, K2PtCl6) followed by a reduction step (NaBH4) was used to obtain the metal colloids. Results and conclusions: Denitration experiments were performed in a 350 mL PTFE batch reactor under inert standard operational conditions, ultraviolet irradiations (λ=254 nm (UV-C); λ=365 nm (UV-A)), and presence/absence of hydrogen gas as a reducing agent, contrary to most studies using oxalic or formic acid. Samples were analyzed by Ionic Chromatography. Blank experiments using respectively P25 (dark conditions), hydrogen only and UV irradiations without hydrogen demonstrated a clear influence of the presence of hydrogen on nitrate reduction. Also, they demonstrated that UV irradiation increased the selectivity to N2. Interestingly, the best activity was obtained under ultraviolet lamps, especially at a closer wavelength to visible light irradiation (λ = 365 nm) and H2. 2% Ag/P25 leaded to the highest NO3- conversion among the monometallic catalysts. However, nitrite quantities have to be diminished. On the other hand, practically no nitrate conversion was observed with the monometallics based on Pt/P25. Therefore, the amount of 2% Ag was chosen for the bimetallic catalysts. Regarding the bimetallic catalysts, it is observed that the metal impregnation order, amount and Pt precursor highly affects the results. Higher selectivity to the desirable N2 gas is obtained when Pt was firstly added, especially with K2PtCl6 as Pt precursor. This suggests that when Pt is secondly added, it covers the Ag particles, which are the most active in this reaction. It could be concluded that Ag allows the nitrate reduction step to nitrite, and Pt the nitrite reduction step toward the desirable N2 gas.

Keywords: heterogeneous catalysis, hydrogenation, nanocatalyst, nitrate removal, photocatalysis

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Authors: Xiaoyun Hui, Fiona Gentle, Clemens Engelke, Margaret C. Graham

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Although past work has shown that phosphorus (P), an important nutrient, may form complexes with aqueous humic substances (HS), the principal component of natural organic matter, the nature of such interactions is poorly understood. Humic complexation may not only enhance P concentrations but it may change its bioavailability within such waters and, in addition, influence its transport within catchment settings. This project is examining the relationships and associations of P, HS, and iron (Fe) in Loch Meadie, Sutherland, North Scotland, a mesohumic freshwater loch which has been assessed as reference condition with respect to P. The aim is to identify characteristic spectroscopic parameters which can enhance the performance of the model currently used to predict reference condition TP levels for highly-coloured Scottish lochs under the Water Framework Directive. In addition to Loch Meadie, samples from other reference condition lochs in north Scotland and Shetland were analysed. By including different types of reference condition lochs (clear water, mesohumic and polyhumic water) this allowed the relationship between total phosphorus (TP) and HS to be more fully explored. The pH, [TP], [Fe], UV/Vis absorbance/spectra, [TOC] and [DOC] for loch water samples have been obtained using accredited methods. Loch waters were neutral to slightly acidic/alkaline (pH 6-8). [TP] in loch waters were lower than 50 µg L-1, and in Loch Meadie waters were typically <10 µg L-1. [Fe] in loch waters were mainly <0.6 mg L-1, but for some loch water samples, [Fe] were in the range 1.0-1.8 mg L-1and there was a positive correlation with [TOC] (r2=0.61). Lochs were classified as clear water, mesohumic or polyhumic based on water colour. The range of colour values of sampled lochs in each category were 0.2–0.3, 0.2–0.5 and 0.5–0.8 a.u. (10 mm pathlength), respectively. There was also a strong positive correlation between [DOC] and water colour (R2=0.84). The UV/Vis spectra (200-700 nm) for water samples were featureless with only a slight “shoulder” observed in the 270–290 nm region. Ultrafiltration was then used to separate colloidal and truly dissolved components from the loch waters and, since it contained the majority of aqueous P and Fe, the colloidal component was fractionated by gel filtration chromatography method. Gel filtration chromatographic fractionation of the colloids revealed two brown-coloured bands which had distinctive UV/Vis spectral features. The first eluting band had larger and more aromatic HS molecules than the second band, and in addition both P and Fe were primarily associated with the larger, more aromatic HS. This result demonstrated that P was able to form complexes with Fe-rich components of HS, and thus provided a scientific basis for the significant correlation between [Fe] and [TP] that the previous monitoring data of reference condition lochs from Scottish Environment Protection Agency (SEPA) showed. The distinctive features of the HS will be used as the basis for an improved spectroscopic tool.

Keywords: total phosphorus, humic substances, Scottish loch water, WFD model

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Authors: Nikolai A. Khlebnikov, Vladimir N. Krasilnikov, Evgenii V. Polyakov, Anastasia A. Maltceva

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Carbon materials with advanced surfaces are widely used both in modern industry and in environmental protection. The physical-chemical nature of these materials is determined by the morphology of primary atomic and molecular carbon structures, which are the basis for synthesizing the following materials: zero-dimensional (fullerenes), one-dimensional (fiber, tubes), two-dimensional (graphene) carbon nanostructures, three-dimensional (multi-layer graphene, graphite, foams) with unique physical-chemical and functional properties. Experience shows that the microscopic morphological level is the basis for the creation of the next mesoscopic morphological level. The dependence of the morphology on the chemical way and process prehistory (crystallization, colloids formation, liquid crystal state and other) is the peculiarity of the last called level. These factors determine the consumer properties of carbon materials, such as specific surface area, porosity, chemical resistance in corrosive environments, catalytic and adsorption activities. Based on the developed ideology of thin precursor synthesis, the authors discuss one of the approaches of the porosity control of carbon-containing materials with a given aggregates morphology. The low-temperature thermolysis of precursors in a gas environment of a given composition is the basis of the above-mentioned idea. The processes of carbothermic precursor synthesis of two different compounds: tungsten carbide WC:nC and zinc oxide ZnO:nC containing an impurity phase in the form of free carbon were selected as subjects of the research. In the first case, the transition metal (tungsten) forming carbides was the object of the synthesis. In the second case, there was selected zinc that does not form carbides. The synthesis of both kinds of transition metals compounds was conducted by the method of precursor carbothermic synthesis from the organic solution. ZnO:nC composites were obtained by thermolysis of succinate Zn(OO(CH2)2OO), formate glycolate Zn(HCOO)(OCH2CH2O)1/2, glycerolate Zn(OCH2CHOCH2OH), and tartrate Zn(OOCCH(OH)CH(OH)COO). WC:nC composite was synthesized from ammonium paratungstate and glycerol. In all cases, carbon structures that are specific for diamond- like carbon forms appeared on the surface of WC and ZnO particles after the heat treatment. Tungsten carbide and zinc oxide were removed from the composites by selective chemical dissolution preserving the amorphous carbon phase. This work presents the results of investigating WC:nC and ZnO:nC composites and carbon nanopowders with tubular, tape, plate and onion morphologies of aggregates that are separated by chemical dissolution of WC and ZnO from the composites by the following methods: SEM, TEM, XPA, Raman spectroscopy, and BET. The connection between the carbon morphology under the conditions of synthesis and chemical nature of the precursor and the possibility of regulation of the morphology with the specific surface area up to 1700-2000 m2/g of carbon-structured materials are discussed.

Keywords: carbon morphology, composite materials, precursor synthesis, tungsten carbide, zinc oxide

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Authors: Ines Raies, Eric Kohler, Marc Fleury, Béatrice Ledésert

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In this work, the impact of clay minerals on the formation damage of sandstone reservoirs is studied to provide a better understanding of the problem of deep geothermal reservoir permeability reduction due to fine particle dispersion and migration. In some situations, despite the presence of filters in the geothermal loop at the surface, particles smaller than the filter size (<1 µm) may surprisingly generate significant permeability reduction affecting in the long term the overall performance of the geothermal system. Our study is carried out on cores from a Triassic reservoir in the Paris Basin (Feigneux, 60 km Northeast of Paris). Our goal is to first identify the clays responsible for clogging, a mineralogical characterization of these natural samples was carried out by coupling X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS). The results show that the studied stratigraphic interval contains mostly illite and chlorite particles. Moreover, the spatial arrangement of the clays in the rocks as well as the morphology and size of the particles, suggest that illite is more easily mobilized than chlorite by the flow in the pore network. Thus, based on these results, illite particles were prepared and used in core flooding in order to better understand the factors leading to the aggregation and deposition of this type of clay particles in geothermal reservoirs under various physicochemical and hydrodynamic conditions. First, the stability of illite suspensions under geothermal conditions has been investigated using different characterization techniques, including Dynamic Light Scattering (DLS) and Scanning Transmission Electron Microscopy (STEM). Various parameters such as the hydrodynamic radius (around 100 nm), the morphology and surface area of aggregates were measured. Then, core-flooding experiments were carried out using sand columns to mimic the permeability decline due to the injection of illite-containing fluids in sandstone reservoirs. In particular, the effects of ionic strength, temperature, particle concentration and flow rate of the injected fluid were investigated. When the ionic strength increases, a permeability decline of more than a factor of 2 could be observed for pore velocities representative of in-situ conditions. Further details of the retention of particles in the columns were obtained from Magnetic Resonance Imaging and X-ray Tomography techniques, showing that the particle deposition is nonuniform along the column. It is clearly shown that very fine particles as small as 100 nm can generate significant permeability reduction under specific conditions in high permeability porous media representative of the Triassic reservoirs of the Paris basin. These retention mechanisms are explained in the general framework of the DLVO theory

Keywords: geothermal energy, reinjection, clays, colloids, retention, porosity, permeability decline, clogging, characterization, XRD, SEM-EDS, STEM, DLS, NMR, core flooding experiments

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Authors: J. Yang, M. Monnot, T. Eljaddi, L. Simonian, L. Ercolei, P. Moulin

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The application of membrane technology to wastewater treatment has expanded rapidly under increasing stringent legislation and environmental protection requirements. At the same time, the water resource is becoming precious, and water reuse has gained popularity. Particularly, ultrafiltration (UF) is a very promising technology for water reuse as it can retain organic matters, suspended solids, colloids, and microorganisms. Nevertheless, few studies dealing with operating optimization of UF as a tertiary treatment for water reuse on a semi-industrial scale appear in the literature. Therefore, this study aims to explore the permeate water quality and to optimize operating parameters (maximizing productivity and minimizing irreversible fouling) through the operation of a UF pilot plant under real conditions. The fully automatic semi-industrial UF pilot plant with periodic classic backwashes (CB) and air backwashes (AB) was set up to filtrate the secondary effluent of an urban wastewater treatment plant (WWTP) in France. In this plant, the secondary treatment consists of a conventional activated sludge process followed by a sedimentation tank. The UF process was thus defined as a tertiary treatment and was operated under constant flux. It is important to note that a combination of CB and chlorinated AB was used for better fouling management. The 200 kDa hollow fiber membrane was used in the UF module, with an initial permeability (for WWTP outlet water) of 600 L·m-2·h⁻¹·bar⁻¹ and a total filtration surface of 9 m². Fifteen filtration conditions with different fluxes, filtration times, and air backwash frequencies were operated for more than 40 hours of each to observe their hydraulic filtration performances. Through comparison, the best sustainable condition was flux at 60 L·h⁻¹·m⁻², filtration time at 60 min, and backwash frequency of 1 AB every 3 CBs. The optimized condition stands out from the others with > 92% water recovery rates, better irreversible fouling control, stable permeability variation, efficient backwash reversibility (80% for CB and 150% for AB), and no chemical washing occurrence in 40h’s filtration. For all tested conditions, the permeate water quality met the water reuse guidelines of the World Health Organization (WHO), French standards, and the regulation of the European Parliament adopted in May 2020, setting minimum requirements for water reuse in agriculture. In permeate: the total suspended solids, biochemical oxygen demand, and turbidity were decreased to < 2 mg·L-1, ≤ 10 mg·L⁻¹, < 0.5 NTU respectively; the Escherichia coli and Enterococci were > 5 log removal reduction, the other required microorganisms’ analysis were below the detection limits. Additionally, because of the COVID-19 pandemic, coronavirus SARS-CoV-2 was measured in raw wastewater of WWTP, UF feed, and UF permeate in November 2020. As a result, the raw wastewater was tested positive above the detection limit but below the quantification limit. Interestingly, the UF feed and UF permeate were tested negative to SARS-CoV-2 by these PCR assays. In summary, this work confirms the great interest in UF as intensified tertiary treatment for water reuse and gives operational indications for future industrial-scale production of reclaimed water.

Keywords: semi-industrial UF pilot plant, water reuse, fouling management, coronavirus

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Authors: Pamela Chia, Tay Yoong Chuan

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Introduction: Severe pulmonary hypertension (PH) patients requiring non-cardiac surgery risk have increased mortality rates ranging. These patients are plagued with cardiorespiratory failure, dysrhythmias and anticoagulation potentially with concurrent sepsis and renal insufficiency, perioperative morbidity. We present a deaf-mute patient with severe idiopathic PH emergently prepared for ruptured ectopic laparotomy. Case Report: A 20 year-old female, 62kg (BMI 25 kg/m2) with severe idiopathic PH (2DE Ejection Fraction was 41%, Pulmonary Artery Systolic Pressure (PASP) 105 mmHg, Right ventricle strain and hypertrophy) and selective mutism was rushed in for emergency laparotomy after presenting to the emergency department for abdominal pain. The patient had an NYHA Class II with room air SpO2 93-95%. While awaiting lung transplant, the patient takes warfarin, Sildanefil, Macitentan and even Selexipag for rising PASP. At presentation, vital signs: BP 95/63, HR 119 SpO2 88% (room air). Despite decreasing haemoglobin 14 to 10g/dL, INR 2.59 was reversed with prothrombin concentrate, and Vitamin K. ECG revealed Right Bundle Branch Block with right ventricular strain and x-ray showed cardiomegaly, dilated Right Ventricle, Pulmonary Arteries, basal atelectasis. Arterial blood gas showed compensated metabolic acidosis pH 7.4 pCO2 32 pO2 53 HCO3 20 BE -4 SaO2 88%. The cardiothoracic surgeon concluded no role for Extracorporeal Membrane Oxygenation (ECMO). We inserted invasive arterial and central venous lines with blood transfusion via an 18G cannula before the patient underwent a midline laparotomy, haemostasis of ruptured ovarian cyst with 2.4L of clots under general anesthesia and FloTrac cardiac output monitoring. Rapid sequence induction was done with Midazolam/Propofol, remifentanil infusion, and rocuronium. The patient was maintained on Desflurane. Blood products and colloids were transfused for further 1.5L blood loss. Postoperatively, the patient was transferred to the intensive care unit and was extubated uneventfully 7hours later. The patient went home a week later. Discussion: Emergency hemostasis laparotomy in anticoagulated WHO Class I PH patient awaiting lung transplant with no ECMO backup poses tremendous stress on the deaf-mute patient and the anesthesiologist. Balancing hemodynamics avoiding hypotension while awaiting hemostasis in the presence of pulmonary arterial dilators and anticoagulation requires close titration of volatiles, which decreases RV contractility. We review the contraindicated anesthetic agents (ketamine, N2O), choice of vasopressors in hypotension to maintain Aortic-right ventricular pressure gradients and nitric oxide use perioperatively. Conclusion: Interdisciplinary communication with a deaf-mute moribund patient and anesthesia considerations pose many rare challenges worth sharing.

Keywords: pulmonary hypertension, case report, warfarin reversal, emergency surgery

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Authors: Renata Gerhardt, Detlev Belder

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Raman spectroscopy has attracted much attention as a structurally descriptive and label-free detection method. It is particularly suited for chemical analysis given as it is non-destructive and molecules can be identified via the fingerprint region of the spectra. In this work possibilities are investigated how to integrate Raman spectroscopy as a detection method for chip-based chromatography, making use of a droplet interface. A demanding task in lab-on-a-chip applications is the specific and sensitive detection of low concentrated analytes in small volumes. Fluorescence detection is frequently utilized but restricted to fluorescent molecules. Furthermore, no structural information is provided. Another often applied technique is mass spectrometry which enables the identification of molecules based on their mass to charge ratio. Additionally, the obtained fragmentation pattern gives insight into the chemical structure. However, it is only applicable as an end-of-the-line detection because analytes are destroyed during measurements. In contrast to mass spectrometry, Raman spectroscopy can be applied on-chip and substances can be processed further downstream after detection. A major drawback of Raman spectroscopy is the inherent weakness of the Raman signal, which is due to the small cross-sections associated with the scattering process. Enhancement techniques, such as surface enhanced Raman spectroscopy (SERS), are employed to overcome the poor sensitivity even allowing detection on a single molecule level. In SERS measurements, Raman signal intensity is improved by several orders of magnitude if the analyte is in close proximity to nanostructured metal surfaces or nanoparticles. The main gain of lab-on-a-chip technology is the building block-like ability to seamlessly integrate different functionalities, such as synthesis, separation, derivatization and detection on a single device. We intend to utilize this powerful toolbox to realize Raman detection in chip-based chromatography. By interfacing on-chip separations with a droplet generator, the separated analytes are encapsulated into numerous discrete containers. These droplets can then be injected with a silver nanoparticle solution and investigated via Raman spectroscopy. Droplet microfluidics is a sub-discipline of microfluidics which instead of a continuous flow operates with the segmented flow. Segmented flow is created by merging two immiscible phases (usually an aqueous phase and oil) thus forming small discrete volumes of one phase in the carrier phase. The study surveys different chip designs to realize coupling of chip-based chromatography with droplet microfluidics. With regards to maintaining a sufficient flow rate for chromatographic separation and ensuring stable eluent flow over the column different flow rates of eluent and oil phase are tested. Furthermore, the detection of analytes in droplets with surface enhanced Raman spectroscopy is examined. The compartmentalization of separated compounds preserves the analytical resolution since the continuous phase restricts dispersion between the droplets. The droplets are ideal vessels for the insertion of silver colloids thus making use of the surface enhancement effect and improving the sensitivity of the detection. The long-term goal of this work is the first realization of coupling chip based chromatography with droplets microfluidics to employ surface enhanced Raman spectroscopy as means of detection.

Keywords: chip-based separation, chip LC, droplets, Raman spectroscopy, SERS

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