Enzymatic Transesterification of Ethyl Ferulate with Fish Oil and Reaction Optimization by Response Surface Methodology

Ispitana je enzimska transesterifikacija ulja dobivenog iz jetre bakalara etil ferulatom (EF), primjenom katalizatora Novozym® 435. Svrha je rada bila istražiti mogućnost primjene ove sinteze u industrijskoj proizvodnji feruloil ribljeg ulja. Produkti reakcije karakterizirani su modificiranom HPLC-ESI-TOF-MS metodom. Ispitan je utjecaj dodatka glicerola na sastav nastalih feruloil acilglicerola. Biokonverzija EF bila je kudikamo veća u prisutnosti glicerola, a osobito s povećanjem udjela nastalog feruloil ribljeg ulja. Stoga je radi optimiranja reakcije u sustav dodana ekvimolarna količina glicerola. Ispitan je zajednički utjecaj temperature (od 40 do 70 °C), vremena reakcije (1-5 dana), udjela enzima (2-20 %) i molarnog omjera ribljeg ulja i EF (1-5). Primjenom metode odzivnih površina određeni su najpogodniji parametri za maksimalni prinos feruolil ribljeg ulja, i to: temperatura od 70 °C, udjel enzima od 4,3 %, molarni omjer supstrata od 4,7 i vrijeme reakcije od 5 dana. Pri tim je uvjetima postignut udjel EF od 92,4 %, feruloil ribljeg ulja od 80,4 %, a smanjen udjel nusprodukata na samo 11,4 %.The enzymatic transesterification of ethyl ferulate (EF) with fish oil from cod liver was investigated with Novozym® 435 as catalyst under solvent-free conditions. The purpose of the study is to evaluate the synthesis system for the production of feruloyl fish oil in industry. The modified HPLC method was first set up to characterise the reaction products together with liquid chromatography electrospray time-of-flight mass spectrometry (HPLC-ESI-TOF-MS). The influence of the addition of glycerol to the system on the feruloyl acylglycerol profile was investigated in terms of transesterification performance. The bioconversion rate of EF can be significantly increased with the increased formation of feruloyl fish oil products when appropriate amount of glycerol is present in the reaction. Therefore, an equivalent molar amount of glycerol was added to EF for the practical optimization of the system. The mutual effects of temperature (40 to 70 °C), reaction time (1 to 5 days), enzyme load (2 to 20 %) and molar ratio of fish oil and EF in the substrate (1 to 5) were thus studied with the assistance of response surface methodology (RSM) for the purpose of maximizing the formation of feruloyl fish oil. The models were well fitted and verified. The optimized conditions were found to be: temperature 70 °C, enzyme load 4.3 %, substrate ratio 4.7, and reaction time 5 days. Under these conditions, the maximum conversion of EF reached 92.4 %, and the formation of feruloyl fish oil reached 80.4 %, but the formation of by-product was minimized to 11.4 % only

Exposure to ambient concentrations of particulate air pollution does not influence vascular function or inflammatory pathways in young healthy individuals

<p>Abstract</p> <p>Background</p> <p>Particulate air pollution is associated with increased risk of cardiovascular events although the involved mechanisms are poorly understood. The objective of the present study was to investigate the effects of controlled exposure to ambient air fine and ultrafine particles on microvascular function and biomarkers related to inflammation, haemostasis and lipid and protein oxidation.</p> <p>Methods</p> <p>Twenty-nine subjects participated in a randomized, two-factor crossover study with or without biking exercise for 180 minutes and with 24 hour exposure to particle rich (number concentrations, NC: 11600 ± 5600 per cm³, mass concentrations: 13.8 ± 7.4 μg/m³and 10.5 ± 4.8 μg/m³for PM_10-2.5and PM_2.5, respectively) or particle filtered (NC: 555 ± 1053 per cm³) air collected above a busy street. Microvascular function was assessed non-invasively by measuring digital peripheral artery tone following arm ischemia. Biomarkers included haemoglobin, red blood cells, platelet count, coagulation factors, C-reactive protein, fibrinogen, interleukin-6, tumour necrosis factor α, lag time to copper-induced oxidation of plasma lipids and protein oxidation measured as 2-aminoadipic semialdehyde in plasma.</p> <p>Results</p> <p>No statistically significant differences were observed on microvascular function or the biomarkers after exposure to particle rich or particle filtered air.</p> <p>Conclusion</p> <p>This study indicates that exposure to air pollution particles at outdoor concentrations is not associated with detectable systemic inflammation, lipid or protein oxidation, altered haemostasis or microvascular function in young healthy participants.</p

Modeling the Size Distribution and Chemical Composition of Secondary Organic Aerosols during the Reactive Uptake of Isoprene-Derived Epoxydiols under Low-Humidity Condition

Reactive uptake of isoprene epoxydiols (IEPOX), which are isoprene oxidation products, onto acidic sulfate aerosols is recognized to be an important mechanism for the formation of isoprene-derived secondary organic aerosol (SOA). While a mechanistic understanding of IEPOX-SOA formation exists, several processes affecting their formation remain uncertain. Evaluating mechanistic IEPOX-SOA models with controlled laboratory experiments under longer atmospherically relevant time scales is critical. Here, we implement our latest understanding of IEPOX-SOA formation within a box model to simulate the measured reactive uptake of IEPOX on polydisperse ammonium bisulfate seed aerosols within an environmental Teflon chamber. The model is evaluated with single-particle measurements of size distribution, volume, density, and composition of aerosols due to IEPOX-SOA formation at time scales of hours. We find that the model can simulate the growth of particles due to IEPOX multiphase chemistry, as reflected in increases of the mean particle size and volume concentrations, and a shift of the number size distribution to larger sizes. The model also predicts the observed evolution of particle number mean diameter and total volume concentrations at the end of the experiment. We show that in addition to the self-limiting effects of IEPOX-SOA coatings, the mass accommodation coefficient of IEPOX and accounting for the molar balance between inorganic and organic sulfate are important parameters governing the modeling of the IEPOX-SOA formation. Thus, models which do not account for the molar sulfate balance and/or diffusion limitations within IEPOX-SOA coatings are likely to predict IEPOX-SOA formation too high

Holocene sea-ice dynamics in Petermann Fjord in relation to ice tongue stability and Nares Strait ice arch formation

The Petermann 2015 expedition to Petermann Fjord and adjacent Hall Basin recovered a transect of cores, extending from Nares Strait to underneath the 48&thinsp;km long ice tongue of Petermann glacier, offering a unique opportunity to study ice&ndash;ocean&ndash;sea ice interactions at the interface of these realms. First results suggest that no ice tongue existed in Petermann Fjord for large parts of the Holocene, raising the question of the role of the ocean and the marine cryosphere in the collapse and re-establishment of the ice tongue. Here we use a multi-proxy approach (sea-ice-related biomarkers, total organic carbon and its carbon isotopic composition, and benthic and planktonic foraminiferal abundances) to explore Holocene sea ice dynamics at OD1507-03TC-41GC-03PC in outer Petermann Fjord. Our results are in line with a tight coupling of the marine and terrestrial cryosphere in this region and, in connection with other regional sea ice reconstructions, give insights into the Holocene evolution of ice arches and associated landfast ice in Nares Strait. The late stages of the regional Holocene Thermal Maximum (6900&ndash;5500&thinsp;cal&thinsp;yr&thinsp;BP) were marked by reduced seasonal sea ice concentrations in Nares Strait and the lack of ice arch formation. This was followed by a transitional period towards Neoglacial cooling from 5500&ndash;3500&thinsp;cal&thinsp;yr&thinsp;BP, where a southern ice arch might have formed, but an early seasonal breakup and late formation likely caused a prolonged open water season and enhanced pelagic productivity in Nares Strait. Between 3500 and 1400&thinsp;cal&thinsp;yr&thinsp;BP, regional records suggest the formation of a stable northern ice arch only, with a short period from 2500&ndash;2100&thinsp;cal&thinsp;yr&thinsp;BP where a southern ice arch might have formed intermittently in response to atmospheric cooling spikes. A stable southern ice arch, or even double arching, is also inferred for the period after 1400&thinsp;cal&thinsp;yr&thinsp;BP. Thus, both the inception of a small Petermann ice tongue at &sim;&thinsp;2200&thinsp;cal&thinsp;yr&thinsp;BP and its rapid expansion at &sim;&thinsp;600&thinsp;cal&thinsp;yr&thinsp;BP are preceded by a transition towards a southern ice arch regime with landfast ice formation in Nares Strait, suggesting a stabilizing effect of landfast sea ice on Petermann Glacier. &nbsp;</p

Synergistic hydrothermal liquefaction of waste materials

Synthetic polymers constitute one of the largest fractions of solid waste worldwide. From 1950 to 2015, roughly 12 Gton of these materials were deposited either in landfills or in the environment. The absolute majority of these materials are energetically dense, fossil-derived and non-biodegradable, which causes accumulation in the environment, threatening both marine and terrestrial ecosystems. Chemical recycling of these materials can be a management strategy to alleviate pollution and to reuse otherwise wasted energy in the form of solid materials. Agricultural crop residues are composed of both wet and dry streams, summing up to 3600 Mton year-1 (2013 estimate) of wasted resources globally. Besides that, around 3120 MTon year-1 (2017 estimate) of animal manure is generated worldwide. Nowadays, these agribusiness byproducts are underutilized and their conversion to liquid biofuels may present an untapped opportunity to provide the sustainability needed in sectors dependent on liquid hydrocarbons as an energy source. This thesis focuses on understanding how synthetic polymers and agricultural waste interact under hydrothermal liquefaction (HTL) conditions, identifying opportunities and evaluating the engineering challenges to apply the technology in combined processing of waste streams. This work evaluates the possibility of recovering monomer-like structures from synergistic combined HTL (co-HTL) of synthetic materials and lignocellulosic biomasses. It also evaluates how biocrudes derived from highly synergistic co-HTL behave in downstream processing for biofuel production when compared to single-feedstock biocrudes. HTL uses the reactivity of hot-compressed water in near-critical conditions to convert carbon-based materials into useful short chain organic compounds. The interaction of different feedstock materials under this condition allows a beneficial process efficiency and enlarges the opportunities to apply this process in waste handling scenarios. Literature about HTL processing of synthetic polymers present significant achievements within the field, however the non-standardized approach for several studies lead to contradictory results, generating a knowledge gap between laboratory results and practical applications. Here, results of subcritical HTL processing are presented for the 12 most used synthetic polymers worldwide, both individually and combined with lignocellulosic materials. When evaluating synthetic polymers alone, it is found that materials containing heteroatoms in the backbone of the polymer structure are prone to hydrolysis under subcritical water, while carbon-carbon bonds are preserved. In practice, polymers derived from addition polymerization such as polyolefins and polystyrene do not depolymerize under subcritical water, while condensation polymers and others containing heteroatoms in the backbone are decomposed into molecules similar to their original monomers. When these materials are combined with lignocellulosic ones, the synthetic parts containing nitrogen heteroatoms tend to synergistically interact with the organic-derived molecules and act synergistically increasing biocrude production. The reactivity of nitrogen species in synthetic polymers was directly proportional to the intensity of the synergies verified. The largest synergy identified was for polyurethane combined processing due to the presence of highly reactive amines bonded to aromatic groups. This finding led to an improved combinedprocessing of polyurethane foam and lignocellulosic materials, reaching pilot processing carbon and energy efficiencies of 71 and 75%, respectively. The combination of wet and dry agribusiness waste fractions in HTL processing was evaluated using cow manure and wheat straw, respectively, as representatives. Their combination also leads to enhanced biocrude and carbon recovery during subcritical HTL processing through nitrogen species reactions with lignocellulosic-derived compounds. The formation of heteroatom-containing aromatics acts as a carbon carrier to the biocrude products. With this approach, pilot HTL processing carbon yields were enhanced from 40 to 60 wt%, while also providing superior total energy efficiencies (up to 50% based on organic input and output including heating utilities). This increase in carbon efficiency generates further benefits in the production of hydrotreated products, with biomass-to-hydrotreated products carbon balances increasing from 34 wt% for wheat straw in single HTL to 43 wt% in co-HTL of wheat straw and cow manure. The distillation of hydrotreated products depicts that the nitrogen-containing molecules tend to have higher concentration in heavier fractions, which may be an opportunity for more targeted processing of these fractions. Overall, production of biofuels enlarged via co-HTL mainly due to HTL superior carbon and energy yields. Both synthetic-organic and organic-organic waste combined HTL, the reactions involving nitrogen compounds generate high synergistic effects towards biocrude formation. When increasing product stability through nitrogenated species, a consequent increased difficulty for their removal in following hydrotreatment oil upgrading is also verified. Nevertheless, the enhanced carbon and energy recovery and enlarged scope of HTL technologies attainedvia combination of waste materials is an opportunity to take advantage of these sub-utilized streams

Synergistic hydrothermal liquefaction of waste materials

Synthetic polymers constitute one of the largest fractions of solid waste worldwide. From 1950 to 2015, roughly 12 Gton of these materials were deposited either in landfills or in the environment. The absolute majority of these materials are energetically dense, fossil-derived and non-biodegradable, which causes accumulation in the environment, threatening both marine and terrestrial ecosystems. Chemical recycling of these materials can be a management strategy to alleviate pollution and to reuse otherwise wasted energy in the form of solid materials. Agricultural crop residues are composed of both wet and dry streams, summing up to 3600 Mton year-1 (2013 estimate) of wasted resources globally. Besides that, around 3120 MTon year-1 (2017 estimate) of animal manure is generated worldwide. Nowadays, these agribusiness byproducts are underutilized and their conversion to liquid biofuels may present an untapped opportunity to provide the sustainability needed in sectors dependent on liquid hydrocarbons as an energy source. This thesis focuses on understanding how synthetic polymers and agricultural waste interact under hydrothermal liquefaction (HTL) conditions, identifying opportunities and evaluating the engineering challenges to apply the technology in combined processing of waste streams. This work evaluates the possibility of recovering monomer-like structures from synergistic combined HTL (co-HTL) of synthetic materials and lignocellulosic biomasses. It also evaluates how biocrudes derived from highly synergistic co-HTL behave in downstream processing for biofuel production when compared to single-feedstock biocrudes. HTL uses the reactivity of hot-compressed water in near-critical conditions to convert carbon-based materials into useful short chain organic compounds. The interaction of different feedstock materials under this condition allows a beneficial process efficiency and enlarges the opportunities to apply this process in waste handling scenarios. Literature about HTL processing of synthetic polymers present significant achievements within the field, however the non-standardized approach for several studies lead to contradictory results, generating a knowledge gap between laboratory results and practical applications. Here, results of subcritical HTL processing are presented for the 12 most used synthetic polymers worldwide, both individually and combined with lignocellulosic materials. When evaluating synthetic polymers alone, it is found that materials containing heteroatoms in the backbone of the polymer structure are prone to hydrolysis under subcritical water, while carbon-carbon bonds are preserved. In practice, polymers derived from addition polymerization such as polyolefins and polystyrene do not depolymerize under subcritical water, while condensation polymers and others containing heteroatoms in the backbone are decomposed into molecules similar to their original monomers. When these materials are combined with lignocellulosic ones, the synthetic parts containing nitrogen heteroatoms tend to synergistically interact with the organic-derived molecules and act synergistically increasing biocrude production. The reactivity of nitrogen species in synthetic polymers was directly proportional to the intensity of the synergies verified. The largest synergy identified was for polyurethane combined processing due to the presence of highly reactive amines bonded to aromatic groups. This finding led to an improved combinedprocessing of polyurethane foam and lignocellulosic materials, reaching pilot processing carbon and energy efficiencies of 71 and 75%, respectively. The combination of wet and dry agribusiness waste fractions in HTL processing was evaluated using cow manure and wheat straw, respectively, as representatives. Their combination also leads to enhanced biocrude and carbon recovery during subcritical HTL processing through nitrogen species reactions with lignocellulosic-derived compounds. The formation of heteroatom-containing aromatics acts as a carbon carrier to the biocrude products. With this approach, pilot HTL processing carbon yields were enhanced from 40 to 60 wt%, while also providing superior total energy efficiencies (up to 50% based on organic input and output including heating utilities). This increase in carbon efficiency generates further benefits in the production of hydrotreated products, with biomass-to-hydrotreated products carbon balances increasing from 34 wt% for wheat straw in single HTL to 43 wt% in co-HTL of wheat straw and cow manure. The distillation of hydrotreated products depicts that the nitrogen-containing molecules tend to have higher concentration in heavier fractions, which may be an opportunity for more targeted processing of these fractions. Overall, production of biofuels enlarged via co-HTL mainly due to HTL superior carbon and energy yields. Both synthetic-organic and organic-organic waste combined HTL, the reactions involving nitrogen compounds generate high synergistic effects towards biocrude formation. When increasing product stability through nitrogenated species, a consequent increased difficulty for their removal in following hydrotreatment oil upgrading is also verified. Nevertheless, the enhanced carbon and energy recovery and enlarged scope of HTL technologies attainedvia combination of waste materials is an opportunity to take advantage of these sub-utilized streams

Aromatic organosulfates in atmospheric aerosols: Synthesis, characterization, and abundance

Aromatic organosulfates are identified and quantified in fine particulate matter (PM2.5) from Lahore, Pakistan, Godavari, Nepal, and Pasadena, California. To support detection and quantification, authentic standards of phenyl sulfate, benzyl sulfate, 3-and 4-methylphenyl sulfate and 2-, 3-, and 4-methylbenzyl sulfate were synthesized. Authentic standards and aerosol samples were analyzed by ultra-performance liquid chromatography (UPLC) coupled to negative electrospray ionization (ESI) quadrupole time-of-flight (ToF) mass spectrometry. Benzyl sulfate was present in all three locations at concentrations ranging from 4 – 90 pg m−3. Phenyl sulfate, methylphenyl sulfates and methylbenzyl sulfates were observed intermittently with abundances of 4 pg m−3, 2-31 pg m−3, 109 pg m−3, respectively. Characteristic fragment ions of aromatic organosulfates include the sulfite radical (•SO3−, m/z 80) and the sulfate radical (•SO4−,m/z 96). Instrumental response factors of phenyl and benzyl sulfates varied by a factor of 4.3, indicating that structurally-similar organosulfates may have significantly different instrumental responses and highlighting the need to develop authentic standards for absolute quantitation organosulfates. In an effort to better understand the sources of aromatic organosulfates to the atmosphere, chamber experiments with the precursor toluene were conducted under conditions that form biogenic organosulfates. Aromatic organosulfates were not detected in the chamber samples, suggesting that they form through different pathways, have different precursors (e.g. naphthalene or methylnaphthalene), or are emitted from primary sources