Apparent Molecular Weight Distribution Research Articles

Effects of hydrolysis degree on the functional properties of hydrolysates from sour cherry kernel protein concentrate

During the processing of sour cherries into different foodstuffs, a large amount of kernels is produced as waste material, which creates a significant disposal problem for the food industry. Sour cherry kernels containing 25.3–35.5% of protein can be used as a functional protein source in food production. Therefore, we aimed to study the effects of hydrolysis degree on the sour cherry kernel protein hydrolysates.
 Proteins were extracted from the defatted flour by isoelectric precipitation. The resulting protein concentrate was hydrolyzed (5, 10, and 15% hydrolysis) using Alcalase to yield hydrolysates. We determined their oil and water holding, emulsifying, gelation, and foaming properties, as well as apparent molecular weight distribution and proximate compositions.
 No protein fractions greater than an apparent molecular weight of about 22 kDa were present in the hydrolysates. The hydrolysis of the protein concentrate mostly led to an increase in protein solubility. As the degree of hydrolysis increased from 5 to 15%, the water holding capacity of the hydrolysates decreased from 2.50 ± 0.03 to 2.03 ± 0.02 g water/g, indicating its deterioration. 
 The hydrolysates obtained at different degrees of hydrolysis had a better solubility than the intact protein concentrate. The oil holding capacity, the foaming stability, and the least gelation concentration of the protein concentrate could not be considerably improved by hydrolysis. In contrast, its emulsifying activity index and foaming capacity could be increased with a limited degree of hydrolysis (up to 10%).

Asphaltene agglomeration through physical-chemical and rheological testing

A better understanding of the changes in binder chemistry and microstructure triggered by aging is fundamental as it increases the cracking susceptibility of asphalt materials and reduces pavement durability. In this context, this paper presents the findings of a collaborative study that delves further into the alterations in binder chemistry, microstructure, and rheology of laboratory – and field-aged binders using innovative experimental and fundamental theory techniques. An increase in polarity leading to a shift in the apparent molecular weight distribution (AMWD) towards higher molecular weights, which implies molecular agglomerations, could be observed as a result of aging via Saturates, Aromatics, Resins, and Asphaltene Determinator (SAR-AD) and Size Exclusion Chromatography (SEC), respectively. As for the theoretical methods, the δ-method and Molecular Agglomeration Index (MAI) that estimate the AMWD and incidence of molecular agglomeration, respectively, show satisfactory relationship with the SAR-AD and SEC results. This reinforces the soundness of the δ-method and MAI.

Apparent Molecular Weight Distributions in Bituminous Binders.

Molecular weight distributions are widely used to evaluate the effects of aging or modifiers in bituminous binders. As with polymers, the most common techniques to obtain the distributions can be subdivided into two main groups, depending on whether or not they use a solvent. In the first group, the dimension of the molecules is evaluated in a diluted unperturbed state, while, in the second, the dimension derives from the bulk, where aggregated or interacting molecules may behave as single entities. However, the calibration curves used in the bulk are tuned in order to homogenize the results derived from the two approaches. This sort of contradiction, plus the high number of experimental uncertainties, suggest that the term “apparent” should be used for both distributions. These aspects are well known in the field of polymers but have received less attention in the case of bitumens, which are even more complex. This paper pinpoints the advantages and disadvantages of the two techniques, thus highlighting the most appropriate use. Bulk methods are preferred when evaluating properties that are strictly dependent on the microstructure, such as the level of aging and the effects of additives or modifiers. Diluted methods should be used when the molecular size matters, such as in quantifying the presence of polymers or rejuvenators. Both techniques should be used for comparative studies only.

Diffusion of soluble organic substrates in aerobic granular sludge: Effect of molecular weight

Aerobic granular sludge (AGS) is an advanced biofilm-based technology for wastewater treatment. Diffusion of substrates into the granules is a key aspect of this technology. Domestic wastewater contains soluble organic substrates of different sizes that could potentially diffuse into the granules. In this study, the relation between the molecular weight of a substrate and its diffusion coefficient within the granule was studied with model substrates (polyethylene glycols (PEGs) with a molecular weight between 62 and 10 000 Da). The diffusion coefficients of the model substrates within granules from a full-scale installation were measured with the ‘transient uptake of a non-reactive solute’ method. The diffusion coefficients in the granules were not significantly different from the diffusion coefficients in water, at least up to 4000 Da molecular weight. This indicates that these PEGs were not obstructed by the granule matrix. The 10 kDa PEG behaved differently from the lighter PEGs, as it could not penetrate the entire granule. Furthermore, the granule structure was characterized with Environmental Scanning Electron Microscopy (ESEM). The granules displayed an open structure with large macropores and semi-solid regions, which contained microbial cells. The diffusion results suggest that most diffusing molecules were unobstructed in the macropores and barely obstructed in the semi-solid regions. Only the diffusion of the 10 kDa PEG seemed to be hindered by the semi-solid regions, but not by the macropores. Lastly, the apparent molecular weight distribution of domestic wastewater soluble COD was determined with ultrafiltration membranes of 100, 10, and 1 kDa molecular weight cut-off. The influent fractionation revealed that a large part (61–69%) of the influent soluble COD was lighter than 1 kDa. As molecules lighter than 1 kDa diffuse easily, the majority of the influent soluble COD can be considered as diffusible COD. These findings provide new insight into the availability of influent COD for granular sludge.

Molecular Agglomeration Index: Quantification of the Incidence of Asphaltene Molecular Agglomeration in Aged Asphalt Binders Through Rheological Measurements

The phase angle (φ) has long been recognized as a powerful tool to detect variations in asphalt binders’ chemistry and microstructure. A recent study applied unsupervised multivariate approaches to uncover hidden pattern structures in data sets and settled the most relevant reduced frequency to investigate the evolution of the phase angle master curve with aging. Considering that study’s findings, this paper revisits the δ-method—that is, an approach that estimates the apparent molecular weight distribution (AMWD) of a given asphalt binder based on its rheology—and proposes a simple indicator that quantifies the incidence of asphaltene molecular agglomeration named Molecular Agglomeration Index (MAI). Laboratory- and field-aged binders were tested and a limiting value for MAI indicating an increased binder cracking susceptibility is established in agreement with other failure criteria found in the literature.

Apparent Molecular Weight Distributions for Investigating Aging in Polymer-Modified Bitumen

The oxidative aging of bituminous binders affects the performance and durability of pavements. In the case of polymer-modified binders, aging involves both bitumen and polymers and has a strong impact on the whole architecture of the material. Rheology may help in understanding these structural changes, and interesting information may be obtained by analysing the evolution of apparent molecular weight distributions. This was demonstrated with a bituminous binder modified with a poly(styrene-butadiene) block copolymer and subjected to prolonged artificial aging. Isothermal frequency sweep tests were used to construct master curves of the phase angle and magnitude of the complex modulus. The master curves were then used to calculate relaxation spectra and apparent molecular weight distributions of the binders, as well as simulated temperature sweep tests. A comparison of the behaviour of the base and modified bitumen highlighted the role of the polymer in aging. Polymer degradation significantly damages the elastomeric network, yet the residual polymer chains still interact with the bitumen molecules and reduce their oxidative aging. The apparent molecular weight distributions were deconvoluted to create an aging index specifically developed for polymer-modified bitumen.

Evolution of rheological parameters and apparent molecular weight distribution in the bitumen from reclaimed asphalt with rejuvenation and re-ageing

The paper aims at analysing the evolution of the rheological behaviour of the bitumen extracted from reclaimed asphalt (RA) with rejuvenation (blending of virgin and RA bitumen, with addition of a rejuvenator) and re-ageing. The complex modulus of the binders was measured through a DSR device, while RTFOT and PAV protocols were followed to reproduce the bitumen ageing. Three rheological models were used in order to study the evolution of their parameters in the various steps. In addition, the apparent molecular weight distribution (AMWD), determined through δ-method, was analysed. The results showed that the rejuvenator could reduce RA bitumen stiffness but had low effect on the phase angle. After long-term re-ageing, the rejuvenated RA bitumen showed comparable rheological behaviour with respect to the bitumen initially recovered from RA. However, the AMWD analysis showed that the rejuvenator did not adequately disrupt the asphaltene clusters in the aged bitumen.

Physical-chemical properties and in vitro digestibility of phosphorylated and glycosylated soy protein isolate

Increased demand for highly functional soy protein isolate (SPI) in the food industry draws extra attention to SPI modification. The structural properties and in vitro digestibility of phosphorylated and glycosylated SPI were investigated in this study. The phosphorylation was carried out with sodium tripolyphosphate addition at 45 °C for 4 h. Glucose and dextran were used for glycosylation at 100 °C for 1 h. Apparent molecular weight distribution was determined by size exclusion-high performance liquid chromatography. Thiol content and surface hydrophobicity were also determined. The apparent molecular weight and thiol content of phosphorylated SPI increased with the increase of phosphorylation degree. Meanwhile, phosphorylation negatively affected gastrointestinal digestibility, especially gastric digestibility. The fraction of glycosylated SPI was prone to be low molecular weight, suggesting glycosylation inhibited SPI aggregation, which resulted from the attenuated surface hydrophobicity. The digestibility of SPI was increased by glycosylation. Glucose-based glycosylation contributed to lower intestinal digestion compared with dextran-based glycosylated SPI. This work highlighted that the phosphorylation and glycosylation to SPI primarily affected the in vitro pepsin or pancreatin digestion, inspiring to produce modified SPI with balanced functional and nutritional properties for the food industry.

Use of Linear Viscoelastic Functions to Estimate the Aging Resistance and Internal Structure of Bituminous Binders

Rheology is the most widely used technique to evaluate the performance and aging of bituminous binders. Since there are many available rheological tests, there is also a wide range of aging indexes and it is not easy to choose the most appropriate one, because a single value may hardly be adequate for different properties or operating conditions. In order to generalize the usefulness of an index, a good starting point is deriving it from a set of data, such as the master curves of linear viscoelastic functions. Then, the problem is the quantification of aging in a single numerical value from continuous curves, covering a wide range of frequencies/temperatures. In this work, a summary of the aging indexes derived from the master curves is reported and discussed. The indexes are applied to a bituminous binder either with or without the addition of an organo-modified layered silicate. The apparent molecular weight distributions and relaxation spectra were also calculated from the master curves and used to characterize the effect of aging on the binder properties and structure. In this way, an interesting parallelism was observed between the SARA fractions and the populations derived from a deconvolution analysis of the apparent molecular weight distributions.

Deconvolution of Size Exclusion Chromatograms: New Insights into the Molecular Weight Distribution of Dissolved Organic Matter in Ozone and Biological Activated Carbon

Size exclusion chromatography (SEC) is a useful tool for understanding the apparent molecular weight (AMW) distribution of dissolved organic matter (DOM). However, the limitation that a single anal...

Manure Fertilization Gives High-Quality Earthworm Coprolites with Positive Effects on Plant Growth and N Metabolism

Humic substances (HS) are important soil components playing pivotal roles in guaranteeing long-term soil fertility. In this study, the chemical and biological properties of HS extracted from earthworm coprolites collected in soils subjected to different fertilization inputs (no fertilization, NF; fertilization with farmyard manure, FM; mineral input, M; mixed inputs, FMM, half farmyard manure plus half mineral input) were investigated. Results indicated a relationship between fertilization input and composition, molecular complexity and apparent molecular weight distribution of HS produced by earthworms. Coprolites from FM and FMM soils were the most enriched in organic carbon (OC), and HS from coprolites of FM soil were the highest in humic carbon (HC). Also, soil amendment with manure increased carboxylate and aromatic groups in HS, and the fraction with a high degree of polycondensation, thus indicating a positive impact of manure on plant residues’ degradation processes. These HS were the only to display hormone-like activity, which likely accounted for their most pronounced positive effects on plant growth and metabolism, including accumulation of chlorophylls, mineral nutrition, and activity of nitrogen assimilation enzymes, in oat (Avena sativa L.) plants growing in a soil-less system. We conclude that manure input favored the turnover of OC towards the humification process that led to the production of high-quality coprolites and HS with superior biological activity, and suggests that OC in coprolites and HC in HS from earthworms might be used as reliable indicators of soil fertility.

Characterization of fluorescent dissolved organic matters in metalworking fluid by fluorescence excitation-emission matrix and high-performance liquid chromatography

In recent years, precise environment supervision has gradually become vital in water pollution control, which requires the clear identification of dissolved organic matters (DOM) in wastewater. Metalworking fluid (MWF) is a type of wastewater with high toxicity. Over ten million m3 of MWF is discharged per year. However, its DOM characteristics have not yet been systematically investigated. Therefore, in this study, the fluorescent DOM (FDOM) of MWF was firstly characterized by excitation-emission matrix-parallel factor analysis (EEM-PARAFAC) and high-performance liquid chromatography (HPLC). Three fluorescent components (C1-C3) of the MWF from three metalworking plants (BO, TH, and YD) were identified. The peaks measured for C1 and C3 were attributed to tryptophan-like (Peak T) and humic/fulvic acid-like (Peak A + C) peaks, respectively, and the peaks at C2 were identified as humic-like (Peak A + M) or tryptophan-like (Peak T) peaks. There were differences in the C2 and C3 components of MWF from the three metalworking plants. The FDOM of MWF from the three metalworking plants exhibited similar polarity, but different apparent molecular weight distributions. In addition, the highest intensities of the three fluorescent peaks were sensitive to variations in the pH, humic acid (HA) concentrations, and metal ion levels (Cu2+, Fe3+, and Ni2+). The findings of this study not only indicate the FDOM characteristics of MWF, but also provide a promising method and valuable guidance for the practical monitoring of MWF in natural water bodies.

Organic matter removal and membrane fouling mitigation during algae-rich surface water treatment by powdered activated carbon adsorption pretreatment: Enhanced by UV and UV/chlorine oxidation

In this work, UV and UV/chlorine (UV/Cl) were employed to enhance powdered activated carbon (PAC) adsorption pretreatment prior to ultrafiltration process for algae-contaminated surface water treatment. Their performance on membrane fouling mitigation and organic pollutant rejection was systematically evaluated. A comparative experiment was conducted under varying pollution degrees of algal extracellular organic matter (EOM) contamination in surface river water. The results indicated that UV/PAC and UV/Cl/PAC pretreatment effectively enhanced the removal of dissolved organic carbon (DOC) and UV-absorbing at 254 nm (UV254). The characteristics of feed water after pretreatments were investigated through apparent molecular-weight (MW) distribution and fluorescence parallel factor analysis (PARAFAC). In regard to membrane fouling mitigation, UV/Cl/PAC noticeably decreased reversible and irreversible fouling resistance simultaneously and UV/PAC preferred reducing reversible membrane fouling. Combined fouling modeling was operated to scrutinize the fouling mitigation mechanisms and standard pore blocking was proved to be dominant during the filtration process. Moreover, the UV/Cl and UV/Cl/PAC pretreatments were proved positive for emerging micropollutants degradation and disinfection by-products formation potential reduction. The results suggested that UV and UV/Cl are likely strategies to enhance the efficiency of PAC adsorption pretreatments prior to ultrafiltration during algae-contaminated water treatment.

Comparison of the effects of ozone, biological activated carbon (BAC) filtration and combined ozone-BAC pre-treatments on the microfiltration of secondary effluent

The effects of ozonation (O3), biological activated carbon (BAC) filtration and combined O3 and BAC (O3-BAC) pre-treatments on the microfiltration (MF) treatment of secondary effluent using a polyvinylidene fluoride (PVDF) membrane were studied. The permeability of the membrane was quantified and compared to the removal of humic substances (HS), biopolymers (BPs), dissolved organic carbon (DOC), absorbance at 254 nm (UVA254), and colour by these pre-treatments. The apparent molecular weight distribution (AMWD) was determined to further characterise the secondary effluent before and after each treatment. The unified membrane fouling indices (UMFI) after O3, BAC and the O3-BAC pre-treatments were also determined to evaluate the relative effectiveness of different pre-treatments on fouling reduction. The overall removal of colour and UVA254 in the MF of the O3 pre-treated secondary effluent was found to be 83% and 52% respectively, compared to 75% and 47% respectively for MF with BAC pre-treatment and 38% and 14% respectively without pre-treatment. The O3-BAC pre-treatment yielded the highest normalized permeability after 100 min of operation (0.76) and the lowest UMFI (1 × 10−3 m2/L). This result indicates that the O3-BAC pre-treatment could reduce the frequency of chemical cleaning and may extend the membrane lifetime.

Quantification of asphalt binder ageing from apparent molecular weight distributions using a new approximated analytical approach of the phase angle

This paper aims to explore the effect of ageing on macromolecular organisation of pure petroleum asphalts by interpreting their rheological behaviours. Phase angle measurements are used to determine apparent molecular weight distributions (AMWD) assuming a special relationship between relaxation times and molecular sizes. This procedure is called the ‘delta method’. Four asphalt binders have been characterised in their original state and after lab ageing using conventional tests simulating ageing during the mixing process (RTFOT) and after several years of road service (PAV). Rheological properties have been measured with a visco-analyser METRAVIB under annular shearing and tension-compression mode of loadings. Measurements have been performed from –20°C to 60°C with a frequency sweep from 1 to 80 Hz. An analytical approximation of the phase angle, derived from the Huet-Such model, is used to calculate the AMWDs for each sample. A deconvolution procedure is then applied in order to identify four populations of molecular objects. This procedure allows to identify an increase of large molecular objects with ageing. The deconvolution procedure allows proving that it is the effect of smaller molecules that agglomerate themselves with the increase of the polar species content due to oxidation. This work shows that it is possible to get useful information on the asphalt macromolecular structure from linear viscoelastic measurements.

Waterlogging and soil reduction affect the amount and apparent molecular weight distribution of dissolved organic matter in wetland soil: a laboratory study

The release of dissolved organic matter (DOM) from wetland soils is an important pathway for the input of organic compounds into adjacent aquatic environments. In the present study we investigated, under controlled laboratory conditions, the quantity and quality of DOM released from a wetland soil subject to waterlogging and reducing conditions. Three soil redox conditions (oxic, moderately reducing and advanced reducing) were distinguished based on nitrate, ferrous ions and sulfate concentrations in soil solution. Under each redox condition, the quantity (dissolved organic carbon (DOC), humic substances and peptides plus proteins (P-PN) and quality (aromaticity; specific ultraviolet absorbance at 254 nm (SUVA254nm)) and apparent molecular weight (aMW) distribution) of DOM were investigated. The results showed that soil redox condition affects the amount and properties of mobilised DOM. The rate of DOM release and SUVA254 values were highest during the transition from oxic to moderately reducing conditions, whereas both stabilised during progression to advanced reducing conditions. In addition, the mobilised DOM is expected to be more reactive because of an increase in polar substituents in aromatic structures between oxic and moderately reducing conditions. During the development of moderately reducing conditions, dissolved humic substances increased significantly, whereas their aMW distribution (between 500 and 6000 ) remained constant for each of the three different redox conditions. In contrast, the quantity of dissolved P-PN remained low and steady under the three redox conditions, whereas the aMW distribution of protein-like and microbial by-product-like compounds decreased during the development of reducing conditions (aMW of compounds between 100 and >100 000).

Ageing evolution of foamed warm mix asphalt combined with reclaimed asphalt pavement

The combination of high rates of reclaimed asphalt pavement (RAP) and warm mix asphalt (WMA) technologies is still ambiguous in terms of durability. With the aim of clarifying this issue, a study comparing a hot mix asphalt with a WMA prepared using the foaming process technology. Both mixes contain 50% of RAP and are submitted to a laboratory ageing procedure. The long term related performance of the mixtures is compared by means of complex modulus and fatigue testing. Penetration and ring and ball tests are undertaken on the recovered bitumens, as well as the ageing evolution, characterised by the Fourier Transform Infrared analysis. Finally, the Apparent Molecular Weight Distribution (AMWD) of the binders is calculated from rheological measurements using the δ-method. Results show a relation between ageing evolution and mechanical performance. After ageing, the overall tendencies are similar for both processes.

Evaluación del efecto rejuvenecedor de bio-materiales sobre ligantes para mezclas con alto contenido de asfalto recuperado

The interest in using bio-materials in pavement engineering has grown significantly over the last decades due to environmental concerns about the use of non-recoverable natural resources. In this paper, bio-materials are used together with Reclaimed Asphalt (RA) to restore some of the properties of the aged bitumen present in mixtures with high RA content. For this purpose, two bio-materials are studied and compared to conventional and polymer modified bitumens. Blends of these materials with RA bitumen were produced and studied to simulate a 50% RA mixture. The rejuvenating effect of the two bio-materials on RA has been assessed and compared with the effect of the conventional binders. Apparent Molecular Weight Distribution of the samples (obtained by the ?-method) and different rheological parameters were used for this purpose. Results revealed the power of bio-materials to rejuvenate RA bitumen, showing their capability to be used as fresh binders in high-RA content mixtures.

Hydrophobic features of EPS extracted from anaerobic granular sludge: an investigation based on DAX-8 resin fractionation and size exclusion chromatography.

The hydrophobic fractionation of extracellular polymeric substances (EPS) extracted from anaerobic granular sludge was performed on the DAX-8 resin (two elution pH conditions, i.e., pH2 and pH5 were tested). The impact of seven different EPS extraction methods on EPS hydrophobicity features was assessed. The results showed that the extraction methods and bulk solution pH influenced dramatically the biochemical composition of the EPS, and in turn, the hydrophobicity determined. Besides, EPS extracting reagents i.e., formaldehyde, ethanol, sodium dodecyl sulfate (SDS), and Tween 20 not only introduced extra carbon content in the total organic carbon (TOC) measurement but also interacted with the DAX-8 resin. By comparing the apparent molecular weight (aMW) distribution of untreated and pH-adjusted EPS samples, more complete EPS aMW information was preserved at pH5. Thus, elution at pH5 was preferred in this study for the qualitative analysis of EPS hydrophobic features. The hydrophobic fraction of EPS retained by the resin at pH5 was ascribed to a wide aMW range, ranging from >440 to 0.3kDa. Within this range, EPS molecules ranging from 175 to 31kDa were mostly retained by the DAX-8 resin, which indicates that these EPS molecules are highly hydrophobic.

Role of microbial reducing activity in antimony and arsenic release from an unpolluted wetland soil: a lab scale study using sodium azide as a microbial inhibiting agent

Environmental contextAntimony and arsenic are toxic elements occurring naturally in the environment. We found that arsenic release to water from an unpolluted wetland soil is related to microbial reducing activity only, whereas antimony can still be released when this activity is inhibited, suggesting the involvement of additional processes. The findings show that microbial/non-microbial mechanisms control arsenic and antimony release and can thereby impact water quality at wetland outlets. AbstractIn wetland soils, the mobility of geogenic metal(loid)s is usually associated with direct or indirect microbial-induced processes (solubilisation of mineral and organic components, pH induced desorption, competition effects, dissimilatory reduction). To identify the role of microbial reducing activity in As and Sb release, we conducted two series of soil incubations (sodium azide-treated (NaN3-T) and non-treated (NT)) in closed batches for 36 days. During the incubation period, we monitored the evolution of dissolved As, Sb, Mn, FeII, organic carbon (DOC), humic substances (HS) and proteins (PN) with their apparent molecular weight distribution (aMW) as well as pH, reduction potential (Eh) and alkalinity. Results showed that the release of As and Sb occurred when microbially reducing conditions prevailed (NT soil Eh ~0mV and FeII>40mg L–1) and was inhibited for As in the absence of microbial reducing activity (NaN3-T soil; Eh>250mV and Fe<1mg L–1). In contrast, Sb behaved differently since its release was only slowed down when microbially reducing conditions were inhibited. We concluded that soil microbial reducing activity fully controls the release of As and to a lesser extent that of Sb when NaN3 is used as a microbial inhibiting agent. Since Sb release and dissolved organic matter (DOM) solubilisation (NaN3-induced artefact) occurred simultaneously in the absence of microbially reducing conditions, we concluded that organic matter could be one key factor controlling Sb mobilisation in the given conditions, which is not the case for As.