Valorization of rendering industry wastes and co-products for industrial chemicals, materials and energy: review.

Over the past decades, strong global demand for industrial chemicals, raw materials and energy has been driven by rapid industrialization and population growth across the world. In this context, long-term environmental sustainability demands the development of sustainable strategies of resource utilization. The agricultural sector is a major source of underutilized or low-value streams that accompany the production of food and other biomass commodities. Animal agriculture in particular constitutes a substantial portion of the overall agricultural sector, with wastes being generated along the supply chain of slaughtering, handling, catering and rendering. The recent emergence of bovine spongiform encephalopathy (BSE) resulted in the elimination of most of the traditional uses of rendered animal meals such as blood meal, meat and bone meal (MBM) as animal feed with significant economic losses for the entire sector. The focus of this review is on the valorization progress achieved on converting protein feedstock into bio-based plastics, flocculants, surfactants and adhesives. The utilization of other rendering streams such as fat and ash rich biomass for the production of renewable fuels, solvents, drop-in chemicals, minerals and fertilizers is also critically reviewed.

High throughput application of ASTM D8332: Detailed prototype design and operating conditions for microplastic sampling of riverine systems.

Microplastic sampling strategies for aquatic systems commonly employ small mesh nets to collect suspended microparticles. These methods work well for marine sampling campaigns; however, complex water systems such as freshwater rivers, effluent discharges, and stormwater ponds characterized by high total suspended solids and fast-moving water can cause the nets to clog, rip, or tear. Published in 2020, ASTM D8332 is an alternative approach to sampling complex water systems for microplastics involving pumping large volumes of water across a cascading stack of sieves to collect suspended particles. Here we show that ASTM D8332 can be applied to sample freshwater rivers for microplastic collection. A high throughput sampling prototype developed in this work is capable of pumping 1500 L of river water in 45 min to collect particles as small as 45 µm. The system is lightweight, modular, and easily transportable. It has a discrete power supply, allowing for the collection of microplastics anywhere along the river, including municipal discharges. The design minimizes the amount of plastic in the flow path and provides a practical way to measure field contamination. Finally, we outline lessons learned through extensive field trials and testing using this system sampling the North Saskatchewan River in Edmonton, Alberta. •Existing small mesh nets face limitations in freshwater rivers, encountering clogging and tearing issues from high suspended solids and fast moving water.•Using a standardized method, ASTM D8332 - a pumping-based approach is efficient for microplastic collection in freshwater rivers.•Lightweight, modular, plastic free prototype system pumps 1500 L of river water in 45 min, collecting particles as small as 45 µm. Successfully tested in the North Saskatchewan River.

Ruminant-Waste Protein Hydrolysates and Their Derivatives as a Bio-Flocculant for Oil Sands Tailing Management.

Reclamation of tailings ponds is a critical issue for the oil industry. After years of consolidation, the slurry in tailings ponds, also known as fluid fine tailings, is mainly comprised of residual bitumen, water, and fine clay particles. To reclaim the lands that these ponds occupy, separation of the solid particles from the liquid phase is necessary to facilitate water removal and recycling. Traditionally, synthetic polymers have been used as flocculants to facilitate this process, but they can have negative environmental consequences. The use of biological polymers may provide a more environmentally friendly approach to flocculation, and eventual soil remediation, due to their natural biodegradability. Peptides derived from specified risk materials (SRM), a proteinaceous waste stream derived from the rendering industry, were investigated to assess their viability for this application. While these peptides could achieve >50% settling within 3 h in bench-scale settling tests using kaolinite tailings, crosslinking peptides with glutaraldehyde greatly improved their flocculation performance, leading to a >50% settling in only 10 min. Settling experiments using materials obtained through different reactant ratios during crosslinking identified a local optimum molar reactant ratio of 1:32 (peptide amino groups to glutaraldehyde aldehyde groups), resulting in 81.6% settling after 48 h. Taken together, these data highlight the novelty of crosslinking waste-derived peptides with glutaraldehyde to generate a value-added bioflocculant with potential for tailings ponds consolidation.

A sustainable colloidal material with sorption and nutrient-supply capabilities for in situ groundwater bioremediation.

Microbial degradation of subsurface organic contaminants is often hindered by the low availability of both contaminants and nutrients, especially phosphorus (P). The use of activated carbon and traditional P fertilizers to overcome these challenges has proved ineffective; therefore, we sought to find an innovative and effective solution. By heating bone meal-derived organic residues in water in a closed reactor, we synthesized nonporous colloids composed of aromatic and aliphatic structures linked to P groups. X-ray absorption near edge spectroscopy analysis revealed that the materials contain mostly bioavailable forms of P (i.e., adsorbed P and magnesium-bearing brushite). The capacity of the materials to adsorb organic contaminants was investigated using benzene and batch isotherm experiments. The adsorption isotherms were fitted to the linearized Freundlich model; isotherm capacity (logKF ) values for the materials ranged between 1.6 and 2.8 µg g-1 . These results indicate that the colloidal materials have a high affinity for organic contaminants. This, coupled with their possession of bioavailable P, should make them effective amendments for in situ groundwater bioremediation. Also, the materials' chemical properties suggest that they are not recalcitrant, implying that they will not become potential contaminants when released into the environment.

Using Specified Risk Materials-Based Peptides for Oil Sands Fluid Fine Tailings Management.

Fluid fine tailings are produced in huge quantities by Canada's mined oil sands industry. Due to the high colloidal stability of the contained fine solids, settling of fluid fine tailings can take hundreds of years, making the entrapped water unavailable and posing challenges to public health and the environment. This study focuses on developing value-added aggregation agents from specified risk materials (SRM), a waste protein stream from slaughterhouse industries, to achieve an improved separation of fluid fine tailings into free water and solids. Settling results using synthetic kaolinite slurries demonstrated that, though not as effective as hydrolyzed polyacrylamide, a commercial flocculant, the use of SRM-derived peptides enabled a 2-3-fold faster initial settling rate than the blank control. The pH of synthetic kaolinite tailings was observed to be slightly reduced with increasing peptides dosage in the test range (10-50 kg/ton). The experiments on diluted fluid fine tailings (as a representation of real oil sands tailings) demonstrated an optimum peptides dosage of 14 kg/ton, which resulted in a 4-fold faster initial settling rate compared to the untreated tailings. Overall, this study demonstrates the novelty and feasibility of using SRM-peptides to address intractable oil sands fluid tailings.

The Effect of an Adsorbent Matrix on Recovery of Microorganisms from Hydrocarbon-Contaminated Groundwater.

The microbial degradation of recalcitrant hydrocarbons is an important process that can contribute to the remediation of oil and gas-contaminated environments. Due to the complex structure of subsurface terrestrial environments, it is important to identify the microbial communities that may be contributing to biodegradation processes, along with their abilities to metabolize different hydrocarbons in situ. In this study, a variety of adsorbent materials were assessed for their ability to trap both hydrocarbons and microorganisms in contaminated groundwater. Of the materials tested, a porous polymer resin (Tenax-TA) recovered the highest diversity of microbial taxa in preliminary experiments and was selected for additional (microcosm-based) testing. Oxic and anoxic experiments were prepared with groundwater collected from a contaminated aquifer to assess the ability of Tenax-TA to adsorb two environmental hydrocarbon contaminants of interest (toluene and benzene) while simultaneously providing a surface for microbial growth and hydrocarbon biodegradation. Microorganisms in oxic microcosms completely degraded both targets within 14 days of incubation, while anoxically-incubated microorganisms metabolized toluene but not benzene in less than 80 days. Community analysis of Tenax-TA-associated microorganisms revealed taxa highly enriched in sessile hydrocarbon-degrading treatments, including Saprospiraceae, Azoarcus, and Desulfoprunum, which may facilitate hydrocarbon degradation. This study showed that Tenax-TA can be used as a matrix to effectively trap both microorganisms and hydrocarbons in contaminated environmental systems for assessing and studying hydrocarbon-degrading microorganisms of interest.

Mechanistic study on demulsification of water-in-diluted bitumen emulsions by ethylcellulose.

In our previous study, ethylcellulose (EC), an effective, nontoxic, and biodegradable natural polymer, was found effective in dewatering water-in-diluted bitumen emulsions. In this study, the demulsification mechanism of water-in-diluted bitumen emulsions by EC is investigated. In situ experiments using a micropipet apparatus provided direct evidence on both flocculation and coalescence of water droplets in diluted bitumen by EC. The addition of EC was found to decrease naphtha-diluted bitumen-water interfacial tension significantly. At the molecular level, AFM imaging revealed disruption of the continuous interfacial films formed from surface-active components of bitumen by EC. Our study clearly indicates that the demulsification by EC is through both flocculation and coalescence of water droplets, attained by competitive adsorption of EC at the oil-water interface and disruption of the original protective interfacial films formed from the surface-active components of bitumen.

Surface and thermal enhancement of the cellulosic component of thermo mechanical pulp using a rapid method: Iodomethane modification.

The feasibility of employing chemical methods for enhancement of cellulose-based materials is dependent on the availability, price, and green index of the modifying agent. This study details the use of iodomethane, an inexpensive organo halide, to increase the hydrophobicity of thermo mechanical (TMP) samples, which renders them better structural elements for composite materials. For this system, we studied the influence of various concentration of iodomethane, concentration of caustic, and reaction time. Infrared spectroscopy suggested reaction of the organo halide with the hydroxyl groups of cellulose and lignin components of TMP. Pulp samples treated for 4 h or at low caustic concentration showed the least improvements plausibly due to pulp degradation or poor pulp swelling, respectively. On the other hand, pulp treated at 3 h using high concentrations of caustic were characterized with surfaces that were more hydrophobic. Thus, this study outlines a fast and organic solvent-free (clean up) method that can be used to enhance pulp samples for composite applications.

Modification of the cellulosic component of hemp fibers using sulfonic acid derivatives: Surface and thermal characterization.

The aim of this study was to characterize the surface, morphological, and thermal properties of hemp fibers treated with two commercially available, inexpensive, and water soluble sulfonic acid derivatives. Specifically, the cellulosic component of the fibers were targeted, because cellulose is not easily removed during chemical treatment. These acids have the potential to selectively transform the surfaces of natural fibers for composite applications. The proposed method proceeds in the absence of conventional organic solvents and high reaction temperatures. Surface chemical composition and signature were measured using gravimetric analysis, X-ray photoelectron spectroscopy (XPS) and Fourier transform infra-red spectroscopy (FTIR). XPS data from the treated hemp fibers were characterized by measuring the reduction in O/C ratio and an increase in abundance of the C-C-O signature. FTIR confirmed the reaction with the emergence of peaks characteristic of disubstituted benzene and amino groups. Grafting of the sulfonic derivatives resulted in lower surface polarity. Thermogravimetric analysis revealed that treated fibers were characterized by lower percent degradation between 200 and 300 °C, and a higher initial degradation temperature.

Two-stage thermal conversion of inedible lipid feedstocks to renewable chemicals and fuels.

The aim of this work was to study the conversion of inedible, low cost lipid feedstocks to renewable hydrocarbons using a two stage thermal hydrolysis-pyrolysis method. Beef tallow, yellow grease, brown grease and cold pressed camelina oil were first hydrolyzed and the fatty acids produced were recovered and pyrolyzed in batch reactors. The pyrolysis products were identified and quantified using gas chromatography and mass spectrometry. The pyrolysis product yields were similar for all the feedstock used with the organic liquid fraction (OLF) accounting for 76-80% of the product. The OLF consisted predominantly of n-alkanes. Approximately 30% OLF constituted a gasoline-equivalent fraction and 50% a diesel fraction. Other fuel property test showed that the OLF met the specifications set out by the Canadian general standards board. This research demonstrated a novel two-stage thermal hydrolysis-pyrolysis conversion method for producing OLF from inedible and low-value lipids.

Two-step thermal conversion of oleaginous microalgae into renewable hydrocarbons.

The aim of this study was to evaluate the conversion of microalgal biomass to renewable chemicals and fuels through a two-step reaction and separation process. High density Chlorella protothecoides culture with 40% lipid accumulation (dwb) was produced in 10 L bioreactors and hydrolyzed in batch stainless steel reactors under subcritical conditions. After hydrolysis, fatty acids free of sulfur and low in nitrogen and salts, were recovered by hexane extraction. The fatty acids were pyrolyzed at 410°C for 2h under N2 yielding n-alkanes, α-olefins and internal olefins and low molecular weight fatty acids. This study demonstrated the direct conversion of microalgal biomass into valuable platform chemicals and fuels compatible with the existing industrial hydrocarbon infrastructure.

Surface tension phenomena in the xylem sap of three diffuse porous temperate tree species.

In plant physiology models involving bubble nucleation, expansion or elimination, it is typically assumed that the surface tension of xylem sap is equal to that of pure water, though this has never been tested. In this study we collected xylem sap from branches of the tree species Populus tremuloides, Betula papyrifera and Sorbus aucuparia over 3 months. We measured the instantaneous surface tension and followed changes over a period of 0.5-5 h using the pendant drop technique. In all three species the instantaneous surface tension was equal to or within a few percent of that of pure water. Further, in B. papyrifera and S. aucuparia the change over time following drop establishment, although significant, was very small. In P. tremuloides, however, there was a steep decline in surface tension over time that leveled off towards values 21-27% lower than that of pure water. This indicated the presence of surfactants. The values were lower for thinner distal branch segments than for proximal ones closer to the trunk. In some species it appears valid to assume that the surface tension of xylem sap is equal to that of water. However, in branch segments of P. tremuloides close to the terminal bud and hence potentially in other species as well, it may be necessary to take into account the presence of surfactants that reduce the surface tension over time.

Irreversible Collapse of Poly(vinyl stearate) Monolayers at the Air-Water Interface.

The collapse of Langmuir monolayers of poly(vinyl stearate) (PVS) at the air-water interface has been investigated by combined measurements of the surface pressure-area isotherms and Brewster angle microscopy (BAM). Atomic force microscopy (AFM) has been used to gain out-of-plane structural information on collapsed films transferred onto a solid substrate by a modified version of the inverse Langmuir-Schaefer deposition method. At high areas per monomer repeat unit, BAM imaging revealed that the films are heterogeneous, with large solidlike domains (25-200 mum in diameter) coexisting with liquidlike domains. Upon film compression, the domains coalesced to form a homogeneous monolayer before the film collapsed at constant pressure, forming irreversible three-dimensional (3D) structures. BAM images showed that two 3D structures coexisted: buckles of varying width extending across the surface and perpendicular to the direction of the compression and dotted islandlike structures. Upon expansion, the film fractured and both 3D protrusions persisted, explaining the marked hysteresis recorded in the Langmuir isotherms. Experiments with AFM confirmed the 3D nature of both protrusions and revealed that many buckles contain substructures corresponding to narrow buckles whose heights are a multiple of a single bilayer. Additionally, many multilayer islands with diameters spanning from 0.2 mum to over 3.5 mum were characterized by varying heights between 2 nm and up to over 50 nm. The key to the formation of the irreversible 3D structures is the presence of large inhomogeneities in the PVS monolayer, and a generalized phenomenological model is proposed to explain the collapse observed.