Chemical properties of biocrude oil from the hydrothermal liquefaction of Spirulina algae, swine manure, and digested anaerobic sludge

This study explores the influence of wastewater feedstock composition on hydrothermal liquefaction (HTL) biocrude oil properties and physico-chemical characteristics. Spirulina algae, swine manure, and digested sludge were converted under HTL conditions (300 °C, 10-12 MPa, and 30 min reaction time). Biocrude yields ranged from 9.4% (digested sludge) to 32.6% (Spirulina). Although similar higher heating values (32.0-34.7 MJ/kg) were estimated for all product oils, more detailed characterization revealed significant differences in biocrude chemistry. Feedstock composition influenced the individual compounds identified as well as the biocrude functional group chemistry. Molecular weights tracked with obdurate carbohydrate content and followed the order of Spirulina < swine manure < digested sludge. A similar trend was observed in boiling point distributions and the long branched aliphatic contents. These findings show the importance of HTL feedstock composition and highlight the need for better understanding of biocrude chemistries when considering bio-oil uses and upgrading requirements.     

Fractions composition study of the pyrolysis oil obtained from sewage sludge treatment plant

In this work the parameters of Low Temperature Conversion - LTC were applied in a centrifuged sludge from a sewage treatment plant located in Rio de Janeiro, Brazil. Before the conversion, the sludge was dried and analyzed by TGA to observe its behavior with increasing temperature. The chemical composition of the crude pyrolysis oil was analyzed by FTIR, ¹H NMR and GC-MS. The results showed that the oil is a mixture of hydrocarbons, oxygenated and nitrogenated compounds. Using a catalytic treatment it was possible to fractionate the oil where the predominant constituents were hydrocarbons showing that the cracking was effective. An important result was the difference between the calorific value of dry sludge (10 MJ kg⁻¹), the pyrolysis oil (36 MJ kg⁻¹) and one of the fractions separated by catalytic cracking (40 MJ kg⁻¹) when compared with commercial diesel (45 MJ kg⁻¹).     

The hydrolytic route to Co-porphyrin-doped SnO2 gas-sensing materials: Chemical study of Co-porphyrin versus Sn(IV) oxide interactions

SnO₂ and SnO₂ + Co-porphyrin solids were prepared from SnCl₄ in propanol and hydrolyzed to sol. Thermal behavior of samples obtained at 110 °C was studied in the 20-600 °C interval by thermal analysis coupled with mass spectrometry for identification of released species. The original samples maintain residual Sn-OR, Sn-OH and Sn-Cl groups up to 350 °C. The sample doped with 1% Co-porphyrin differs for a significant presence of residual Sn-Cl species, accounting for SnCl₄ release in the 300-340 °C range.¹¹⁹Sn solid state NMR analysis reveals disordered SnO₂ species in the sample heated at 250 °C and non-uniform SnO₆ units in the SnO₂ + Co-porphyrin sample at 110 °C, due to persistence of Sn-OR and Sn-OH groups. This complexity is lost at 250 °C. X-ray diffraction analysis confirms all these data. The sensing efficiency of these materials versus alcohols is ascribed to the presence of an open, incomplete SnO₂ structure, which is more pronounced in the Co-porphyrin-doped sample.     

Characterization of lignin-rich residues remaining after continuous super-critical water hydrolysis of poplar wood (Populus albaglandulosa) for conversion to fermentable sugars

Poplar wood flour (Populous albaglandulosa) was treated with sub- and super-critical water (subcritical: 325, 350 °C; super-critical: 380, 400, 425 °C) for 60 s at 220 ± 10 atm. Hydrochloric acid (0.05% v/v) was added to samples as acidic catalyst. The final products were separated into water soluble fraction and undegraded solids. The yields of undegraded solids were thoroughly dependent on temperature severity and mainly composed of lignin fragments. Average molecular weights of the lignins were between 1500 and 4400 Da, which was only 1/3-1/8-fold of poplar milled wood lignin (13,250 Da). DFRC (Derivatization Followed by Reductive Cleavage) analysis revealed that C6C3 phenols (coniferyl and sinapyl alcohol) were rarely detected in the lignins, indicating occurrence of two probable lignin reactions during SCW hydrolysis: lignin fragmentation via splitting of β-O-4 linkage and loss of propane side chains. These results were also confirmed by ¹H and ¹³C NMR spectroscopic analysis.     

Characterization of compost produced from separated pig manure and a variety of bulking agents at low initial C/N ratios

The aim of this study was to investigate the composting of separated pig manure solids with or without a variety of bulking agents at a low initial C/N ratio (12.5-23.3). Compost stability was investigated using an oxygen uptake rate (OUR) test and compost maturity was investigated using a germination index test. All treatments showed typical patterns of compost temperature. Temperatures above 60 °C were achieved by Day 2, followed by a thermophilic phase (50-60 °C), which lasted for 1 to 2 weeks followed by a cooling phase. The stability of one of treatments which did not contain any bulking agent - OUR of 25 mmol O₂ kg⁻¹ OM hour⁻¹ - was negatively affected by its initial high water content (69%). The addition of a bulking agent and initial water content below 60% were necessary to compost the separated solid fraction of pig manure at a low initial C/N ratio.     

Physicochemical properties of extrusion-modified konjac glucomannan

Konjac glucomannan was extruded and subsequently ground under four conditions denoted: KGM1 (33% solids, 90 °C), KGM2 (24% solids, 90 °C), KGM3 (24% solids, 90 °C, die restriction), and KGM4 (24% solids, 110 °C). SEM and particle size analysis showed that extruded KGM had slightly larger and rougher particles. The water absorption index was decreased to 47.92-128.80, as compared to 153.64 for the control (KGMC). The crystallinity index increased to 2.97 and 3.42 for KGM3 and KGM4 samples, as compared to 1.72 for the control. Zero-shear viscosity of 0.5% solutions decreased to 0.36-3.01 Pa s. All samples were shear-thinning and data were best fitted by the Cross model. Based on capillary viscometry, molecular weights were decreased to 2.7 × 10⁵-9.9 × 10⁵, as compared to 1.2 × 10⁶ for the control. In most cases, properties were most altered by higher temperature and shear, and to a lesser extent by lower solids in the feed.     

Comparing the potential production and value of high-energy liquid fuels and protein from marine and freshwater macroalgae

The biomass production and biochemical properties of marine and freshwater species of green macroalgae (multicellular algae), cultivated in outdoor conditions, were evaluated to assess the potential conversion into high-energy liquid biofuels, specifically biocrude and biodiesel and the value of these products. Biomass productivities were typically two times higher for marine macroalgae (8.5–11.9 g m⁻² d⁻¹, dry weight) than for freshwater macroalgae (3.4–5.1 g m⁻² d⁻¹, dry weight). The biochemical compositions of the species were also distinct, with higher ash content (25.5–36.6%) in marine macroalgae and higher calorific value (15.8–16.4 MJ kg⁻¹) in freshwater macroalgae. Lipid content was highest for freshwater Oedogonium and marine Derbesia. Lipids are a critical organic component for biocrude production by hydrothermal liquefaction (HTL) and the theoretical biocrude yield was therefore highest for Oedogonium (17.7%, dry weight) and Derbesia (16.2%, dry weight). Theoretical biocrude yields were also higher than biodiesel yields for all species due to the conversion of the whole organic component of biomass, including the predominant carbohydrate fraction. However, all marine species had higher biomass productivities and therefore had higher projected biocrude productivities than freshwater species, up to 7.1 t of biocrude ha⁻¹ yr⁻¹ for Derbesia. The projected value of the six macroalgae was increased by 45–77% (up to US$7700 ha⁻¹ yr⁻¹) through the extraction of protein prior to the conversion of the residual biomass to biocrude. This study highlights the importance of optimizing biomass productivities for high-energy fuels and targeting additional coproducts to increase value.     

Comparative cryopreservation study of trochophore larvae from two species of bivalves: Pacific oyster (Crassostrea gigas) and Blue mussel (Mytilus galloprovincialis)

Oysters and mussels are among the most farmed species in aquaculture industry around the world. The aim of this study was to test the toxicity of cryoprotective agents to trochophore larvae from two different species of bivalves and develop an improved cryopreservation protocol to ensure greater efficiency in the development of cryopreserved trochophores (14 h old oyster larvae and 20 h old mussel larvae) to normal D-larvae for future developments of hatchery spat production. The cryopreservation protocol producing the best results for oyster trochophores (60.0 ± 6.7% normal D-larvae) was obtained by holding at 0 °C for 5 min then cooling at 1 °C min⁻¹ to −10 °C and holding for 5 min before cooling at 0.5 °C to −35 °C, holding 5 min and then plunging into liquid nitrogen (LN), using 10% ethylene glycol. For mussel experiments, no significant differences were found when cooling at 0.5 °C min⁻¹ or at 1 °C min⁻¹ for CPA combinations with 10% ethylene glycol and at 0.5 °C min⁻¹. Using these combinations, around half of trochophores were able to develop to normal D-larvae post-thawing (48.9 ± 7.6% normal D-larvae).     

Chemical structures of water-soluble polysaccharides from Rhizoma Panacis Japonici

Five polysaccharide samples, coded as RPS1, RPS2, RPS3, RPS4, and RPS5, were isolated stepwise from Rhizoma Panacis Japonici (RPJ) by using 0.15 M NaCl aqueous solution at 25 °C, boiling water at 120 °C, 0.5 M NaOH/0.01 M NaBH₄ at 10 °C, 1.0 M NaOH/0.02 M NaBH₄ at 10 °C, and 19 M HCOOH at 4 °C, respectively. The yields were 0.39%, 1.08%, 2.41%, 0.32%, and 0.04% for RPS1 to RPS5, respectively. The chemical structures of the polysaccharides were highly branched α-(1→4)-d-glucan heteropolysaccharides and the values of degree of branch (DB) were in the range of 35-45% for RPS1 to RPS5. All of the polysaccharides were water soluble, and their solubility decreased from RPS1 to RPS5. The weight average molecular mass were 3.5 × 10⁴, 1.47 × 10⁵, 1.24 × 10⁶, 9.26 × 10⁵, and 1.36 × 10⁶ for RPS1 to RPS5, respectively.     

Biomass adaptation over anaerobic co-digestion of sewage sludge and trapped grease waste

The feasibility of sewage sludge co-digestion using intermediate waste generated inside a wastewater treatment plant, i.e. trapped grease waste from the dissolved air flotation unit, has been assessed in a continuous stirred lab reactor operating at 35 °C with a hydraulic retention time of 20 days. Three different periods of co-digestion were carried out as the grease waste dose was increased. When the grease waste addition was 23% of the volatile solids fed (organic loading rate 3.0 kg_COD m⁻³ d⁻¹), an increase in methane yield of 138% was reported. Specific activity tests suggested that anaerobic biomass had adapted to the co-substrate. The adapted inoculum showed higher acetoclastic methanogenic and β-oxidation synthrophic acetogenic activities but lower hydrogenotrophic methanogenic activity. The results indicate that a slow increase in the grease waste dose could be a strategy that favours biomass acclimation to fat-rich co-substrate, increases long chain fatty acid degradation and reduces the latter’s inhibitory effect.     

Heat tolerance, behavioural temperature selection and temperature-dependent respiration in larval Octopus huttoni

This study reports temperature effects on paralarvae from a benthic octopus species, Octopus huttoni, found throughout New Zealand and temperate Australia. We quantified the thermal tolerance, thermal preference and temperature-dependent respiration rates in 1-5 days old paralarvae. Thermal stress (1 °C increase h⁻¹) and thermal selection (∼10-24 °C vertical gradient) experiments were conducted with paralarvae reared for 4 days at 16 °C. In addition, measurement of oxygen consumption at 10, 15, 20 and 25 °C was made for paralarvae aged 1, 4 and 5 days using microrespirometry. Onset of spasms, rigour (CT_max) and mortality (upper lethal limit) occurred for 50% of experimental animals at, respectively, 26.0±0.2 °C, 27.8±0.2 °C and 31.4±0.1 °C. The upper, 23.1±0.2 °C, and lower, 15.0±1.7 °C, temperatures actively avoided by paralarvae correspond with the temperature range over which normal behaviours were observed in the thermal stress experiments. Over the temperature range of 10 °C-25 °C, respiration rates, standardized for an individual larva, increased with age, from 54.0 to 165.2 nmol larvae⁻¹ h⁻¹ in one-day old larvae to 40.1-99.4 nmol h⁻¹ at five days. Older larvae showed a lesser response to increased temperature: the effect of increasing temperature from 20 to 25 °C (Q₁₀) on 5 days old larvae (Q₁₀=1.35) was lower when compared with the 1 day old larvae (Q₁₀=1.68). The lower Q₁₀ in older larvae may reflect age-related changes in metabolic processes or a greater scope of older larvae to respond to thermal stress such as by reducing activity. Collectively, our data indicate that temperatures >25 °C may be a critical temperature. Further studies on the population-level variation in thermal tolerance in this species are warranted to predict how continued increases in ocean temperature will limit O. huttoni at early larval stages across the range of this species.     

Intraspecific tolerance of Metarhizium anisopliae conidia to the upper thermal limits of summer with a description of a quantitative assay system

Conidial tolerance to the upper thermal limits of summer is important for fungal biocontrol agents, whose conidia are formulated into mycoinsecticides for field application. To develop an efficient assay system, aerial conidia of eight Metarhizium anisopliae, four M. anisopliae var. anisopliae, and six M. anisopliae var. acridum isolates with different host and geographic origins were wet-stressed for ≤180 min at 48 °C or incubated for 14 d colony growths at 10-35 °C. The survival ratios (relative to unstressed conidia) of each isolate, examined at 15-min intervals, fit a logistic equation (r² ≥ 0.975), yielding median lethal times (LT₅₀s) of 14.3-150.3 min for the 18 isolates stressed at 48 °C. Seven grasshopper isolates from Africa had a mean LT₅₀ of 110 (73-150) min, but could not grow at 10 or 15 °C. The mean LT₅₀ of five non-grasshopper isolates capable of growing at 10-35 °C was 16 (10-26) min only. Three isolates with typically low (type I), medium (type II), and high (type III) levels of tolerance to 48 °C were further assayed for ≤4-d tolerance of their conidia to the wet stress at 38, 40, 42, or 45 °C. The resultant LT₅₀s decreased to 20, 53 and 167 min at 48 °C from 507, 1612, and 8256 min at 38 °C for types I, II and III, respectively. For the distinguished types, the logarithms of the LT₅₀s were significantly correlated to the temperatures of 38-48 °C with an inverse linearity (r² ≥ 0.88). The method developed to assay quantitatively fungal thermotolerance would be useful for screening of fungal candidates for improved pest control in summer.     

Temperature dependence of the rotation and hydrolysis activities of F1-ATPase

F₁-ATPase, a water-soluble portion of the enzyme ATP synthase, is a rotary molecular motor driven by ATP hydrolysis. To learn how the kinetics of rotation are regulated, we have investigated the rotational characteristics of a thermophilic F₁-ATPase over the temperature range 4-50°C by attaching a polystyrene bead (or bead duplex) to the rotor subunit and observing its rotation under a microscope. The apparent rate of ATP binding estimated at low ATP concentrations increased from 1.2 × 10⁶ M⁻¹ s⁻¹ at 4°C to 4.3 × 10⁷ M⁻¹ s⁻¹ at 40°C, whereas the torque estimated at 2 mM ATP remained around 40 pN·nm over 4-50°C. The rotation was stepwise at 4°C, even at the saturating ATP concentration of 2 mM, indicating the presence of a hitherto unresolved rate-limiting reaction that occurs at ATP-waiting angles. We also measured the ATP hydrolysis activity in bulk solution at 4-65°C. F₁-ATPase tends to be inactivated by binding ADP tightly. Both the inactivation and reactivation rates were found to rise sharply with temperature, and above 30°C, equilibrium between the active and inactive forms was reached within 2 s, the majority being inactive. Rapid inactivation at high temperatures is consistent with the physiological role of this enzyme, ATP synthesis, in the thermophile.     

Sulfate reduction and trichloroethylene biodegradation by a marine microbial community from hydrothermal vents sediments

Sulfate reduction (SR) and trichloroethylene (TCE) biodegradation at two different temperatures (37 and 70 °C) were investigated in enrichment cultures prepared with two different samples of sediments collected from hydrothermal vents. The unadapted sediments were incubated with sulfate (4 g L⁻¹) as the electron acceptor before TCE addition to enrich them in biomass and to establish a constant sulfate reduction (SR, 87% sulfate conversion and specific H₂S concentration of 90.81 ± 8.19 mg H₂S g VSS⁻¹), afterwards TCE was added at an initial concentration of 300 ??mol L⁻¹. The best results for TCE biodegradation were obtained at 37 °C. At this temperature, SR was up to 92%, whereas TCE biodegradation reached 75% and ethane was detected as the main degradation product. Under thermophilic conditions (70 °C) TCE biodegradation reached up to approximately 60% and the SR was 30% in 30 days of incubation with the chlorinated solvent. Along with these results, the 16S rDNA analysis from samples at 37 °C showed the presence of bacteria belonging to the genera: Clostridium, Bacillus and Desulfuromonas. The overall results on TCE degradation and SR suggest that cometabolic TCE degradation is carried out by sulfate or sulfur reducers and fermentative bacteria at mesophilic conditions.     

A kinetic evaluation of anaerobic treatment of swine wastewater at two temperatures in a temperate climate zone

A static granular bed reactor (SGBR) was used to treat swine wastewater at 24 and 16 °C. At 24 °C, the organic loading rate (OLR) was 0.7-5.4 kg COD/m³ day and the average chemical oxygen demand (COD) removal efficiency was 88.5%, respectively. Meanwhile, at 16 °C, the OLR was 1.6-4.0 kg COD/m³ day and the average COD removal efficiency was 68.0%, respectively. The SGBR acted as a bioreactor as well as a biofilter. After backwashing, the recovery of COD removal was not a function of an OLR but recovery time, while that of TSS removal was not a function of either recovery time or the OLR. The maximum substrate utilization rate (k_max) ratio was 1.89 between 24 and 16 °C, and the half velocity constant (K_s) ratio was 1.22, and the maximum specific growth rate (μ_max) ratio was 4.71. In addition, the temperature-activity coefficient in this study was determined to be 1.09.     

Pyrolysis of grape bagasse: effect of pyrolysis conditions on the product yields and characterization of the liquid product

In this study, pyrolysis of grape bagasse was investigated with the aim to study the product distribution and their chemical compositions and to identify optimum process conditions for maximizing the bio-oil yield. Particular investigated process variables were temperature (350-600 °C), heating rate (10-50 °C/min) and nitrogen gas flow rate (50-200 cm³/min). The maximum oil yield of 27.60% was obtained at the final pyrolysis temperature of 550 °C, sweeping gas flow rate of 100 cm³/min and heating rate of 50 °C/min in a fixed-bed reactor. The elemental analysis and heating value of the bio-oils were determined, and then the chemical composition of the bio-oil was investigated using chromatographic and spectroscopic techniques such as column chromatography, ¹H NMR and FTIR. The fuel properties of the bio-oil such as flash point, viscosity and density were also determined. The bio-oils obtained from grape bagasse were presented as an environmentally friendly feedstock candidate for bio-fuels.     

Determination of thermal properties of composting bulking materials

Thermal properties of compost bulking materials affect temperature and biodegradation during the composting process. Well determined thermal properties of compost feedstocks will therefore contribute to practical thermodynamic approaches. Thermal conductivity, thermal diffusivity, and volumetric heat capacity of 12 compost bulking materials were determined in this study. Thermal properties were determined at varying bulk densities (1, 1.3, 1.7, 2.5, and 5 times uncompacted bulk density), particle sizes (ground and bulk), and water contents (0, 20, 50, 80% of water holding capacity and saturated condition). For the water content at 80% of water holding capacity, saw dust, soil compost blend, beef manure, and turkey litter showed the highest thermal conductivity (K) and volumetric heat capacity (C) (K: 0.12–0.81 W/m °C and C: 1.36–4.08 MJ/m³ °C). Silage showed medium values at the same water content (K: 0.09–0.47 W/m °C and C: 0.93–3.09 MJ/m³ °C). Wheat straw, oat straw, soybean straw, cornstalks, alfalfa hay, and wood shavings produced the lowest K and C values (K: 0.03–0.30 W/m °C and C: 0.26–3.45 MJ/m³ °C). Thermal conductivity and volumetric heat capacity showed a linear relationship with moisture content and bulk density, while thermal diffusivity showed a nonlinear relationship. Since the water, air, and solid materials have their own specific thermal property values, thermal properties of compost bulking materials vary with the rate of those three components by changing water content, bulk density, and particle size. The degree of saturation was used to represent the interaction between volumes of water, air, and solids under the various combinations of moisture content, bulk density, and particle size. The first order regression models developed in this paper represent the relationship between degree of saturation and volumetric heat capacity (r = 0.95–0.99) and thermal conductivity (r = 0.84–0.99) well. Improved knowledge of the thermal properties of compost bulking materials can contribute to improved thermodynamic modeling and heat management of composting processes.     

Cryopreservation of Greenshell™ mussel (Perna canaliculus) trochophore larvae

The Greenshell™ mussel (Perna canaliculus) is the main shellfish species farmed in New Zealand. The aim of this study was to evaluate the effects of cryoprotectant concentration, loading and unloading strategy as well as freezing and thawing method in order to develop a protocol for cryopreservation of trochophore larvae (16–20 h old). Toxicity tests showed that levels of 10–15% ethylene glycol (EG) were not toxic to larvae and could be loaded and unloaded in a single step. Through cryopreservation experiments, we designed a cryopreservation protocol that enabled 40–60% of trochophores to develop to D-larvae when normalized to controls. The protocol involved: holding at 0 °C for 5 min, then cooling at 1 °C min⁻¹ to −10 °C, holding for a further 5 min, then cooling at 0.5 °C min⁻¹ to −35 °C followed by a 5 min hold and then plunging into liquid nitrogen. A final larval rearing experiment of 18 days was conducted to assess the ability of these frozen larvae to develop further. Results showed that only 2.8% of the frozen trochophores were able to develop to competent pediveligers.     

Longevity and temperature response of pollen as affected by elevated growth temperature and carbon dioxide in peanut and grain sorghum

It is important to understand the effects of environmental conditions during plant growth on longevity and temperature response of pollen. Objectives of this study were to determine the influence of growth temperature and/or carbon dioxide (CO₂) concentration on pollen longevity and temperature response of peanut and grain sorghum pollen. Plants were grown at daytime maximum/nighttime minimum temperatures of 32/22, 36/26, 40/30 and 44/34 °C at ambient (350 μmol mol⁻¹) and at elevated (700 μmol mol⁻¹) CO₂ from emergence to maturity. At flowering, pollen longevity was estimated by measuring in vitro pollen germination at different time intervals after anther dehiscence. Temperature response of pollen was measured by germinating pollen on artificial growth medium at temperatures ranging from 12 to 48 °C in incubators at 4 °C intervals. Elevated growth temperature decreased pollen germination percentage in both crop species. Sorghum pollen had shorter longevity than peanut pollen. There was no influence of CO₂ on pollen longevity. Pollen longevity of sorghum at 36/26 °C was about 2 h shorter than at 32/22 °C. There was no effect of growth temperature or CO₂ on cardinal temperatures (T_min, T_opt, and T_max) of pollen in both crop species. The T_min, T_opt, and T_max identified at different growth temperatures and CO₂ levels were similar at 14.9, 30.1, and 45.6 °C, respectively for peanut pollen. The corresponding values for sorghum pollen were 17.2, 29.4, and 41.7 °C. In conclusion, pollen longevity and pollen germination percentage was decreased by growth at elevated temperature, and pollen developed at elevated temperature and/or elevated CO₂ did not have greater temperature tolerance.     

The metabolic cost of fever in Pekin ducks

Fever is an energetically expensive component of the mammalian immune system’s acute phase response. Like mammals, birds also develop fever when exposed to pathogens, but, as yet, the energy requirements of febrile mediation in birds are not known. We injected ducks (Anas platyrhynchos; n=8) with 100 μ kg⁻¹ LPS or sterile isotonic saline and recorded their core body temperatures while measuring their O₂ consumption and CO₂ production in an open-flow respirometric circuit. Lipopolysaccharide elicited robust increases in the core body temperatures of our birds. The metabolic rate of the ducks increased about 80 min after treatment with LPS, relative to the metabolic rate of saline injected birds, and peaked 100 min later when the highest body temperatures were recorded. Our ducks increased their energy expenditure by 33.1% for about 3 h to mount a febrile response that, on average, increased their body temperature 1.4 °C. Studies with humans and rats, kept at thermoneutral temperatures, found a 10-15% increase in metabolic rate for every 1 °C increase in body temperature. The increase in metabolic rate, reported here (23%/°C), is noticeably higher and we conclude that febrile mediation is metabolically more expensive in Pekin ducks than in mammals.