Partial wet oxidation of dairy manure as a pretreatment process to produce acetic acid 'a Source Growth of Methanogens'.

Wet oxidation can be an effective process for the pretreatment of complex biomass such as lignocellulose. However, studies on the use of wet oxidation for treating solid waste such as dairy manure are limited. The use of partial wet oxidation to convert dairy manure into low molecular weight carboxylic acids as final products were investigated. This work focuses on the performance of the sub-critical wet oxidation treatment of dairy cattle manure as a conversion/pretreatment process to release matter from the lignocellulosic fraction rather than a destructive process. The operating conditions were controlled at the short residence time and optimal temperature in the presence of oxygen under a pressure of 120 psi. The thermal hydrolysis under wet oxidation significantly affected conversion manure slurry into organic acids. The concentration of acetic acid reached 1778 mg L-1, achieved at 190°C (60 minutes reaction time) as the reaction temperature increased within the range of 150°C-200°C, total organic carbon was reduced and monomers in the process liquids decreased. On the other hand, soluble COD in process liquids increased with an increment in reaction temperature. The results provide insights into technical options to pretreat dairy manure to improve biochemical conversion yield.

Updated view of tars for psoriasis: what have we learned over the last decade?

Tars are one of the most effective, unknown, and oldest therapies for psoriasis. They include coal tar (CT) and biomass-derived products. These treatments, particularly the CT, have proven to be cost-effective with long remission times compared to other systemic or topical treatments. However, they have hardly evolved in recent years, as they are not well-embraced by clinicians or patients because of concerns regarding cosmesis and safety. This review summarizes current knowledge about the chemical characterization, mechanism of action, toxicity, and clinical studies supporting the use of tars for psoriasis over the last decade. Trends within these above aspects are reviewed, and avenues of research are identified. CT is rich in polycyclic aromatic hydrocarbons, whereas biomass-derived tars are rich in phenols. While the activation of the aryl hydrocarbon receptor is involved in the antipsoriatic effect of CT, the mechanism of action of biomass-derived products remains to be elucidated. No conclusive evidence exists about the risk of cancer in psoriasis patients under CT treatment. Large, randomized, double-blind, controlled clinical trials are necessary to promote the inclusion of tars as part of modern therapies for psoriasis.

Novel Amorphous Carbons for the Adsorption of Phosphate: Part I. Elucidation of Chemical Structure of N-Metal-Doped Chars.

Due to phosphate's necessity in agriculture and its danger to the environment, the development of adsorbents for its removal has been the subject of intensive research activity. Although the introduction of nitrogen functionality to chars and modification of biochar with metals have proven to change the character of the char structure, making it more active toward nutrients, there is no study regarding the doping of biochar with metals and nitrogen simultaneously for the adsorption of phosphates. This paper is the first of two in which we report the production, characterization, and evaluation of N-metal-doped biochars from cellulose for phosphate removal from liquid effluents. In this part, we describe the production and characterization of N-Ca-, N-Fe-, and N-Mg-doped biochars. The elemental composition and surface area of each of the materials produced is reported. Elemental and surface characterization of the chars are reported with the largest N content appearing at a temperature of 800 °C (12.5 wt %) and a maximum surface area for biochar produced at 900 °C (1314 m2/g). All of the adsorbents were visualized by scanning electron microscope (SEM), confirming that although there are some crystals on the surface of the biochar produced, most of the N, Mg, and Ca are part of the polyaromatic ring structure. Transmission electron microscope (TEM) images clearly show the formation of nanoclusters with the metals in the case of N-Fe and N-Ca biochars. The N-Mg biochars show a uniform distribution of the Mg through the carbon surface. X-ray photoelectron spectroscopy (XPS) studies of the biochars produced with metals and varying nitrogen levels clearly show Mg and Ca peaks shifting their position in the presence of N, suggesting the formation of stable structures between metals and N in the carbon polyaromatic ring system. To elucidate the nature of these structures, we conducted DFT-based calculations on different configurations of the nitrogenated structures. The calculated binding energy shifts were found to closely match the XPS experimental binding energy, confirming the likelihood of these structures in biochar. Finally, based on our experimental and modeling results, we hypothesize that an important fraction of the Mg and Ca is introduced to these biochars at the edges. Another fraction of Mg and Ca is in the form of phthalocyanine-like internal structures. More experimental studies are needed to confirm the formation of these very interesting structures and their potential use as adsorbents or catalysts.

Microbial lipid biosynthesis from lignocellulosic biomass pyrolysis products.

Lipids are a biorefinery platform to prepare fuel, food and health products. They are traditionally obtained from plants, but those of microbial origin allow for a better use of land and C resources, among other benefits. Several (thermo)chemical and biochemical strategies are used for the conversion of C contained in lignocellulosic biomass into lipids. In particular, pyrolysis can process virtually any biomass and is easy to scale up. Products offer cost-effective, renewable C in the form of readily fermentable molecules and other upgradable intermediates. Although the production of microbial lipids has been studied for 30 years, their incorporation into biorefineries was only described a few years ago. As pyrolysis becomes a profitable technology to depolymerize lignocellulosic biomass into assimilable C, the number of investigations on it raises significantly. This article describes the challenges and opportunities resulting from the combination of lignocellulosic biomass pyrolysis and lipid biosynthesis with oleaginous microorganisms. First, this work presents the basics of the individual processes, and then it shows state-of-the-art processes for the preparation of microbial lipids from biomass pyrolysis products. Advanced knowledge on separation techniques, structure analysis, and fermentability is detailed for each biomass pyrolysis fraction. Finally, the microbial fatty acid platform comprising biofuel, human food and animal feed products, and others, is presented. Literature shows that the microbial lipid production from anhydrosugars, like levoglucosan, and short-chain organic acids, like acetic acid, is straightforward. Indeed, processes achieving nearly theoretical yields form the latter have been described. Some authors have shown that lipid biosynthesis from different lignin sources is biochemically feasible. However, it still imposes major challenges regarding strain performance. No report on the fermentation of pyrolytic lignin is yet available. Research on the microbial uptake of pyrolytic humins remains vacant. Microorganisms that make use of methane show promising results at the proof-of-concept level. Overall, despite some issues need to be tackled, it is now possible to conceive new versatile biorefinery models by combining lignocellulosic biomass pyrolysis products and robust oleaginous microbial cell factories.

Characteristics and mechanisms of phosphorous adsorption by rape straw-derived biochar functionalized with calcium from eggshell.

Biochar modified with calcium source is acted as an effective adsorbent for phosphorous recovery. In this research, eggshell is used as a low-cost and environmentally friendly calcium source to replace chemical reagents such as CaCO3, Ca(OH)2 and CaCl2 used in the modified biochar production. Biochar derived from rape straw and modified with eggshell shows prominent phosphorous adsorption performance (e.g., equilibrium adsorption amount, 109.7 mg/g). The kinetic and isotherm analysis demonstrate that chemical adsorption process is performed as the main controlled step for the modified biochar adsorption, and the phosphate adsorption process is composed of both monolayer adsorption and multi-layer adsorption. Moreover, it is found from the physicochemical structures comparison before and after phosphate adsorption that Ca-P precipitation, hydrogen bonding and electrostatic attraction are identified as main adsorption mechanisms. In addition, the adsorbed phosphates are mainly distributed inside the space with pore sizes of 15-50 nm.

Lignin Depolymerization: A Comparison of Methods to Analyze Monomers and Oligomers.

Catalytic liquefaction of lignin is an attractive process to produce fuels and chemicals, but it forms a wide range of liquid products from monomers to oligomers. Oligomers represent an important fraction of the products and their analysis is complex. Therefore, rapid characterization methods are needed to screen liquefaction conditions based on the distribution in monomers and oligomers. For this purpose, UV spectroscopy is proposed as a fast and simple method to assess the composition of lignin-derived liquids. UV absorption and fluorescence were studied on various model compounds and liquefaction products. Liquefaction of Soda lignin was conducted in an autoclave, in ethanol and with Pt/C catalyst (H2 , 250 °C, 110 bar). Liquids were sampled at isothermal conditions every 30 min for 4 h. UV fluorescence spectroscopy is related to GC-MS, gel-permeation chromatography (GPC), MALDI-TOF MS, and NMR characterizations. A depolymerization index is proposed from UV spectroscopy to rapidly assess the relative distribution of monomers and oligomers.

Contributions to Lignomics: Stochastic Generation of Oligomeric Lignin Structures for Interpretation of MALDI-FT-ICR-MS Results.

The lack of standards to identify oligomeric molecules is a challenge for the analysis of complex organic mixtures. High-resolution mass spectrometry-specifically, Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS)-offers new opportunities for analysis of oligomers with the assignment of formulae (Cx Hy Oz ) to detected peaks. However, matching a specific structure to a given formula remains a challenge due to the inability of FT-ICR MS to distinguish between isomers. Additional separation techniques and other analyses (e.g., NMR spectroscopy) coupled with comparison of results to those from pure compounds is one route for assignment of MS peaks. Unfortunately, this strategy may be impractical for complete analysis of complex, heterogeneous samples. In this study we use computational stochastic generation of lignin oligomers to generate a molecular library for supporting the assignment of potential candidate structures to compounds detected during FT-ICR MS analysis. This approach may also be feasible for other macromolecules beyond lignin.

Nitrogen doped char from anaerobically digested fiber for phosphate removal in aqueous solutions.

This study explores the use of an engineered char produced from the pyrolysis of anaerobically digested fiber (ADF) to adsorb phosphate from aqueous solutions. Two series of engineered chars were produced. The first series was a CO2 activated (CA) char produced via slow pyrolysis between 350 and 750 °C. The second series was a nitrogen doped (ND) char activated in the presence of ammonia at comparable temperatures. Proximate analysis, elemental composition, gas physisorption, Inductively coupled plasma mass spectrometry (ICP-MS), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), Fourier Transform Infrared Spectroscopy (FTIR) and X-ray powder diffraction (XRD) techniques were used to characterize properties of resulting products. The surface area of the carbon product increased after nitrogen doping through ammonization (166.6-463.1 m2/g) compared to CO2 activated chars (156.5-413.1 m2/g). Phosphate adsorption isotherms for both CO2 activated and nitrogen doped chars can be described by the Langmuir- Freundlich and Redlich Peterson adsorption models. Nitrogen doped carbon phosphate sorption capacity in aqueous solutions was twice compared to CO2 activated carbons. As carbonization/activation temperature increased the sorption capacity increased from 3.4 to 33.3 mg g-1 for CA char and 6.3-63.1 mg g-1 for nitrogen doped char.

Investigation of the Antibacterial Activity and Subacute Toxicity of a Quercus crassifolia Polyphenolic Bark Extract for its Potential Use in Functional Foods.

Oak wood is used in barrels for wine aging. During aging, polyphenols are transferred from the barrels to the liquid. Although the bioactivity of oak polyphenols in wines has been extensively studied, no investigation exists on their toxicological properties, which limits their use as functional safe ingredients for other products. In this work, the chemical composition of a polyphenolic extract of Quercus crassifolia bark (QCBe) was studied by GC-MS. Its antibacterial properties on probiotic and pathogenic bacteria and its subacute-oral toxicity were determined as a way to understand the potential impact from its addition to fermented food as a functional ingredient. QCBe shows a selective inhibition of Escherichia coli compared with Lactobacillus bulgaricus and Streptococcus thermophylus. According to the toxicity evaluation, the subacute no-observed-adverse-effect-level was achieved at 11 mg/kg bw/day, whereas the subacute lowest-observed-adverse-effect-level for kidney damage was at 33 mg/kg bw/day. These results suggest that, given the fact an adverse effect was observed after subacute administration of this extract, further longer term toxicological studies are needed to provide sufficient safety evidence for its use in humans. PRACTICAL APPLICATION: Mexico's yogurt market is growing which creates opportunities for the development of some yogurt products as functional foods. As a first step to evaluate its potential use in yogurt formulation, the antibacterial effect of a Quercus crassifolia polyphenolic extract (QCBe) on probiotic bacteria and its subacute-oral toxicity in rats were studied. A low inhibition on probiotic bacteria growth was observed after QCBe addition to Lactobacillus bulgaricus and Streptococcus thermophylus cultures. Exposure to QCBe for a subacute duration resulted in renal injury in rats at dosages greater than or equal to 33 mg/kg/bw/day. This adverse effect indicates the importance of performing further long-term toxicological assessments prior to the addition of QCBe to a food like yogurt, which is regularly eaten by consumers.

Characterization of solid and vapor products from thermochemical conversion of municipal solid waste woody fractions.

The ever-increasing consumption of material goods with economic growth is resulting in an increasing generation of municipal solid waste (MSW) and the rapid filling of landfills. Fractions of municipal solid waste containing wood-based products have the potential to be used for the development of value added products. In this paper we produced and characterized biochar and pyrolysis vapors from municipal solid waste (MSW) woody fractions to demonstrate their suitability towards soil amendments. Carbonization work focused on compost overs, molded wood pallets, treated wood, sawmill cut ends, wood derived fuels, furniture, painted wood, plywood, oriented strand board and particle boards from Washington State recycling facilities. The goal of this research is to use these biochars as soil amendments; however, there are concerns with both the potential presence of condensed organic pollutants and trace metals. The presence of trace metals and polycyclic aromatic hydrocarbons (PAH) in all the biochars produced were examined. GC-MS analyses of liquid extracts did not reveal the presence of soluble PAH compounds. High concentrations of mercury (Hg) and arsenic (As) were found in the biochar made from painted wood and treated wood, respectively. Among the methods tested for the removal of trace metals, acid washing was found to be the most effective. The volatiles released from the analyzed MSW fractions were also analyzed in Py-GC-MS studies. Among these volatile compounds, many contained Cl, N, or S, which could be potential sources of pollution if the pyrolysis vapors are combusted.

The Alcohol-to-Jet Conversion Pathway for Drop-In Biofuels: Techno-Economic Evaluation.

The alcohol-to-jet (ATJ) process is a method for the conversion of alcohols to an alternative jet fuel blendstock based on catalytic steps historically utilized by the petroleum refining and petrochemical industry. This pathway provides a means for producing a sustainable alternative jet fuel (SAJF) from a wide variety of resources and offers a near-term opportunity for alcohol producers to enter the SAJF market and for the aviation sector to meet growing SAJF demand. Herein, the technical background is reviewed and selected variations of ATJ processes evaluated. Simulation and modeling were employed to assess some ATJ conversion schemes, with a particular focus on comparisons between the use of an ethanol or isobutanol intermediate. Although the utilization of isobutanol offers a 34 % lower conversion cost for the catalytic upgrading process, the cost of alcohol production is estimated to contribute more than 80 % of the total cost at the refinery. The cost of feedstock and alcohol production has a dominant effect on the overall process economics.

Bio-Oil Hydrotreatment for Enhancing Solubility in Biodiesel and the Oxydation Stability of Resulting Blends.

The major challenge for the pyrolytic conversion of lignocellulosic materials into crude bio-oil is the poor quality of the final product. Several strategies (addition of solvents, production of emulsions, and extraction with biodiesel) have been studied to improve its fuel properties. The extraction with biodiesel is an interesting solution because it allows direct utilization of some bio-oil fractions as fuels. However, fraction extracted with biodiesel is typically between 10 and 18 wt. %. In this paper we studied mild hydrotreatment of pyrolysis oil to enhance its solubility in biodiesel. The study was conducted with BTG and Amaron oils hydrotreated at temperatures between 200 and 325°C in the presence of Ru/C catalyst. Hydrotreated oils generated three phases: top oil (light hydrocarbons), middle aqueous phase and bottom heavy oil phase. Each of the phases was characterized and the content of acetic acid, phenols, aromatic compounds, and linear alkane hydrocarbons quantified. The upgraded bio-oils were more soluble in biodiesel than the crude bio-oils, obtaining blends with up to 48 and 38 wt. % for the BTG and Amaron bio-oil, respectively. Some of the fuel properties of the resulting blends are also reported here.

Charcoal from anaerobically digested dairy fiber for removal of hydrogen sulfide within biogas.

Anaerobically digested fibrous solid (AD fiber) is an abundant material that offers potential to produce value-added products such as biochar. The objective of this paper is to better understand how thermochemical processing conditions affect the capacity of biochars derived from AD fiber to adsorb H2S from biogas. AD fiber was pyrolyzed in an electric tube reactor at temperatures up to 600 °C and 60 min. The chars were employed for H2S scrubbing tests from a synthetic biogas. Results showed that the chars' capacity for H2S removal is comparable to that of activated carbon. An additional step consisting of impregnation of the chars with Na2CO3 resulted in an improved capacity for H2S removal. To study the effect of ash, the AD fiber was also subjected to an alternative thermal treatment, hot water extraction (HWE), at 200 °C for 60 min. The resulting HWE material showed no removal of H2S from biogas, indicating that the ash and the environment employed for the thermal treatment of AD fiber play an important role in the char's performance for H2S removal. Results also suggest that a portion of the S in the charcoal after the H2S sorption process exists as free or adsorbed S (i.e., not chemically bonded to the charcoal).

Quantitative Effects of Biochar Oxidation and Pyrolysis Temperature on the Transport of Pathogenic and Nonpathogenic Escherichia coli in Biochar-Amended Sand Columns.

The present study quantifies the transport of Escherichia coli pathogenic O157:H7 and nonpathogenic K12 strains in water-saturated Quincy sand (QS) columns amended with oxidized (OX) or unoxidized (UO) pine wood (PW) or pine bark (PB) biochar produced at either 350 or 600 °C. Our results showed that (1) the addition of oxidized biochar into QS columns enhanced the transport of E. coli O157:H7 by 3.1 fold compared to the unoxidized counterparts, likely because of an increase in the repulsive forces due to their higher negative charge densities. (2) The retention of E. coli O157:H7 was 3.3 fold higher than that of E. coli K12 in all biochar-amended sand columns. (3) Increased application rates of unoxidized PW600 biochar from 0 to 20 wt % led to a reduction in the transport of E. coli O157:H7 and K12 from 98 to 10% and from 95 to 70%, respectively. Our data showed that mixing sand with PW350-UO at a 20 wt % application rate almost completely retained the pathogenic E. coli in the subsurface, suggesting that utilizing sand mixed with biochar can act as a promising biofilter capable of protecting natural aquafers from pathogens.

The role of biochar porosity and surface functionality in augmenting hydrologic properties of a sandy soil.

This paper reports studies to elucidate the potential relationships between porosity and surface functionality of biochar and soil water retention characteristics. The biochars studied were produced from pine wood (PW), hybrid poplar wood (HP), and pine bark (PB) at temperatures of 350°C and 600°C. The resulting materials were then oxidized under air at 250°C to generate oxygenated functional groups on the surface. All biochar were thoroughly characterized (surface and bulk properties) and their hydrological properties measured in blends with Quincy sand. We prepared 39 microcosms for this study to examine the effect of biochar functionalities and porosity on the hydro-physical properties of Quincy sand. Each biochar was thoroughly mixed with the soil at 20gkg-1. The field capacity, wilting point, and total available soil moisture of the bio-char/Quincy sand mixtures were measured for both dry and wet ranges. The soil water potentials and soil water contents were fitted using the model of van Genuchten. Our results indicated that the amount of oxygenated functional groups on the surface of biochars clearly differentiated the biochars in terms of hydrophilicity, with the oxidized biochars being superior, followed by the low-temperature biochars, while the high temperature biochars possessed lowest hydrophilicity. As a result, oxidized biochars exhibited better wettability compared to unoxidized biochars, regardless their feedstock source. Significant correlation occurred between the total acidic functional groups on biochar surface and water contents at different matric potentials. Over a wide range of soil water potentials, oxidized biochar-soil mixtures held more water than the unoxidized biochar-soil mixtures except in the region between -0.1 and -5kPa of ψ, which is near saturation. Soil water contents at different matric potentials were significantly inter-correlated (P<0.01) and correlated with bulk densities of biochar-amended soil samples.

Effect of acid additives on sugarcane bagasse pyrolysis: Production of high yields of sugars.

The aim of this work was to improve sugarcane bagasse thermochemical conversion to pyrolytic sugars production, particularly to levoglucosan. The experiments were carried out evaluating the effect of acid washing with HNO3 (0.1wt.%) followed by H2SO4 addition (0.1, 0.2 and 0.3wt.%) at pyrolysis temperatures of 350, 400, 450, 500, 550 and 600°C was studied by Py-GC/MS. The experimental results showed that HNO3 washing, followed by H2SO4 concentration of 0.2wt.% at 350°C resulted in an increase in levoglucosan yield between 5 and 7 times the yield obtained when the raw bagasse was processed. Thus, these results are very attractive to improve pyrolytic sugars production in sugarcane bagasse by previously acid treatment to pyrolysis technology.

Engineering levoglucosan metabolic pathway in Rhodococcus jostii RHA1 for lipid production.

Oleaginous strains of Rhodococcus including R. jostii RHA1 have attracted considerable attention due to their ability to accumulate triacylglycerols (TAGs), robust growth properties and genetic tractability. In this study, a novel metabolic pathway was introduced into R. jostii by heterogenous expression of the well-characterized gene, lgk encoding levoglucosan kinase from Lipomyces starkeyi YZ-215. This enables the recombinant R. jostii RHA1 to produce TAGs from the anhydrous sugar, levoglucosan, which can be generated efficiently as the major molecule from the pyrolysis of cellulose. The recombinant R. jostii RHA1 could grow on levoglucosan as the sole carbon source, and the consumption rate of levoglucosan was determined. Furthermore, expression of one more copy of lgk increased the enzymatic activity of LGK in the recombinant. However, the growth performance of the recombinant bearing two copies of lgk on levoglucosan was not improved. Although expression of lgk in the recombinants was not repressed by the glucose present in the media, glucose in the sugar mixture still affected consumption of levoglucosan. Under nitrogen limiting conditions, lipid produced from levoglucosan by the recombinant bearing lgk was up to 43.54 % of the cell dry weight, which was comparable to the content of lipid accumulated from glucose. This work demonstrated the technical feasibility of producing lipid from levoglucosan, an anhydrosugar derived from the pyrolysis of lignocellulosic materials, by the genetically modified rhodococci strains.

Simulation of the ozone pretreatment of wheat straw.

Wheat straw is a potential feedstock in biorefinery for sugar production. However, the cellulose, which is the major source of sugar, is protected by lignin. Ozonolysis deconstructs the lignin and makes cellulose accessible to enzymatic digestion. In this study, the change in lignin concentration with different ozonolysis times (0, 1, 2, 3, 5, 7, 10, 15, 20, 30, 60min) was fit to two different kinetic models: one using the model developed by Garcia-Cubero et al. (2012) and another including an outer mass transfer barrier or "cuticle" region where ozone mass transport is reduced in proportion to the mass of unreacted insoluble lignin in the cuticle. The kinetic parameters of two mathematical models for predicting the soluble and insoluble lignin at different pretreatment time were determined. The results showed that parameters derived from the cuticle-based model provided a better fit to experimental results compared to a model without a cuticle layer.

Effect of biochar on leaching of organic carbon, nitrogen, and phosphorus from compost in bioretention systems.

Compost is used in bioretention systems to improve soil quality, water infiltration, and retention of contaminants. However, compost contains dissolved organic matter, nitrate, and phosphorus, all of which can leach out and potentially contaminate ground and surface waters. To reduce the leaching of nutrients and dissolved organic matter from compost, biochar may be mixed into the bioretention systems. Our objective was to test whether biochar and co-composted biochar mixed into mature compost can reduce the leaching of organic carbon, nitrogen, and phosphorus. There was no significant difference between the effects of biochar and co-composted biochar amendments on nutrient leaching. Further, biochar amendments did not significantly reduce the leaching of dissolved organic carbon, nitrate, and phosphorus as compared to the compost only treatment. The compost-sand mix was the most effective in reducing nitrate and phosphorus leaching among the media.

Recent developments in fast pyrolysis of ligno-cellulosic materials.

Pyrolysis is a thermochemical process to convert ligno-cellulosic materials into bio-char and pyrolysis oil. This oil can be further upgraded or refined for electricity, transportation fuels and chemicals production. At the time of writing, several demonstration factories are considered worldwide aiming at maturing the technology. Research is focusing on understanding the underlying processes at all relevant scales, ranging from the chemistry of cell wall deconstruction to optimization of pyrolysis factories, in order to produce better quality oils for targeted uses. Among the several bio-oil applications that are currently investigated the production and fermentation of pyrolytic sugars explores the promising interface between thermochemistry and biotechnology.