Kinetics of syntrophic acetogenesis in a saline medium

BACKGROUND: The anaerobic degradation kinetics of volatile fatty acids (VFA) in a saline (24 g NaCl dm^?3) and mesophilic (37 °C) medium was studied under batch test conditions. The acetate production kinetics without inhibition by propionic, butyric and valeric acids was determined. The inhibition of acetate production during syntrophic acetogenesis by VFA and pH was studied. The acetogenesis without inhibition was modelled using a Monod equation. The pH inhibition was represented by a Michaelis pH function, while the inhibition by acetic acid (HAc) was represented by a non‐competitive model. RESULTS: The specific maximum degradation rate and saturation constant (k_{max, VFA}, K_{S, max}) values were (5.89, 15.95), (7.97, 25.99) and (7.75 g VFA g^?1 volatile suspended solids day^?1, 11.52 mg VFA dm^?3) for propionic, butyric and valeric acids respectively, with maximum velocity at pH 7. The inhibition constants (K_{I, HAc}) were 1295, 671 and 572 mg HAc dm^?3 for propionic, butyric and valeric acids respectively. CONCLUSION: VFA and pH can be inhibitory for acetogenesis under these conditions. Copyright © 2008 Society of Chemical Industry     

Anaerobic acidogenesis of dairy wastewater: the effects of variations in hydraulic retention time with no pH control

The performance of a laboratory‐scale mesophilic acidogenic reactor was evaluated in this study, in terms of volatile fatty acid production and distribution, with respect to variations in hydraulic retention time (HRT). The continuous flow‐completely mixed anaerobic reactor, coupled with a conventional gravity settling tank and a continuous recycling system, was operated in a hydraulic retention time ranging between 24 and 12 h, and up to an organic loading rate of about 9.3 kg COD m^?3 d^?1, without pH control. The acid production gradually increased proportionally to the organic loading rate, with decrease in hydraulic retention time. The highest degree of acidification and the rate of acid production were 56% and 3.1 g dm^?3 d^?1 at 12 h of HRT. Variations in hydraulic retention time affected volatile fatty acid production and distribution substantially, for the range investigated. Acetic, propionic, butyric and valeric acids were commonly produced during acidogenesis of dairy wastewater. Copyright © 2004 Society of Chemical Industry     

Effects of butyric acid stress on anaerobic sludge for hydrogen production from kitchen wastes

BACKGROUND: Anaerobic digestion is an alternative technology to achieve the dual benefits of hydrogen production and waste stabilization from kitchen wastes. In this work, the butyric acid stress on anaerobic sludge was investigated in order to improve the tolerance of sludge against organic acids, and to enhance hydrogen accumulation. RESULTS: The tolerance of butyric acid in anaerobic sludge increased with the stress concentration, however, it decreased at concentrations greater than of 4.0 g L^?1. The maximum hydrogen yield reached 63.72 mL g^?1 VS at 4.0 g L^?1 stress, representing an increase of 114% compared with the control group. The concentration of volatile solids (VS) of the sludge and SCOD increased steadily with time up to 20 h. At 4.0 g L^?1 butyric acid stress, the maximum activity of β‐glucosidase, BAA‐hydrolysing protease and dehydrogenase enzyme were 14912.1 µmol PNP g^?1 TS h^?1, 134.14 µmol NH₄‐N g^?1 TS h^?1 and 7316.42 µg TF g^?1 TS h^?1, which were 2.78, 1.90 and 2.01 times that of the control, respectively. CONCLUSIONS: The feasibility of butyric acid stress on anaerobic sludge to increase hydrogen production from kitchen wastes was demonstrated. Remarkably, 4.0 g L^?1 butyric acid stress was found to be favorable for improving the tolerance of butyric acid in sludge as well as hydrogen yield in the experiment. Copyright © 2010 Society of Chemical Industry     

The effect of raw glycerol concentration on the production of 1,3‐propanediol by Clostridium butyricum

Raw glycerol, the main by‐product of the bio‐diesel production process, was converted to 1,3‐propanediol by Clostridium butyricum F2b. In batch cultures, 47.1 g dm^?3 of 1,3‐propanediol were produced. Continuous cultures were conducted at a constant dilution rate (= 0.04 h^?1) and various inlet glycerol concentrations with 1,3‐propanediol produced at levels up to 44.0 g dm^?3. At increasing glycerol concentrations in the inlet medium, biomass yield decreased. This decrease was attributed to the microbial metabolism being directed towards the biosynthesis of organic acids (and hence carbon losses as CO₂) instead of biochemical anabolic reactions. An autonomous analytical model was developed, and quantified the effect of inlet glycerol concentration on the production of biomass and metabolites. Indeed, high inlet substrate concentrations positively affected the biosynthesis, principally of butyric acid and to a lesser extent that of acetic acid. In contrast, at increased glycerol concentrations, the relative increase of 1,3‐propanediol production per unit of substrate consumed was lower as compared with that of acetic and, mainly, butyric acid. This could be explained by the fact that the butyric acid pathway represents an alternative and competitive one to that of 1,3‐propanediol for re‐generation of NADH₂ equivalents in the microbial cell. Copyright © 2004 Society of Chemical Industry     

Unexploited Thapsia garganica,Orlaya maritima,and Retama raetam Seeds: Potential Sources of Unsaturated Fatty Acid and Natural Antioxidants

Total lipid contents, fatty acid compositions, phenolic profiles and antioxidants activities of seeds from Thapsia garganica, Orlaya maritima, and Retama raetam were investigated. The oil values were more than 26 %, except seeds of R. raetam (ca. 3 %). Unsaturated fatty acids accounted for the majority of the fatty acids (more than 75 %). Oleic and linoleic acid were the predominant fatty acids. Total phenolic compounds (24–104 mg GAE g^?1 DR), total flavonoids (4–102 mg QE g^?1g DR), total tannins (28–85 mg GAE g^?1 DR) and condensed tannins (0.62–131 mg CE g^?1 DR) were also determined. The antioxidant activities using different assays were evaluated. The predominant detected classes were the phenolic acids (42–85 %) and the flavonoids (11–48 %). The major phenolic acids were caffeic, trans‐4‐hydroxy‐3‐methoxycinnamic, p‐coumaric, and gallic acid. The predominant flavonoids were quercetin, luteolin, naringin, apigenin, and kaempferol. This study brings attention to the medicinal importance of these species as a source of oil and antioxidant molecules.     

Volatile fatty acids of frass of certain omnivorous insects

The frass of the following omnivorous insects reared on natural and artificial diets was analyzed for volatile fatty acids:Blattella germanica, Acheta domesticus, Blaberus discoidalis. Acetic, propionic, isobutyric, butyric, isovaleric, and valeric acids were identified in all frass samples. The possible significance of volatile fatty acids in frass is discussed.     

Aggregation of larvae of the house cricket,Acheta domesticus (L.), by propionic acid present in the excreta

Acetic, propionic, butyric, isobutyric, valeric, and isovaleric acids have been identified in extracts of the excreta of the house cricket,Acheta domesticus (L.), by gas-liquid chromatography. Solutions of propionic acid applied to filter paper aggregated 1- to 2-week-old larvae, while solutions of acetic, butyric, valeric, and isovaleric acids were without effect.     

The effect of organic loading rate on the anaerobic digestion of two‐phase olive mill solid residue derived from fruits with low ripening index

A study of the effect of organic loading rate on the performance of anaerobic digestion of two‐phase olive mill solid residue (OMSR) was carried out in a laboratory‐scale completely stirred tank reactor. The reactor was operated at an influent substrate concentration of 162 g chemical oxygen demand (COD) dm^?3. The organic loading rate (OLR) varied between 0.8 and 11.0 g COD dm^?3 d^?1. COD removal efficiency decreased from 97.0% to 82.6% when the OLR increased from 0.8 to 8.3 g COD dm^?3 d^?1. It was found that OLRs higher than 9.2 g COD dm^?3 d^?1 favoured process failure, decreasing pH, COD removal efficiency and methane production rates (Q_M). Empirical equations described the effect of OLR on the process stability and the effect of soluble organic matter concentration on the total volatile fatty acids (TVFA)/total alkalinity (TAlk) ratio (ρ). The results obtained demonstrated that rates of substrate uptake were correlated with concentration of biodegradable COD, through an equation of the Michaelis–Menten type. The kinetic equation obtained was used to simulate the anaerobic digestion process of this residue and to obtain the theoretical COD degradation rates in the reactor. The small deviations obtained (equal to or lower than 10%) between values calculated through the model and experimental values suggest that the proposed model predicts the behaviour of the reactor accurately. Copyright © 2007 Society of Chemical Industry     

Valeric acid extraction with tri‐n‐butyl phosphate impregnated in a macroporous resin: II. Studies in fixed bed columns

Extraction and back‐extraction of valeric acid in a fixed bed packed with Amberlite XAD‐4 resin impregnated with tri‐n‐butyl phosphate were experimentally studied at 25 °C. The effects of the feed flow rate, acid concentration in the feed solution and extractant concentration in the impregnated resin on the breakthrough curves, were investigated. The bed saturation capacity was larger under the conditions of higher extractant concentration in the resin phase and higher acid concentration in the feed solution. A dynamic model that considers intraparticle diffusion and external liquid film diffusion as limiting steps in mass transfer rates was successfully applied. The intraparticle effective diffusivities (10^?9 dm² s^?1) were from one to three orders of magnitude lower than the diffusivities in the external liquid film (10^?8–10^?6 dm² s^?1). A fast and complete back‐extraction of valeric acid from the saturated bed was carried out with sodium hydroxide solutions. The operational life of the impregnated resin was also studied. Copyright © 2005 Society of Chemical Industry     

Anaerobic biodegradation of phenol in sulfide‐rich media

In the refinery industry, the washing processes of middle‐distillates using caustic solutions generate phenol‐ and sulfide‐containing waste streams. The spent caustic liquors generated contain phenols at concentrations higher than 60 g dm^?3(638.3 mmol dm^?3). For sulfur compounds, the average sulfide concentration was 48 g dm^?3(1500 mmol dm^?3) in these streams. The goal of this study was to evaluate the specific impact of phenol and sulfide concentrations towards the phenol‐biodegradation activity of a phenol‐acclimated anaerobic granular sludge. An inhibition model was used to calculate the phenol and sulfide inhibitory concentrations that completely stopped the phenol‐biodegradation activity (IC100). A maximum phenol‐biodegradation activity of 83 µmol g^?1 VSS h^?1 was assessed and the IC100 values were 21.8 mmol dm^?3 and 13.4 mmol dm^?3 for phenol and sulfide respectively. The limitation of the phenol biodegradation flow by phenol inhibition seemed to be related to the more important sensitivity of phenol‐degrading bacteria. The up‐flow anaerobic sludge bed reactor operating in a non‐phenol‐dependent inhibition condition did not present any sensitivity to sulfide concentrations below 9.6 mmol dm^?3. At this residual concentration, the pH and bisulfide ions' concentration might be responsible for the general collapsing of the reactor activity. Copyright © 2004 Society of Chemical Industry     

Acidogenic fermentation of blended food‐waste in combination with primary sludge for the production of volatile fatty acids

The performance of a laboratory‐scale anaerobic acidogenic fermenter fed with a mixture of blended kitchen food‐waste and primary sludge from a sewage treatment plant was investigated for the production of volatile fatty acids (VFA). The operating variables for acidogenic fermentation were kitchen food‐waste content (10 and 25 wt %), hydraulic retention time (HRT: 1, 3 and 5 days), temperature (ambient: 18 ± 2 °C, and mesophilic: 35 ± 2 °C) and pH (varied from 5.2 to 6.7). The experimental results indicated that effluent VFA concentrations and VFA production rates were higher at ambient temperature than at mesophilic conditions. The net amount of VFA with 10 wt % food‐waste increased up to 920 mg dm^?3 with an increase of HRT, but contrasting results (a decrease of 2610 mg dm^?3) were found due to the conversion of VFA into biogas in the case of 25 wt % food‐waste, which increased significantly at HRT of 3–5 days. In terms of biogas composition (CO₂ and CH₄), the organic matter was converted into CO₂ through the oxidative pathway by facultative species at low temperature while mesophilic temperature and optimum pH (6.3–7.8) played a pivotal role in increasing rate of conversion of VFA into biogas by methanogenesis. Rates of VFA production and their conversion are dependent on the food‐waste content in the mixture. Yet, the higher concentration of food‐waste (25% compared with 10%) did not produce VFA proportionally due to the increased rate of conversion of VFA into gaseous products. The maximum VFA production rate (0.318 g VFA_produced g^?1 VS_fed day^?1) was achieved in the 10 wt % food‐waste at ambient temperature and at a 5‐day HRT. Copyright © 2005 Society of Chemical Industry     

Utilization of response surface methodology to optimize the culture media for the production of rhamnolipids by Pseudomonas aeruginosa AT10

Pseudomonas aeruginosa AT10 produced a mixture of surface‐active rhamnolipids when cultivated on mineral medium with waste free fatty acids as carbon source. The development of the production process to an industrial scale included the design of the culture medium. A 2⁴ full factorial, central composite rotational design and response surface modelling method (RSM) was used to enhance rhamnolipid production by Pseudomonas aeruginosa AT10. The components that are critical for the process medium were the carbon source, the nitrogen source (NaNO₃), the phosphate content (K₂ HPO₄/KH₂PO₄ 2:1) and the iron content (FeSO₄·7H₂O). Two responses were measured, biomass and rhamnolipid production. The maximum biomass obtained was 12.06 g dm^?3 DCW, when the medium contained 50 g dm^?3 carbon source, 9 g dm^?3 NaNO₃, 7 g dm^?3 phosphate and 13.7 mg dm^?3 FeSO₄·7H₂O. The maximum concentration of rhamnolipid, 18.7 g dm^?3, was attained in medium that contained 50 g dm^?3 carbon source, 4.6 g dm^?3 NaNO₃, 1 g dm^?3 phosphate and 7.4 mg dm^?3 FeSO₄·7H₂O. © 2002 Society of Chemical Industry     

Effective microbial production of poly(4‐hydroxybutyrate) homopolymer by Ralstonia eutropha H16

The effective microbial production of copolyesters of 3‐hydroxybutyrate (3HB) and 4‐hydroxybutyrate (4HB) with high mole fractions of 4HB units by a wild‐type strain of Ralstonia eutropha H16 was investigated in culture solutions containing 4‐hydroxybutyric acid (4HBA) and various carbon substrates in the presence of a nitrogen source such as ammonium sulfate. The addition of glucose or acetic acid to the culture solution containing 4HBA in the presence of ammonium sulfate resulted in the production of random copolymers of P(3HB‐co‐4HB) with compositions of up to 82 mol% 4HB, but the yield of copolymers was less than 7 wt% of dried cell weights. In contrast, when n‐alkanoic acids such as propionic acid, butyric acid, valeric acid and hexanoic acid, being subject to β‐oxidation metabolism in the cell, were used as the co‐substrates of 4HBA in the presence of ammonium sulfate, a mixture of copolymers with two different 4HB compositions was produced, and copolyesters with compositions of 93–100 mol% 4HB were isolated from chloroform–n‐hexane insoluble fractions in the mixture of copolymers. Especially, when this wild‐type Ralstonia eutropha H16 was cultivated in a medium containing 4HBA (15 g litre⁻¹), propionic acid (5 g litre⁻¹) and ammonium sulfate (5 g litre⁻¹), namely C/N (mol/mol) = 10, the P(4HB) homopolymer was produced at maximally 34 wt% of dry cell weight (7.8 g litre⁻¹), and the conversion yield of 4HBA to P(4HB) homopolymer resulted in values as high as 21 mol%. © 1999 Society of Chemical Industry     

Repellent effect of volatile fatty acids of frass on larvae of german cockroach,Blattella germanica (L.) (Dictyoptera: Blattellidae)

Two- to 12-day-old larvae ofBlattella germanica are repelled by certain volatile fatty acids present in the frass. Propionic, isovaleric, and valeric acids are strongly repellent, isobutyric acid is slightly repellent, and acetic and butyric acids are without effect. These results are discussed in relation to control of population density.     

Molecular Finger Printing of Nutra-Coconut Oil with Improved Health Protective Phytoceuticals and its Efficacy as Frying Medium

Coconut oil is rich in medium chain triglycerides but lacks polyunsaturated fatty acids (PUFA) and bio‐active phytoceuticals. In the present work nutra‐coconut oil was prepared by blending coconut oil and flaxseed oil (70:30) and adding 3000 ppm of flaxseed cake concentrate using ethanol, methanol and 20 % aqueous ethanol. The concentrate prepared from flaxseed was from ethanol as it gave maximum yield. The different bio‐active molecules in flaxseed concentrate observed are polyphenols (39.04 %), tocopherols (4.37 %), ferulic acid (0.17 mg g^?1), p‐coumaric acid (2.24 mg g^?1), chlorogenic acid (16.11 mg g^?1), gallic acid (8.58 mg g^?1), sinapic acid (0.64 mg g^?1) and secoisolariresinol (30.13 mg g^?1). The nutra‐coconut oil was found to have polyphenols (2.86 %), tocopherols (442.96 ppm) and antiradical activity (94 %). The PUFA content was found to increase in nutra‐coconut oil significantly (p < 0.05) (2–22 %). The FT‐IR spectra of nutra‐coconut oil revealed that the peak at 3009 and 1651 cm^?1 was associated with the presence of unsaturated fatty acids. There was no significant (p > 0.05) difference observed in sensory attributes of snack food fried using coconut oil and nutra‐coconut oil indicating that the later could be used as a frying medium and useful for food processing industries.     

Process kinetics of UASB reactors treating non‐inhibitory substrate

The degradation of a non‐inhibitory substrate (sucrose) in upflow anaerobic sludge bed (UASB) reactors with different superficial flow velocites (u_s) was performed to generate experimental data. Additionally, a kinetic model accounting for the mass fraction of methanogens (f) and granule size distribution in UASB reactors is also proposed. At the volumetric loadings of 2.65–21.16 g COD dm^?3 day^?1, both the COD removal efficiency and granule size of the UASB reactors increase with increasing u_s. The f values determined experimentally increase from 0.13–0.24 to 0.27–0.43 if the volumetric loading is increased from 2.65 to 5.29 g COD dm^?3 day^?1. With a further increase in volumetric loading, the f values decline because of the accumulation of volatile fatty acids (VFAs). The predicted residual concentrations of VFAs and COD are in fairly good agreement with the experimental data. From the calculated effectiveness‐factor values, the influence of mass transfer resistance of the substrate sucrose on the overall substrate removal rate should not be neglected. From parametric sensitivity analyses together with the simulated concentration profiles, methanogenesis is the rate‐limiting step. Copyright © 2003 Society of Chemical Industry     

D‐Lactic acid production from waste cardboard

The effects caused by alkaline treatment on the susceptibility of waste cardboard to enzymatic hydrolysis have been studied. Optimised conditions leading to extensive saccharification of both cellulose (870 g kg^?1 conversion) and hemicelluloses (845 g kg^?1 conversion) were identified. Samples treated under selected operational conditions were employed for producing D ‐lactic acid by simultaneous saccharification and fermentation (SSF) in media containing cellulases, β‐glucosidase and Lactobacillus coryniformis ssp torquens cells. SSF fed‐batch experiments led to D ‐lactic acid concentrations up to 23.4 g dm^?3 at a product yield of 514 g lactic acid kg^?1 of potential glucose and a volumetric productivity of 0.48 g dm^?3 h^?1. Copyright © 2004 Society of Chemical Industry     

Lipophilic components in black currant seed and pomace extracts

The nature of the fatty acids and other lipophilic components in extracts from black currant seed and pomace (containing seed) were investigated, with a view to highlighting any potential uses. The same non‐hydroxylated fatty acids were the major components in both types of extract, but total levels were less in pomace (75 582 mg 100 g^?1 oil) than in seed alone (90 972 mg 100 g^?1 oil) and there were less unsaturated fatty acids, including GLA (8653 and 12 625 mg 100 g^?1 oil, respectively), but long chain n‐20:0 – n‐30:0 fatty acids (4080 and 437 mg 100 g^?1 oil, respectively) were greatly increased in pomace. Phytosterols (mainly β‐sitosterol), saturated n‐20:0 – n‐30:0 policosanols, ω‐hydroxy fatty acids (mainly 16‐hydroxy 16:0) and 2‐hydroxy fatty acids (mainly 2‐hydroxy 24:0) were present at much greater levels in pomace (2496, 2097, 958 and 46 mg 100 g^?1 oil, respectively) than in seed (553, 108, 161, and 1 mg 100 g^?1 oil, respectively). The pomace extract is a useful source of fatty acids, phytosterols and policosanols with potential functional properties. Practical applications: The study investigated the lipophilic components in isohexane extracts from black currant seed and pomace (containing seed). Only pomace extracts had substantial amounts of phytosterols and policosanols that have potential as cholesterol‐lowering agents, whereas fatty acids such as GLA, that has anti‐inflammatory properties, are mainly in the seed.     

Protein hydrolysis under anaerobic,saline conditions in presence of acetic acid

The hydrolysis of soluble proteins in an anaerobic, saline (24 g dm^?3 NaCl) and mesophilic (37 °C) environment was studied. The inhibitory effect of a volatile fatty acid, acetic acid (HAc), on the hydrolysis rate and hydrolytic biomass activity for a model saline wastewater with a high protein load (total organic carbon, 1153 mg dm^?3 and 1572 mg dm^?3 proteins) was studied. Initial inhibitor concentrations were tested in the range of 0–2000 mg dm^?3 HAc. The microbiological characterization was performed using a total microorganism count by epifluorescence, and hydrolytic bacterial activity was determined by plate count. The protein hydrolysis was modeled according to first order kinetics. The effect of biomass on hydrolysis was analyzed by varying its concentration in the range of 42–210 mg dm^?3 volatile suspended solids. The following apparent hydrolysis kinetic constants (K_h) for proteins at 37 °C were obtained: 1.3, 0.8, 0.6, 0.2 and 0.1 d^?1 for initial concentrations of 250, 500, 750, 880, and 1000 mg dm^?3 HAc, respectively. At concentrations of HAc greater than 1000 mg dm^?3, total inhibition of hydrolysis was observed. The intrinsic hydrolysis constant ( ) at 37 °C, without inhibition, was 2.3 d^?1. The hydrolysis kinetic constant was not affected by the biomass concentration. The hydrolysis kinetics constant was filted to three models: Luong, Levenspiel and non‐competitive inhibition. The model that best represented the experimental data was Luong, obtaining an inhibition constant (K_I) of 1087 mg dm^?3 of HAc and the exponent γ = 0.54. The hydrolysis was inhibited by the presence of HAc, which corresponds to an intermediate compound of the anaerobic process. Copyright © 2004 Society of Chemical Industry     

Optimization of the production of β‐carotene from molasses by Blakeslea trispora: a statistical approach

The effect of pretreatment of molasses, nitrogen sources, natural oils, fatty acids, antioxidant, precursors, and mixtures of the above substances on β‐carotene production by Blakeslea trispora in shake flask culture was investigated. Also, a central composite design was employed to determine the maximum β‐carotene concentration at optimum values for the process variables (linoleic acid, kerosene, antioxidant). The highest concentration of the carotenoid pigment was obtained in molasses solution treated with invertase. Corn steep liquor and yeast extract at concentrations of 5.0% and 0.5% (w/v), respectively, increased slightly the concentration of β‐carotene, while the natural oils, fatty acids, and precursors (except kerosene) did not improve the production of pigment when they were added separately to the medium. On the other hand, the mixture of linoleic acid, kerosene and antioxidant increased significantly the concentration of β‐carotene. The fit of the model was found to be good. Linoleic acid, kerosene and antioxidant had a strong linear effect on β‐carotene concentration. The concentration of β‐carotene was significantly affected by linoleic acid–antioxidant and kerosene–antioxidant interactions as well as by the negative quadratic effects of these variables. The interaction between linoleic acid–kerosene had no significant linear effect. Maximum β‐carotene concentration (790.0 mg dm^?3) was obtained in culture grown in molasses solution supplemented with linoleic acid (30.74 g dm^?3), kerosene (27.79 g dm^?3) and antioxidant (10.22 g dm^?3). © 2002 Society of Chemical Industry