Mixture Of Volatile Fatty Acids Research Articles

The effect of volatile fatty acid additions on the anaerobic digestion of cellulose and glucose in batch reactors

Batch anaerobic reactor experiments were set up in which the degradation of the primary substrates cellulose and glucose was assayed when dosed with a concentration range from 1 to 20 g l −1 of a synthetic mixture of volatile fatty acids (VFA). Biogas production from the VFA mix and from reactors without VFA additions was used as a baseline control against which the results were compared and interpreted. The 1-l mesophilic (35 °C) reactors were seeded with an actively digesting sludge of sewage origin and monitored for biogas production, gas composition, volatile fatty acid concentration, glucose content and the cellulolytic enzymes carboxymethylcellulase and avicelase. Cellulose reduction was measured from initial and final samples of the reaction mix in each case. VFA caused inhibition of the cellulolytic activity at concentrations ≥2 g l −1, and therefore of the rate of cellulose hydrolysis. The fermentation of glucose was slightly inhibited at VFA concentrations above 4 g l −1. The inhibitory effect on the production of biogas and also on the methane to carbon dioxide ratio was evident above 6 g l −1 VFA in the initial mixture when used as the sole substrate. In combination with paper as primary substrate, biogas production due to the paper was more than halved above 1 g l −1 initial VFA, indicating inhibition of the hydrolysis process. Where glucose was the primary substrate biogas production was more than halved above 8 g l −1 which indicated that the fermentation was less sensitive to inhibition caused by VFA.

Liquid Swine Manure Can Kill Verticillium dahliae Microsclerotia in Soil by Volatile Fatty Acid, Nitrous Acid, and Ammonia Toxicity

ABSTRACT In previous studies, liquid swine manure (LSM) was sometimes shown to reduce Verticillium wilt of potato caused by Verticillium dahliae. We also observed that microsclerotia of this fungus died within 1 day, or between 3 and 6 weeks, after addition of LSM to some acid soils and within 1 week in some alkaline soils. In this study, we demonstrated that a volatile fatty acid (VFA) mixture with an identical concentration of VFAs as that found in an effective LSM reduced germination in an acid soil (pH 5.1) to the same extent as the LSM after 1 day of exposure. Germination was reduced by 45, 75, and 90% in the 10, 20, and 40% ([wt/wt] soil moisture) treatments, respectively, with the latter being equivalent to an application of 80 hl/ha. Addition to this acid soil of 19 LSMs (30% [wt/wt] soil moisture) collected from different producers resulted in complete kill of microsclerotia with 12 manures. Effective manures had a total concentration of nonionized forms of VFAs in soil solution of 2.7 mM or higher. In some acid soils (pH 5.8), addition of LSM (40% [wt/wt] soil moisture) did not kill microsclerotia until 3 to 6 weeks later. Here, a reduction in viability of microsclerotia was attributed to the accumulation of 0.06 mM nitrous acid in the soil solution at 4 weeks. When an LSM was added (40% [wt/wt] soil moisture) to an alkaline soil (pH 7.9) where VFAs are not toxic, microsclerotia germination was reduced by 80% after 1 week. Here the pH increased to 8.9 and the concentration of ammonia reached 30 mM in the soil solution. An ammonium chloride solution having an equivalent concentration of ammonium as the manure was shown to have the same spectrum of toxicity as the manure in assays ranging from pH 7 to 9, both in solutions and above the solutions. At pH 9, the concentration of ammonia reached 18 mM and 100% mortality of microsclerotia occurred. Thus, in acid soils, LSM can kill microsclerotia of V. dahliae by VFA and/or nitrous acid toxicity and in alkaline soils by ammonia toxicity. In order to take advantage of these mechanisms for disease reduction, the manure chemical composition, rate of addition, and soil characteristics need to be determined for each instance of use.

Anaerobic microbial mobilization and biotransformation of arsenate adsorbed onto activated alumina

Due to the enactment of a stricter drinking water standard for arsenic in the United States, larger quantities of arsenic will be treated resulting in larger volumes of treatment residuals. The current United States Environmental Protection Agency recommendation is to dispose spent adsorbent residuals from arsenic treatment into non-hazardous municipal solid waste (MSW) landfills. The potential of microorganisms to alter the speciation affecting the mobility of arsenic in the disposal environment is therefore a concern. The purpose of this paper was to evaluate the potential of an anaerobic microbial consortium to biologically mobilize arsenate (As(V)) adsorbed onto activated alumina (AA), a common adsorbent used for treating arsenic in drinking water. Three anaerobic columns (0.27 l) packed with 100 g dry weight of AA containing 0.657 mg adsorbed As(V) (expressed as arsenic) per gram dry weight were continuously flushed with synthetic landfill leachate for 257 days. The fully biologically active column was inoculated with methanogenic anaerobic sludge (10 g volatile suspended solids l(-1) column) and was operated with a mixture of volatile fatty acids (VFA) in the feed (2.5 g chemical oxygen demand l(-1) feed). At the end of the experiment, 37% of the arsenic was removed from the column, of which 48% was accounted for by arsenical species identified in the column effluent. The most important form of arsenic eluted was arsenite (As(III)), accounting for nearly all of the identified arsenic in periods of high mobilization. Additionally, two methylated metabolites, methylarsonic acid and dimethylarsinic acid were observed. Mobilization of arsenic is attributed to the biological reduction of As(V) to As(III) since literature data indicates that As(III) is more weakly adsorbed to AA compared to As(V). Batch and continuous assays confirmed that VFA, present in landfill leachates, served as an electron donating substrate supporting enhanced rates of As(V) reduction to As(III). Two control columns, lacking inoculum and/or VFA in the feed displayed low mobilization of arsenic compared to the fully biologically active column. Therefore, leachates generated in MSW landfills could potentially result in the biologically catalyzed mobilization of arsenic from As(V)-laden drinking water residuals.

Influence of Animal Origin and Lineage on Survival of Escherichia coli O157:H7 Strains in Strong and Weak Acid Challenges

Twenty-five strains of Escherichia coli O157:H7 isolated from humans, cattle, and pigs were maintained in HCl (pH 2.5) and in a volatile fatty acid (VFA) mixture (pH 4.0) for up to 6 h at 37°C to assess their ability to survive in acidic conditions that simulate those of the stomach and ileum, respectively. In HCl, the average group survival of bovine strains was significantly higher than that of porcine and human strains, whereas in VFAs, porcine strains were significantly more resistant than bovine and human strains. Bovine strains exhibited significantly higher average survival in HCl than in VFAs. The average survival of strains classified as octamer-based genome scanning (OBGS) lineage II was significantly superior to that of strains classified as OBGS lineage I in HCl. The group of lineage I strains was more resistant in VFAs compared with lineage II, but only after 6 h of challenge. The possible involvement of urease in acid resistance of E. coli O157:H7 was also examined. Although the strains possessed the ureC gene, as shown by PCR, this gene did not appear to contribute to acid resistance under the conditions tested. The data indicate that there is a relationship between acid resistance and source or lineage of O157:H7 strains.

Glucose Metabolism in Lactating Cows in Response to Isoenergetic Infusions of Propionic Acid or Duodenal Glucose

A bibliographical study showed that increasing supplies of glucogenic nutrients lead to a curvilinear increase in milk and protein yield. Increased post-hepatic glucose availability may be involved in the increase in milk yield. In the present experiment, 5 dairy cows were arranged in a 5×5 Latin square design to compare the respective effects of 2 amounts of either duodenal glucose or ruminal propionic acid (C3) on glucose metabolism. Treatment consisted of a grass silage-based diet supplemented with glucogenic nutrients infused into the rumen as a mixture of volatile fatty acids (control) or C3 (6.5 and 13 mol/d) or as glucose (3.4 and 6.9 mol/d) infused into the duodenum. Treatments were isoenergetic and isonitrogenous and contained 100 and 115% of energy and protein requirements, respectively, according to the Institut National de la Recherche Agronomique. Glucose appearance rate (Ra) tended to increase with the level of infusions of both glucogenic materials and with the high dose of duodenal glucose. Plasma insulin-like growth factor-I (IGF-I) concentration increased with the infusion of glucogenic materials compared with the control and was significantly higher with glucose than with C3 treatments. This experiment did not indicate whether the increased Ra was the key mechanism to increased milk yield because milk yield only tended to increase and the standard error for Ra was high. With the high dose of glucose infused into the duodenum, the Ra increase was greater than the increased lactose production in milk. Because of that connection, IGF-I may also be involved by favoring the glucose utilization by the mammary gland.

Facile reduction of arsenate in methanogenic sludge.

Due to the recent enactment of a stricter drinking water standard for arsenate, large quantities of arsenate-laden drinking water residuals will be disposed in municipal landfills. The objective of this study was to determine the role of methanogenic consortia on the conversion of arsenate. Methanogenic conditions commonly occur in mature municipal solid waste landfills. The results indicate the rapid and facile reduction of arsenate to arsenite in methanogenic sludge. Endogenous substrates in the sludge were sufficient to support the reductive biotransformation. However the rates of arsenate reduction were stimulated by the addition of exogenous electron donating substrates, such as H2, lactate or a mixture of volatile fatty acids. A selective methanogenic inhibitor stimulated arsenate reduction in microcosms supplied with H2, suggesting that methanogens competed with arsenate reducers for the electron donor. Rates of arsenate reduction increased with arsenate concentration up to 2 mM, higher concentrations were inhibitory. The electron shuttle, anthraquinone-2,6-disulfonate, used as a model of humic quinone moieties, was shown to significantly increase rates of arsenate reduction at substoichiometric concentrations. The presence of sulfur compounds, sulfate and sulfide, did not affect the rate of arsenate transformation but lowered the yield of soluble arsenite, due to the precipitation of arsenite with sulfides. The results taken as a whole suggest that arsenate disposed into anaerobic environments may readily be converted to arsenite increasing the mobility of arsenic. The extent of the increased mobility will depend on the concentration of sulfides generated from sulfate reduction.

Effect of redox mediator, AQDS, on the decolourisation of a reactive azo dye containing triazine group in a thermophilic anaerobic EGSB reactor

The feasibility of thermophilic (55 °C) anaerobic treatment applied to colour removal of a triazine contained reactive azo dye was investigated in two 0.53 l expanded granular sludge blanket (EGSB) reactors in parallel at a hydraulic retention time (HRT) of 10 h. Generally, this group of azo dyes shows the lowest decolourisation rates during mesophilic anaerobic treatment. The impact of the redox mediator addition on colour removal rates was also evaluated. Reactive Red 2 (RR2) and anthraquinone-2,6-disulfonate (AQDS) were selected as model compounds for azo dye and redox mediator, respectively. The reactors achieved excellent colour removal efficiencies with a high stability, even when high loading rates of RR2 were applied (2.7 g RR2 l −1 per day). Although AQDS addition at catalytic concentrations improved the decolourisation rates, the impact of AQDS on colour removal was less apparent than expected. Results show that the AQDS-free reactor R2 achieved excellent colour removal rates with efficiencies around 91%, compared with the efficiencies around 95% for the AQDS-supplied reactor R1. Batch experiments confirmed that the decolourisation rates were co-substrate dependent, in which the volatile fatty acids (VFA) mixture was the least efficient co-substrate. The highest decolourisation rate was achieved in the presence of either hydrogen or formate, although the presence of glucose had a significant impact on the colour removal rates.

Enrichment and immobilization of quinone-respiring bacteria in anaerobic granular sludge

The capacity of an anaerobic granular sludge for serving as an immobilizing mechanism for quinone-respiring bacteria was evaluated. The inoculum was continuously fed with a basal medium containing the humic model compound, anthraquinone-2,6-disulfonate (AQDS), as a terminal electron acceptor. Complete reduction of AQDS was achieved by the granular sludge for a prolonged period in an anaerobic bioreactor provided with a mixture of volatile fatty acids as a substrate. Phylogenetic analysis revealed the enrichment and immobilization of AQDS-respiring bacteria appearing as dominant organisms in the microbial population of the AQDS-supplemented reactor, compared to a reactor control operated under methanogenic conditions. The consistent quinone-reducing capacity observed in the consortium indicates that it is feasible to apply quinone-reducing microorganisms in continuous bioreactors and this ability can potentially be important in wastewaters rich in humic substances. The quinone reducing activity could also be applied to accelerate the conversion of xenobiotics susceptible to reductive biotransformations such as azo dyes and polychlorinated compounds in continuous bioreactors.

Essential metal depletion in an anaerobic reactor

The effect of the absence of trace elements on the conversion of a mixture of volatile fatty acids by a distillery anaerobic granular sludge was investigated. Two UASB reactors were operated under identical operational conditions except for the influent trace metal concentrations, during 140 days. Experiments were carried out in three periods, where different organic loading rates (OLR) were applied to the reactors. The total trace metal concentration steadily decreased at a rate of 48 microg metal/g TS.d in the deprived reactor (down to 35% of their initial value). In contrast, trace metals accumulated in granules present in the control reactor. At the end of the experiment, the COD removal efficiencies were 99% and 77% for the control and deprived reactors, respectively, due to the lack of propionate conversion. Cobalt sorption experiments were carried out in order to study its speciation, and its effects on the speciation of other metals as well. A paper mill wastewater treating granular sludge was also included in the study as a comparison. Results obtained showed that the principal metal forms normally associated with any sludge are a function of each soluble metal concentration in the system, and the characteristics of the particular sludge.

Sulfidogenic volatile fatty acid degradation in a baffled reactor

The effect of staging the sludge bed on volatile fatty acid degradation by sulfidogenic reactors was evaluated in a baffled reactor. In a 5.4 l baffled reactor, containing three equal compartments, a volatile fatty acid (VFA) mixture (acetate:propionate:butyrate ratio 1:2:2 on COD basis; pH 8) was treated under mesophilic (30 degrees C) and sulfidogenic (COD:SO4(2-) ratio: 0.5) conditions for 38 days. At a specific sludge loading rate of 0.50 g COD.gVSS(-1) x d(-1), a COD and sulfate removal of 85% and 30%, respectively, was obtained. In the baffled reactor, staging of the sulfidogenic VFA degradation occurred. Propionate and butyrate were mainly degraded in the first compartment. Their degradation was incomplete, resulting in elevated acetate concentrations in compartment I. In the second and third compartment of the baffled reactor, a net degradation of acetate took place. Acetate was the sole substrate present in compartment III and residual acetate concentrations of about 200 mg/l were present in the effluent at a specific sludge loading of 0.50 g COD x gVSS(-1) x d(-1). Sludges with different maximum specific VFA and acetate degrading activities developed in the first and second compartment. These maximal specific activities were almost equal for sludge present in compartment II and III.

Effect of nisin on two cultures of rumen ciliates.

The effect of nisin (in the form of Nisaplin) was determined using two species of rumen ciliate protozoa in vitro, on their co-culture bacterial population, and volatile fatty acid concentration. Nisaplin did not affect the in vitro growth of Entodinium caudatum at concentrations of 50-400 mg/L during short-term treatment (5 d). Long-term application (30 d) of Nisaplin (100 mg/L) significantly decreased growth of the Epidinium ecaudatum forma caudatum et ecaudatum but not growth of E. caudatum. Nisaplin moderately supported the growth of E. caudatum after omission of wheat gluten (source of amino acids for protozoan growth). An inhibition of Gram-positive facultative anaerobic bacterial population in the protozoan cultures (lactobacilli, enterococci, staphylococci and amylolytic streptococci) was observed during long-term Nisaplin treatment. The concentration of volatile fatty acids significantly increased during the long-term Nisaplin treatment of both cultures. The propionate concentration in the mixture of volatile fatty acids was nearly twice higher on the account of the decreased concentration (from 74 to 63%) of acetate.

Effects of trace element addition on volatile fatty acid conversions in anaerobic granular sludge reactors

The effect of the addition of trace elements on the conversion of a mixture of volatile fatty acids (Acetate, Propionate, Butyrate, in a ratio 3:1:1) by anaerobic granular sludge was investigated. Two Upflow Anaerobic Sludge Bed reactors (pH 7, 30°C) were operated for 140 days at an organic loading rate ranging from 2 g COD l−1 d−1 up to 10 g COD 1−1 d−1 and a hydraulic retention time of 12 hours. One reactor (Rl) was supplied with a trace metal cocktail in the basal medium, whereas trace metals were omitted from the influent of the second reactor (R2). As a result, the trace metal concentration in the granules from R2 steadily decreased at a rate of 48 μg metal g−1 TS d−1 down to 35% of their initial value. In contrast, trace metals accumulated in granules present in Rl. At the end of the experiment, the COD removal efficiencies were 99 and 77% for, respectively, the control (R1) and deprived (R2) reactors. This difference was due to lack of propionate conversion by sludge from R2. No difference in the acetate and butyrate conversion capacity of both reactors was observed. The conversion of acetate, propionate and methanol were stimulated by the continuous addition of metals to the influent, as sludge of R1 had higher maximum specific activity values compared to sludge of R2. However, both sludges had a similar maximum specific activity with buryrate. Surprisingly, maximum specific activity tests using individual trace metals showed that the addition of a particular trace element in the activity test medium did not affect the degradation rates of a specific substrate, i.e. acetate, propionate, butyrate and methanol

Lactational Effect of Propionic Acid and Duodenal Glucose in Cows

Five dairy cows were arranged in a 5×5 Latin square design to compare the effects of two amounts of either duodenal glucose or ruminal propionic acid (C3) on milk yield and composition. Treatments consisted of a grass silage-based diet supplemented with glucogenic nutrients either infused in the rumen as a mixture of volatile fatty acids (control) or pure C3 (1.72 and 3.45 Mcal/d) or in the duodenum as glucose (1.72 and 3.45 Mcal/d). Treatments were isoenergetic and isonitrogenous and contained 100 and 115% of energy and protein requirements according to INRA (1989), respectively. Only C3 treatments significantly modified ruminal volatile fatty acid composition and linearly increased C3 percentage (up to 25.5%). Both treatments substantially decreased milk fat yield and content, and linearly increased milk and protein yields. Although no significant differences between glucose and C3 were highlighted for milk yield and composition, it seems that mechanisms involved in milk fat decrease are different. Indeed, whereas C3 treatments decreased fatty acid production in an homogeneous way, short- and long-chain fatty acids decreased and medium-chain fatty acid production increased with glucose treatments. A bibliographical study confirmed that increasing glucogenic precursors (GP) supply curvilinearly increase milk yield, linearly increase milk protein content (+ 0.04% per Mcal of GP) and curvilinearly decrease milk fat content (− 0.14% per Mcal of GP). Thus, it appears important to account for the nature of energy supplied by the ration in formulation.

Analysis of the microbial community structure and function of a laboratory scale enhanced biological phosphorus removal reactor.

A laboratory scale sequencing batch reactor (SBR) operating for enhanced biological phosphorus removal (EBPR) and fed with a mixture of volatile fatty acids (VFAs) showed stable and efficient EBPR capacity over a four-year-period. Phosphorus (P), poly-beta-hydroxyalkanoate (PHA) and glycogen cycling consistent with classical anaerobic/aerobic EBPR were demonstrated with the order of anaerobic VFA uptake being propionate, acetate then butyrate. The SBR was operated without pH control and 63.67 +/- 13.86 mg P l-1 was released anaerobically. The P% of the sludge fluctuated between 6% and 10% over the operating period (average of 8.04 +/- 1.31%). Four main morphological types of floc-forming bacteria were observed in the sludge during one year of in-tensive microscopic observation. Two of them were mainly responsible for anaerobic/aerobic P and PHA transformations. Fluorescence in situ hybridization (FISH) and post-FISH chemical staining for intracellular polyphosphate and PHA were used to determine that 'Candidatus Accumulibacter phosphatis' was the most abundant polyphosphate accumulating organism (PAO), forming large clusters of coccobacilli (1.0-1.5 micro m) and comprising 53% of the sludge bacteria. Also by these methods, large coccobacillus-shaped gammaproteobacteria (2.5-3.5 micro m) from a recently described novel cluster were glycogen-accumulating organisms (GAOs) comprising 13% of the bacteria. Tetrad-forming organisms (TFOs) consistent with the 'G bacterium' morphotype were alphaproteobacteria, but not Amaricoccus spp., and comprised 25% of all bacteria. According to chemical staining, TFOs were occasionally able to store PHA anaerobically and utilize it aerobically.

The Effects of Change in Volatile Fatty Acid (VFA) Composition on Methanogenic Upflow Filter Reactor (UFAF) Performance

The effects of changes in composition of a volatile fatty acid mixture (namely acetic, propionic and butyric acids) fed to a methanogenic upflow filter reactor (UFAF) were investigated in terms of reactor chemical oxygen demand (COD) removal efficiency and biogas production level. A mixed substrate consisting of differing proportions of VFAs (on a COD basis) was fed to the reactor in semi-continuous mode under constant organic loading rate (OLR) and hydraulic retention time (HRT). At an OLR of 1.2 kg COD m−3.d and HRT of 4 days, increasing propionic acid concentrations of about 312 mg l−1, 617 mg l−1, 951 mg l−1 and 1242 mg l−1 fed to the reactor provided COD removal rates and biogas production levels of, 84.70 %-1301 ml d−1, 80.80 %-1214 ml d−1, 73.65 %-1071 ml d−1 and 65.53 %-942 ml d−1, respectively, indicating inhibitory effects of propionic acid on the methanogenic ecosystem. Subsequent introduction of butyric acid (247 mg l−1) in addition to propionic acid (891 mg l−1) increased the performance of the UFAF, yielding 76.10 % COD removal and 1075 ml d−1 of biogas production. The instability observed in the system towards the end of the study probably originated from operating the reactor at relatively high VFA concentrations for a long period of time. Change in VFA composition did not seem to have significant effects on the effluent MLVSS/MLSS ratio. The upflow anaerobic filter reactor adapted to variations in feed composition in a short period of time.

Physicochemical Characterization of UASB Sludge with Different Size Distributions

Upflow anaerobic sludge blanket (UASB) sludges developed in UASB system are used to treat various wastewaters. Methanogenic microbial consortia in UASB sludges convert organic compounds to methane under anaerobic conditions. Sludge granules are developed by self-granulation of microorganisms and dynamic balance between granule growth and decay results in coexistence of UASB sludges with different sizes in the reactor. In this study, UASB sludges taken from a laboratory-scale UASB reactor were classified into 4 groups based on their diameters and their physicochemical characteristics were investigated. Each group was analyzed for settling ability, specific methanogenic activity (SMA), and elemental content. Settling ability was proportional to diameter of UASB sludges, suggesting effective detainment of larger granular sludges in the reactor. When acetate or glucose was used as a substrate, all groups showed a relatively slight difference in SMA. However SMA with a volatile fatty acid mixture showed a significant increase with sludge diameter, suggesting better establishment of syntrophic relationship in larger granular sludges. Larger granular sludges showed a higher value of SMA upon environmental changes (i.e., pH, temperature, or toxicant concentration). Comparative analysis of elemental contents showed that content (dry weight %) of most tested elements (Fe, Ca, P, Zn, Ni, and Mn) decreased with sludge diameter, suggesting that the elements could be important for initial granulation. Taken together, this study verified experimentally that physicochemical properties of UASB sludges are related to UASB sludge size distributions. Overall results of physicochemical characterization supports that larger granular sludges are better applicable to UASB systems.

Volatile Fatty Acids in Liquid Swine Manure Can Kill Microsclerotia of Verticillium dahliae

ABSTRACT Liquid swine manure added to acidic soils killed microsclerotia of the wilt fungus Verticillium dahliae. We investigated whether volatile fatty acids (VFAs) in the manure were responsible for this toxicity. The survival of microsclerotia was determined after exposure to various dilutions of manure or its VFA components. Acetic, propionic, and isobutyric acids constituted the major VFAs in the manure, while n-butyric, n-valeric, iso-valeric, and n-caproic acids were present in lesser amounts. Formic acid was not detected. The individual VFAs were more toxic to microsclerotia as the solution pH was decreased, indicating that the protonated forms of the VFAs were toxic (e.g., acetic acid and not acetate). The effective concentration reducing germination of microsclerotia by 95% (EC(95)) for formic and n-caproic acids was approximately 4 mM, the most toxic of the acids tested; for n-valeric, the EC(95) was 9.2 mM, isovaleric was 16.1 mM acids, and acetic, propionic, n-butyric, and isobutyric acids were approximately 30 mM. The toxicity of acetic acid, and likely all the others, was directly related to the duration of exposure. Inhibition of microsclerotia germination followed identical trends in solutions of the manure or in a mixture of VFAs with equivalent concentrations of the individual acids found in the manure. Similarly, germination declined to the same extent in the atmosphere above the manure or the VFA mixture, confirming the toxicity of VFAs to microsclerotia. Thus, under acid conditions, VFAs in liquid swine manure can kill microsclerotia of V. dahliae.

Application of redox mediators to accelerate the transformation of reactive azo dyes in anaerobic bioreactors.

Azo dyes are nonspecifically reduced under anaerobic conditions but the slow rates at which reactive azo dyes are converted presents a serious problem for the application of anaerobic technology as a first stage in the complete biodegradation of these compounds. As quinones have been found to catalyze reductive transfers by acting as redox mediators, the application of anthraquinone-2,6-disulfonic acid (AQDS) during continuous anaerobic treatment of the reactive azo dye, Reactive Red 2 (RR2), was evaluated. A mixture of volatile fatty acids was used as the electron-donating primary substrate. Batch experiments demonstrated that AQDS could increase the first-order rate constant of RR2 reductive cleavage by one order of magnitude. In the continuous experiment, treatment of RR2 containing synthetic wastewater in a lab-scale upflow anaerobic sludge blanket (UASB) reactor yielded low dye removal efficiencies (<30%). Consequently, severe toxicity problems occurred, eventually resulting in almost complete inhibition of the methanogenic activity. Addition of catalytic concentrations of AQDS (19 microM) to the reactor influent caused an immediate increase in the dye removal efficiency and recovery of biological activity. Ultimately, RR2 removal efficiency stabilized at 88%, and higher AQDS loads resulted in higher RR2 removal efficiencies (up to 98% at 155 microM AQDS). Examination of the RR2 decolorizing properties of dye-adapted reactor sludge and of nonadapted reactor seed sludge revealed that RR2 decolorization was principally a biologically driven transfer of reducing equivalents from endogenous and added substrates to the dye. Hydrogen, added in bulk, was clearly the preferred electron donor. Bacteria that couple dye decolorization to hydrogen oxidation were naturally present in seed sludge. However, enrichment was required for the utilization of electrons from volatile fatty acids for dye reduction. The stimulatory effect of AQDS on RR2 decolorization by AQDS-unadapted sludge was mainly due to assisting the electron transfer from endogenous substrates in the sludge to the dye. The stimulatory effect of AQDS on RR2 decolorization by sludge from the AQDS-exposed reactor was, in addition, strongly associated with the transfer of electrons from hydrogen and acetate to the dye, probably due to enrichment of specialized AQDS-reducing bacteria.

Continuous detoxification, transformation, and degradation of nitrophenols in upflow anaerobic sludge blanket (UASB) reactors

The anaerobic transformation and degradation of nitrophenols by granular sludge was investigated in upflow anaerobic sludge blanket (UASB) reactors continuously fed with a volatile fatty acid (VFA) mixture as the primary substrate. During the start-up, subtoxic concentrations of 2-nitrophenol (2-NP), 4-nitrophenol (4-NP), and 2, 4-dinitrophenol (2, 4-DNP) were utilized. 4-NP and 2, 4-DNP were readily converted to the corresponding aromatic amine; whereas 2-NP was converted to nonaromatic products via intermediate formation of 2-aminophenol (2-AP). These conversions led to a dramatic detoxification of the mononitrophenols because the reactors treated the nitrophenolics at the concentrations which were over 25 times higher than those that caused severe inhibition. VFA removal efficiencies greater than 99% were achieved in both reactors at loading rates greater than 11.4 g COD per liter of reactor volume per day even at volumetric loading of mononitrophenols up to 910 mg/L . d.The sludges obtained from each of the reactors at the end of the continuous experiments were assayed for their specific nitrophenol reducing activity in the presence of different primary substrates. Reduction rates of 45 and 26 mg/g volatile suspended solids per day were observed for 2-NP and 4-NP, respectively, when utilizing the VFA mixture as primary substrate. Hydrogen, an interspecies-reduced compound, and substrates that provide interspecies-reducing equivalents-such as butyrate, propionate, and ethanol stimulated nitrophenol reduction, whereas acetate and methanol did not. Anaerobic batch biodegradability tests with the 2-NP-adapted sludge revealed that its corresponding aromatic amine, 2-AP, was degraded to methane at a specific rate of 14.5 mg/g VSS . d. Acetate was observed to be the major intermediate during 2-AP degradation in the presence of a specific methanogenic inhibitor 2-bromoethanesulfonate. The results of this study indicate that UASB reactors can be applied to rapidly detoxify and, under certain circumstances, degrade nitroaromatic compounds. (c) 1996 John Wiley & Sons, Inc.

Kinetic study of addition of volatile organic compounds to a nitrifying sludge.

The effects of different concentrations of several volatile organic compounds (VOC) such as ethanol, acetate, propionate, and butyrate ranging from 0 to 2000 mg/L as well as a mixture of volatile fatty acids (MVFA) at a 4:1:1 (acetate:propionate:butyrate) ratio on the nitrification rate in batch cultures were studied. The results showed that ethanol and acetate were consumed in a mixotrophic way by the nitrifying sludge. At a concentration of 500 mg/L, the nitrification rate of inhibition was different for each compound in which propionate and butyrate were the most inhibitory. At 2000 mg/L the inhibition was 80% with ethanol and 100% with acetate, propionate, and butyrate. With similar concentrations of MVFA, the inhibition was also similar to that in acetate. The effect of the addition of pulses of MVFA at a ratio of 4:1:1 during 14 h on the performance of the continuous nitrifying process with a hydraulic retention time of 3 d was also studied. No inhibition of the nitrification process was observed with pulses of 750-3000 mg of MVFA/L in the input of the reactor. The results in batch cultures suggest that the different degrees of inhibition of the nitrification process were related to the type of organic matter added. The noninhibitory effect of the organic matter in the continuous cultures on the nitrification efficiency of the nitrifying sludge might be related to the feeding pattern.