Hydrogen and electricity production from a food processing wastewater using fermentation and microbial fuel cell technologies

Hydrogen can be produced from fermentation of sugars in wastewaters, but much of the organic matter remains in solution. We demonstrate here that hydrogen production from a food processing wastewater high in sugar can be linked to electricity generation using a microbial fuel cell (MFC) to achieve more effective wastewater treatment. Grab samples were taken from: plant effluent at two different times during the day (Effluents 1 and 2; 735+/-15 and 3250+/-90 mg-COD/L), an equalization tank (Lagoon; 1670+/-50mg-COD/L), and waste stream containing a high concentration of organic matter (Cereal; 8920+/-150 mg-COD/L). Hydrogen production from the Lagoon and effluent samples was low, with 64+/-16 mL of hydrogen per liter of wastewater (mL/L) for Effluent 1, 21+/-18 mL/L for Effluent 2, and 16+/-2 mL/L for the Lagoon sample. There was substantially greater hydrogen production using the Cereal wastewater (210+/-56 mL/L). Assuming a theoretical maximum yield of 4 mol of hydrogen per mol of glucose, hydrogen yields were 0.61-0.79 mol/mol for the Cereal wastewater, and ranged from 1 to 2.52 mol/mol for the other samples. This suggests a strategy for hydrogen recovery from wastewater based on targeting high-COD and high-sugar wastewaters, recognizing that sugar content alone is an insufficient predictor of hydrogen yields. Preliminary tests with the Cereal wastewater (diluted to 595 mg-COD/L) in a two-chambered MFC demonstrated a maximum of 81+/-7 mW/m(2) (normalized to the anode surface area), or 25+/-2 mA per liter of wastewater, and a final COD of <30 mg/L (95% removal). Using a one-chambered MFC and pre-fermented wastewater, the maximum power density was 371+/-10 mW/m(2) (53.5+/-1.4 mA per liter of wastewater). These results suggest that it is feasible to link biological hydrogen production and electricity producing using MFCs in order to achieve both wastewater treatment and bioenergy production.     

Using filtrate of waste biosolids to effectively produce bio-hydrogen by anaerobic fermentation

Waste biosolids collected from sewage works is a biomass containing a vast amount of polysaccharides and proteins, and thus is considered a potential substrate for producing hydrogen using anaerobic fermentation. This work demonstrated, contrary to the common assumption, that the solids phase in waste activated biosolids presents extra nutrients for anaerobes; it in fact prohibits effective bio-hydrogen production. Using filtrate after removal of solids from biosolids produces more hydrogen than using the whole biosolids, with the former reaching a level an order of magnitude higher than the literature results.     

Enhanced hydrogen production from waste activated sludge by cascade utilization of organic matter in microbial electrolysis cells

Fermentative hydrogen production from waste activated sludge (WAS) has low H₂ yield because WAS contains limited amounts of carbohydrate suitable for use by hydrogen-producing bacteria. Here, augmentation of hydrogen production from WAS by microbial electrolysis cells (MECs) was implemented. H₂ yields of 3.89 ± 0.39 mg-H₂/g-DS (5.67 ± 0.61 mg-H₂/g-VSS) from raw WAS and 6.78 ± 0.94 mg-H₂/g-DS (15.08 ± 1.41 mg-H₂/g-VSS) from alkaline-pretreated WAS were obtained in the two-chamber MECs (TMECs). This was several times higher than yields obtained previously by fermentation. Single-chamber MECs (SMECs) with low internal resistance showed a H₂ production rate that 13 times that of TMECs with similar H₂ yield when alkaline-pretreated WAS was used. However, methanogenesis was detected after several batch cycles. A yield balance calculation revealed that carbohydrates were not the only substrates for electrohydrogenesis. Protein and its acidification products, such as volatile fatty acids are also responsible for a portion of H₂ generation in MEC. Characterization of WAS in TMECs by three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy with parallel factor analysis indicated that electrohydrogenesis reacted on the extracellular polymeric substances and intracellular substances of WAS. Cascade utilization of organic matter in MECs increased hydrogen production from WAS. MECs showed high hydrogen yield from WAS, fewer H₂ sinks, and insensitivity to temperature. Optimizing MEC configurations and operation conditions and improving the pretreatment processes of WAS are necessary before practical application can take place on a large scale.     

Biological hydrogen production by Clostridium acetobutylicum in an unsaturated flow reactor

A mesophilic unsaturated flow (trickle bed) reactor was designed and tested for H2 production via fermentation of glucose. The reactor consisted of a column packed with glass beads and inoculated with a pure culture (Clostridium acetobutylicum ATCC 824). A defined medium containing glucose was fed at a flow rate of 1.6 mL/min (0.096 L/h) into the capped reactor, producing a hydraulic retention time of 2.1 min. Gas-phase H2 concentrations were constant, averaging 74 +/- 3% for all conditions tested. H2 production rates increased from 89 to 220 mL/hL of reactor when influent glucose concentrations were varied from 1.0 to 10.5 g/L. Specific H2 production rate ranged from 680 to 1270 mL/g glucose per liter of reactor (total volume). The H2 yield was 15-27%, based on a theoretical limit by fermentation of 4 moles of H2 from 1 mole of glucose. The major fermentation by-products in the liquid effluent were acetate and butyrate. The reactor rapidly (within 60-72 h) became clogged with biomass, requiring manual cleaning of the system. In order to make long-term operation of the reactor feasible, biofilm accumulation in the reactor will need to be controlled through some process such as backwashing. These tests using an unsaturated flow reactor demonstrate the feasibility of the process to produce high H2 gas concentrations in a trickle-bed type of reactor. A likely application of this reactor technology could be H2 gas recovery from pre-treatment of high carbohydrate-containing wastewaters.     

Dynamics of nematodes in a high organic loading rotating biological contactors

Nematode diversity and dynamics of a full-scale rotating biological contactor plant (RBC) has been studied. Analysis of biofilm composition showed a well-established zoning of microfauna among the three RBC sections analysed. Nematodes appeared to be the dominant group within the larger microfauna populations with average abundances between 200 and 300ind/mg or 8000 and 17000ind/cm(2). The most abundant nematode species were Diplogasteritus nudicapitatus and Paroigolaimella coprophages and, to a lesser extent, Paroigolaimella bernensis and Steinernema intermedia. The relationship between nematodes and filamentous bacteria (specifically the genus Beggiatoa) was the most significant biotic relationship found, and to a lesser extent, nematodes with ciliates. The relationship between the abundance of nematode species and the physical-chemical variables suggests that nematodes may be good indicators of low pollutant load levels in the entry of the RBC system. Finally, the results indicate that nematodes may have a relevant role for a good biofilm development.     

A pseudo-stoichiometric dynamic model of anaerobic hydrogen production from molasses

Despite many mathematical models available in the literature for simulation and optimization of anaerobic digestion processes, only few can accurately account for hydrogen production. In the present study, experiments were performed in a continuous stirred tank reactor with a hydraulic retention time close to 6 h. pH was regulated to 5.5 and agitation was maintained at 300 rpm. Molasses were used as substrate with feeding concentrations varying between 5 and 20 g L(-1). Experimental data were used to estimate the pseudo-stoichiometric coefficients with a constrained nonlinear optimization. The obtained pseudo-stoichiometric matrix is made of two reactions, one being associated with hydrogen production and the other one with acetate production. Finally, a dynamic model is derived and is demonstrated to simulate very accurately the dynamic evolution of hydrogen production, but also biomass and intermediate compounds (i.e., individual volatile fatty acids) concentrations while being very close to the stoichiometric balance. Finally, the best hydrogen production was [Formula: see text] for a concentration of substrate of 20.09 g L(-1) and a liquid feed flow of 5 L d(-1) (i.e., 1.47 mol-H2 mol-glucose(-1)).     

Alcohol production through volatile fatty acids reduction with hydrogen as electron donor by mixed cultures

In this research we demonstrated a new method to produce alcohols. It was experimentally feasible to produce ethanol, propanol and butanol from solely volatile fatty acids (VFAs) with hydrogen as electron donor. In batch tests, VFAs such as acetic, propionic and butyric acids were reduced by mixed microbial cultures with a headspace of 1.5 bar of hydrogen. Observed alcohol concentrations were 3.69 ± 0.25 mM of ethanol, 8.08 ± 0.85 mM of propanol and 3.66 ± 0.05 mM of n-butanol. The conversion efficiency based on the electron balance was 55.1 ± 5.6% with acetate as substrate, 50.3 ± 4.7% with propionate and 46.7 ± 2.2% with n-butyrate. Methane was the most predominant by-product in each batch experiment, 33.6 ± 9.6% of VFA and hydrogen was converted to methane with acetate as substrate; which was 27.1 ± 7.1% with propionate and 36.6 ± 2.2% with n-butyrate. This VFAs reducing renewable fuel production process does not require carbohydrates like fermentable sugars, but uses biomass with high water content or low sugar content that is unsuitable as feedstock for current fermentation processes. This so-called low-grade biomass is abundantly present in many agricultural areas and is economically very attractive feedstock for the production of biofuels.     

Altering protein conformation to improve fermentative hydrogen production from protein wastewater

One important reason for low hydrogen production from protein wastewater is due to the native folded conformation of protein. In this study the enhancement of bio-hydrogen production from protein wastewater by altering protein conformation via pretreatment was reported. Firstly, the effect of different pretreatment methods (acid, alkali, heat, and ultraviolet) on hydrogen production from synthetic protein wastewater was compared. The hydrogen production from the ultraviolet pretreated wastewater was 111.3 mL/g-protein, which was 3.79-, 3.73-, 3.54-, and 1.36-fold of that from the unpretreated (blank), acid, alkali, and heat pretreated wastewater, respectively. Then, the reasons for ultraviolet pretreatment showing significantly higher hydrogen production than other pretreatments were investigated. It was found that all pretreatments did not cause the cleavage of peptide bond, but the ultraviolet one caused much greater damage of hydrogen bonding networks and unfolding of protein. Thus, during anaerobic fermentation much higher protease activity and protein utilization were observed, which resulted in the bio-hydrogen production being remarkably improved. Further studies indicated that the photo-oxidization of aromatic residues in protein was not the reason for ultraviolet pretreatment remarkably improving bio-hydrogen production. Finally, the application of ultraviolet pretreatment to enhance hydrogen production from real protein wastewater was testified.     

Extracellular biological organic matters in sewage sludge during mesophilic digestion at reduced hydraulic retention time

To operate an anaerobic digester at low hydraulic retention time (HRT) is welcome in practice. This study characterized the extracellular biological organic matter (EBOM) and supernatant organics for a sewage sludge digested in a lab-scale mesophilic digester (5 l) running at an HRT of 20, 15 or 10 d. The hydrophilic and hydrophobic acid fractions were the principal components in the sludge EBOM. The hydrolysis rates for hydrophobic acid fraction related EBOM at 10 d HRT and that of hydrophilic fraction related proteins in supernatant at 20 d HRT limited the anaerobic processes. Improved hydrolysis of soluble hydrophilic fraction assisted improving digester performance at 20 d HRT. To shorten digestion HRT, efficiency of hydrophobic acid fraction hydrolysis has to be practiced.     

Zero-valent iron reduction of nitrate in the presence of ultraviolet light,organic matter and hydrogen peroxide

This paper describes the use of metallic iron (Fe(0)) powder for nitrate removal in a well-mixed batch reactor. Important variables explored include Fe(0) dosage (1-3g/L), UV light intensity (64-128 W), and the presence of propanol (20 mg/L as DOC) and H(2)O(2) (100-200 mg/L). Accumulation of ferrous ions released from the Fe(0) surface can be expressed by an S-curve, which involves lag growth phase, exponential phase, rate-declining phase, and saturation phase. The removal of nitrate increases with increasing Fe(0) dosage; however, the removal makes no difference as the Fe(0) dosage is greater than 2 g/L. UV irradiation retards the dissolution of ferrous ion and the removal of nitrate. The species of propanol, which has a functional group of -OH, plays a role of organic inhibitor for Fe(0) corrosion. The presence of H(2)O(2) appears to inactivate all reactions as the Fe(0) of 10 microm was used; the final H(2)O(2) remains intact throughout the entire reaction period, and there were no removal of nitrate and no dissolution of ferrous ion. Surprisingly, with the use of a larger Fe(0) particle size of 150 microm, the H(2)O(2) was seen to decompose rapidly through Fenton reaction. Nevertheless, the rate of ferrous accumulation or nitrate removal is slow.     

Hydrogen-dependent denitrification of water in an anaerobic submerged membrane bioreactor coupled with a novel hydrogen delivery system

Hydrogen-dependent denitrification has gained significant attention due to its potential economic advantage over heterotrophic denitrification. However, effective hydrogen delivery and biomass retention under anaerobic conditions are significant challenges to implementation of this process. An innovative hydrogenotrophic denitrification system, that addresses these challenges, consisting of an anaerobic submerged membrane bioreactor (MBR) and a novel hydrogen delivery unit, was evaluated for removal of nitrate from a synthetic groundwater feed. The hydrogen delivery unit was designed to release hydrogen-supersaturated water to the reactor and was efficient in hydrogen delivery, providing complete mass transfer. The anaerobic submerged MBR was successful in both reducing nitrate from 25 mg NO(3)-Nl(-1) to below detection and separating biomass from treated water to produce effluent free of suspended solids. Nitrogen gas produced during denitrification was internally recycled to effectively achieve membrane scouring and reactor mixing. The total organic carbon was similar to that of the incoming feed water, averaging approximately 6 mgl(-1).     

Enrichment of anaerobic polychlorinated biphenyl dechlorinators from sediment with iron as a hydrogen source

Little is known about anaerobic polychlorinated biphenyl (PCB) dechlorination, although it is believed that some microorganisms are capable of respiring PCBs, gaining energy for growth from PCB dechlorination. If this is the case, the amendment of appropriate electron donors to contaminated sediment should stimulate dechlorination. The effect of elemental iron (Fe0) addition, an easily amended electron donor, on the microbial dechlorination of the PCB congeners 3,4,5-trichlorobiphenyl (3,4,5-CB) and 2,2',3,4,4',5,5'-heptachlorobiphenyl (2,2',3,4,4',5,5'-CB) was investigated in microcosms containing estuarine sediment from Baltimore Harbor. Results showed that the addition of 0.1 g Fe0/g sediment reduced the lag time for removal of doubly flanked para chlorines by approximately 100 days. Because Fe0 is a source of cathodic hydrogen (H2), the effect of direct H2 addition to sediment microcosms was also tested. The addition of 0.001 atm H2 in the headspace generated the same dechlorination activity and reduction in lag time as the addition of 0.1g Fe0/g. Higher concentrations of Fe0 or H2 increased the lag prior to dechlorination. Additional results showed that an alkaline pH (> or = 7.5), high [Fe2+] (3.3 g/L), or HS- (0.1 mg/L total sulfide) inhibited dechlorination. Elevated concentrations of Fe2+, OH-, and HS- are products of Fe0 oxidation or increased microbial activity (methanogenesis, homoacetogenesis, and sulfate reduction), both of which would result from the amendment of large quantities of Fe0 or H2 to sediment. This research shows that not only can PCB dechlorination be stimulated through the addition of electron donor, but implies that the dechlorinators are enriched by the continuous addition of low concentrations of H2, similar to other known dechlorinators, such as the dehalorespirer Dehalococcoides ethenogenes. These results suggest that the direct addition of controlled amounts of Fe0 to sediments may be an effective remediation tool to reduce the lag period prior to dechlorination at PCB-impacted sites. They also suggest that PCB dechlorinators may be enriched using techniques similar to those used with known dehalorespirers.     

Degradation of phenolic compounds with hydrogen peroxide catalyzed by enzyme from Serratia marcescens AB 90027

In this paper, the degradation of phenolic compounds using hydrogen peroxide as oxidizer and the enzyme extract from Serratia marcescens AB 90027 as catalyst was reported. With such an enzyme/H2O2 combination treatment, a high chemical oxygen demand (COD) removal efficiency was achieved, e.g., degradation of hydroquinone exceeded 96%. From UV-visible and IR spectra, the degradation mechanisms were judged as a process of phenyl ring cleavage. HPLC analysis shows that in the degradation p-benzoquinone, maleic acid and oxalic acid were formed as intermediates and that they were ultimately converted to CO2 and H2O. With the enzyme/H2O2 treatment, vanillin, hydroquinone, catechol, o-aminophenol, p-aminophenol, phloroglucinol and p-hydroxybenzaldehyde were readily degraded, whereas the degradation of phenol, salicylic acid, resorcinol, p-cholorophenol and p-nitrophenol were limited. Their degradability was closely related to the properties and positions of their side chain groups. Electron-donating groups, such as -OH, -NH2 and -OCH3 enhanced the degradation, whereas electron-withdrawing groups, such as -NO2, -Cl and -COOH, had a negative effect on the degradation of these compounds in the presence of enzyme/H2O2. Compounds with -OH at ortho and para positions were more readily degraded than those with -OH at meta positions.     

The effects of organic toxicants on methane production and hydrogen gas levels during the anaerobic digestion of waste activated sludge

Batch serum bottle assays were conducted to examine the response of the anaerobic digestion process to inhibition induced by the pulse addition of four organic toxicants [chloroform, bromoethanesulfonic acid (BES), trichloroacetic acid (TCAA) and formaldehyde]. The impact that increasing levels of inhibition of methane production had on hydrogen response and volatile fatty acid (VFA) accumulation were examined. All of the toxicants, with the exception of formaldehyde, appeared to elicit similar hydrogen response patterns and VFA accumulations for similar levels of inhibition. Results indicate that both the hydrogen and acetate catabolizing methanogenic populations were inhibited to approximately the same extent by chloroform, BES, and TCAA. Severe inhibition of methane production (>70% reduction of methane produced compared to controls) resulted in a rapid accumulation of hydrogen in the gaseous headspace. When inhibition was less severe, hydrogen accumulated to levels only slightly above controls. Based on these preliminary results, there appears to be some limits on the potential of using hydrogen as an early warning indicator of process upset. Results do indicate, however, that monitoring hydrogen in consert with conventional process indicators should improve digester monitoring and may provide more rapid indication of process upsets due to toxic shocks.     

Oxidation kinetics of two pesticides in natural waters by ozonation and ozone combined with hydrogen peroxide

The oxidation of bromoxynil and trifluralin was investigated using ozone (O₃) and O₃ combined with hydrogen peroxide (H₂O₂) in natural waters using batch reactors. The results indicated that these pesticides could not be completely degraded during ozonation, achieving degradation levels lower than 50%. An enhancement of the level of degradation was observed using O₃/H₂O₂ process. A biphasic behaviour of O₃ was also observed. Depending on the experimental conditions, the rate constant for O₃ decomposition was estimated to be between 7.4 × 10⁻⁴ s⁻¹ to 5.8 × 10⁻² s⁻¹, and 3.2 × 10⁻³ s⁻¹ to 4.2 × 10⁻² s⁻¹ for bromoxynil and trifluralin samples, respectively. Acute toxicity analysis performed using Microtox^® showed a decrease in the toxic effects of the samples on the luminescent bacteria during the first few minutes of treatment, followed by an increase of the toxic effects at the end of the reaction for both pesticides. The quantification of oxidation by-products generated during treatment was also addressed. The total molar balances of the degradation by-products versus the initial pesticide concentrations ranged from 60 to 103% under different experimental conditions.     

The photocatalytic degradation of dicamba in TiO2 suspensions with the help of hydrogen peroxide by different near UV irradiations

The direct photolysis and the photocatalytic degradations of dicamba in TiO2 suspensions with and without the use of hydrogen peroxide were studied using two different monochromatic UV irradiations (300 and 350 nm). Both the direct photolysis and photocatalytic degradations of dicamba follow pseudo-first-order decay kinetics. Photolysis reactions were slow but the corresponding photocatalysis rates were increased by about 3 and 5 times in the presence of TiO2 at 300 and 350 nm of UV, respectively. Photocatalytic rates were increased with the pH at acidic to neutral ranges because of the increase of hydroxide ions, but the reaction was gradually retarded at the alkaline medium due to the effect of charges repulsion. The different proton sources causing various degrees of rate retardation were due to the presence of the corresponding counter anions. The results of H2O2-assisted photocatalysis experiments showed that a low H2O2 dosage in photocatalysis using UV 300 nm would enhance the decay rate of dicamba by 2.4 times, but an overdose of H2O2 will retard the rate because of the expenditure of hydroxyl radicals. However, this process was found impracticable at UV 350 nm due to the absorption characteristic of H2O2. A neutral initial pH level was found to favour the H2O2-assisted photocatalysis at UV 300 nm. The reactions were highly retarded at the alkaline medium due to the unstable properties of H2O2.     

Preliminary trial on degradation of waste activated sludge and simultaneous hydrogen production in a newly-developed solar photocatalytic reactor with AgX/TiO2-coated glass tubes

A solar fluidized tubular photocatalytic reactor (SFTPR) with simple and efficient light collector was developed to degrade waste activated sludge (WAS) and simultaneously produce hydrogen. The photocatalyst was a TiO₂ film doped by silver and silver compounds (AgX). The synthesized photocatalyst, AgX/TiO₂, exhibited higher photocatalytic activity than TiO₂ (99.5% and 30.6% of methyl orange removal, respectively). The installation of light collector could increase light intensity by 26%. For WAS treatment using the SFTPR, 69.1% of chemical oxygen demand (COD) removal and 7866.7 μmol H₂/l-sludge of hydrogen production were achieved after solar photocatalysis for 72 h. The SFTPR could be a promising photocatalysis reactor to effectively degrade WAS with simultaneous hydrogen production. The results can also provide a useful base and reference for the application of photocatalysis on WAS degradation in practice.     

Selective suppression of harmful cyanobacteria in an entire lake with hydrogen peroxide

Although harmful cyanobacteria form a major threat to water quality, few methods exist for the rapid suppression of cyanobacterial blooms. Since laboratory studies indicated that cyanobacteria are more sensitive to hydrogen peroxide (H₂O₂) than eukaryotic phytoplankton, we tested the application of H₂O₂ in natural waters. First, we exposed water samples from a recreational lake dominated by the toxic cyanobacterium Planktothrix agardhii to dilute H₂O₂. This reduced the photosynthetic vitality by more than 70% within a few hours. Next, we installed experimental enclosures in the lake, which revealed that H₂O₂ selectively killed the cyanobacteria without major impacts on eukaryotic phytoplankton, zooplankton, or macrofauna. Based on these tests, we introduced 2 mg L⁻¹ (60 μM) of H₂O₂ homogeneously into the entire water volume of the lake with a special dispersal device, called the water harrow. The cyanobacterial population as well as the microcystin concentration collapsed by 99% within a few days. Eukaryotic phytoplankton (including green algae, cryptophytes, chrysophytes and diatoms), zooplankton and macrofauna remained largely unaffected. Following the treatment, cyanobacterial abundances remained low for 7 weeks. Based on these results, we propose the use of dilute H₂O₂ for the selective elimination of harmful cyanobacteria from recreational lakes and drinking water reservoirs, especially when immediate action is urgent and/or cyanobacterial control by reduction of eutrophication is currently not feasible. A key advantage of this method is that the added H₂O₂ degrades to water and oxygen within a few days, and thus leaves no long-term chemical traces in the environment.     

Monitoring organic loading to swimming pools by fluorescence excitation-emission matrix with parallel factor analysis (PARAFAC)

Fluorescence Excitation-Emission Matrix spectroscopy combined with parallel factor analysis was employed to monitor water quality and organic contamination in swimming pools. The fluorescence signal of the swimming pool organic matter was low but increased slightly through the day. The analysis revealed that the organic matter fluorescence was characterised by five different components, one of which was unique to swimming pool organic matter and one which was specific to organic contamination. The latter component had emission peaks at 420 nm and was found to be a sensitive indicator of organic loading in swimming pool water. The fluorescence at 420 nm gradually increased during opening hours and represented material accumulating through the day.