Effect of pH and oxalic acid on the reduction of Fe(3+) by a biomimetic chelator and on Fe(3+) desorption/adsorption onto wood: Implications for brown-rot decay

Fenton reaction is thought to play an important role in wood degradation by brown-rot fungi. In this context, the effect of oxalic acid and pH on iron reduction by a biomimetic fungal chelator and on the adsorption/desorption of iron to/from wood was investigated. The results presented in this work indicate that at pH 2.0 and 4.5 and in the presence of oxalic acid, the phenolate chelator 2,3-dihydroxybenzoic acid (2,3-DHBA) is capable of reducing ferric iron only when the iron is complexed with oxalate to form Fe mono-oxalate (Fe(C(2)O(4))(+)). Within the pH range tested in this work, this complex formation occurs when the oxalate:Fe(3+) molar ratio is less than 20 (pH 2.0) or less than 10 (pH 4.5). When aqueous ferric iron was passed through a column packed with milled red spruce (Picea rubens) wood equilibrated at pH 2.0 and 4.5. it was observed that ferric iron binds to wood at pH 4.5 but not at pH 2.0, and the bound iron could then be released by application of oxalic acid at pH 4.5. The release of bound iron was dependent on the amount of oxalic acid applied in the column. When the amount of oxalate was at least 20-fold greater than the amount of iron bound to the wood, all bound iron was released. When Fe-oxalate complexes were applied to the milled wood column equilibrated in the pH range of 2-4.5, iron from Fe-oxalate complexes was bound to the wood only when the pH was 3.6 or higher and the oxalate:Fe(3+) molar ratio was less than 10. When 2,3-DHBA was evaluated for its ability to release iron bound to the milled wood, it was found that 2,3-DHBA possessed a greater affinity for ferric iron than the wood as 2,3-DHBA was capable of releasing the ferric iron bound to the wood in the pH range 3.6-5.5. These results further the understanding of the mechanisms employed by brown-rot fungi in wood biodegradation processes. (C) 2009 Elsevier Ltd. All rights reserved.

Aqueous two-phase extraction using thermoseparating copolymer: a new system for phenolic compounds removal from hemicelullosic hydrolysate

BACKGROUND: The hydrolysis of hemicellulosic material can provide liquor with high xylose concentration (which can be used as a fermentation medium) and phenolic compounds (Phs), potentially immunostimulating compounds. However, these hydrolysates must be detoxified in order to remove the Phs that can act as inhibitors in bioconversions. RESULTS: Aqueous two-phase systems composed of thermoseparating copolymers were used for rice straw hydrolysate detoxification. The hydrolysis process was able to promote chemical breakdown of 85% of the total hemicellulose content, 14% of the cellulose, and 2% of the lignin. The hydrolysate obtained contained 19.7 g L-1 of xylose and several phenolic compounds, such as vanillin, vanillic acid, ferullic acid, etc. The phenolics extraction was studied as a function of copolymer molar mass (1100 g mol(-1), 2000 g mol(-1) and 2800 g mol(-1)), their percentages (from 5% to 50%) and Phs initial concentration. Phenolic compounds extraction of around 80% was obtained under the following conditions: 20% (w/w) and 35% (w/w) copolymer 1100 g mol-1, 35% (w/w) copolymer 2000 g mol(-1) and 35% (w/w) copolymer 2800 g mol(-1) at 25 degrees C. CONCLUSIONS: The results demonstrated the viability of this method for the removal of Phs from rice straw hydrolysate, which has potential uses in bioconversion processes. (c) 2007 Society of Chemical Industry.

Effects of sulfur additive EP in ester coolants during friction with CBN

A study was undertaken to investigate the effects of the EP additives during tribological tests using a CBN tool against steel. Ester oil with and without sulfur additive were used as lubricants in a tribometer. Tribochemical interactions between the S additive and steel have been investigated under boundary lubrication conditions by SEM and EDX analysis. The relative abundance of different elements on the surface of the CBN tools, which are present in the workpiece material such as Fe (iron) and Cr (chromium), suggests that adhesion occurred when the ester oil without sulfur additive was tested. Tribochemical interactions between the additive and the steel could be observed when using the ester oil containing the sulfur additive. These interactions contribute to the formation of a uniform layer on the CBN tool. This layer is composed by S (sulfur), Fe, and O (oxygen). The presence of these elements indicate that FeO (iron oxide) and FeS (iron sulfide) were formed.

Influence of feed time and sulfate load on the organic and sulfate removal in an ASBR

The removal of sulfate and organic matter was assessed in an ASBR, which treated wastewater containing 500 mg COD L(-1) (3 g COD L(-1) d(-1)) in 8 h-cycles at 30 degrees C. The wastewater was enriched with sulfate at [COD/SO(4)(2-]) ratios of 1.34, 0.67 and 0.34 (8.8,4.5 and 2.2 gSO(4)(2-) L(-1) d(-1)). For each COD/[SO(4)(2-)] ratio fill times used were: 10 min (batch), 3 and 6 h (fed-batch), achieving sulfate reduction of 30%, 72% and 72% (COD/[SO(4)(2-)] of 1.34); 25%, 58% and 55% (COD/[SO(4)(2-)] of 0.67) and 23%, 37% and 27% (COD/[SO(4)(2-)] of 0.34), respectively, and organic matter removal of 87%, 68% and 80% (COD/[SO(4)(2-)] of 1.34); 78%, 75% and 69% (COD/[SO(4)(2-)] of 0.67) and 85%, 84% and 83% (COD/[SO(4)(2-)] of 0.34), respectively. The results showed that fed-batch operation improved sulfate reduction, whereas organic matter removals were similar for batch and fed-batch operation. In addition, increase in sulfate loading in the fed-batch operation improved organic matter removal. (C) 2010 Elsevier Ltd. All rights reserved.

Performance evaluation of packing materials in the removal of hydrogen sulphide in gas-phase biofilters: Polyurethane foam, sugarcane bagasse, and coconut fibre

The main objective of this work was to investigate three packing materials (polyurethane foam, sugar-cane bagasse, and coconut fibre) for biofiltration of a gaseous mixture containing hydrogen sulphide (H(2)S). Mixed cultures were obtained from two sources, aerated submerged biofilters and activated sludge, and were utilised as inoculums. Biofilters reached 100% removal efficiency after two clays of operation. The empty bed residence time was 495 for each of the biofilters. The reactors were operated simultaneously, and the inlet concentrations of H(2)S varied between 184 and 644 ppmv during the long-term continuous operation of the biofilters (100 clays). Average removal efficiencies remained above 99.3%, taking into consideration the entire period of operation. Average elimination capacities reached by the biofilters packed with polyurethane foam, coconut fibre, and sugarcane bagasse were in the range of 17.8-66.6; 18.9-68.8, and 18.7-72.9g m(-3) h(-1), respectively. Finally, we concluded that the packing materials tested in this work are appropriate for the long-term biofiltration of hydrogen sulphide. (C) 2010 Elsevier B.V. All rights reserved.

Microbial processes and bacterial populations associated to anaerobic treatment of sulfate-rich wastewater

A pilot-scale (1.2 m(3)) anaerobic sequencing batch biofilm reactor (ASBBR) containing mineral coal for biomass attachment was fed with sulfate-rich wastewater at increasing sulfate concentrations. Ethanol was used as the main organic source. Tested COD/sulfate ratios were of 1.8 and 1.5 for sulfate loading rates of 0.65-1.90 kgSO(4)(2-)/cycle (48 h-cycle) or of 1.0 in the trial with 3.0 gSO(4)(2-) l(-1). Sulfate removal efficiencies observed in all trials were as high as 99%. Molecular inventories indicated a shift on the microbial composition and a decrease on species diversity with the increase of sulfate concentration. Beta-proteobacteria species affiliated with Aminomonas spp. and Thermanaerovibrio spp. predominated at 1.0 gSO(4)(2-) l(-1). At higher sulfate concentrations the predominant bacterial group was Delta-proteobacteria mainly Desulfovibrio spp. and Desulfomicrobium spp. at 2.0 gSO(4)(2-) l(-1), whereas Desulfurella spp. and Coprothermobacter spp. predominated at 3.0 gSO(4)(2-) l(-1). These organisms have been commonly associated with sulfate reduction producing acetate, sulfide and sulfur. Methanogenic archaea(Methanosaeta spp.)was found at 1.0 and 2.0 gSO(4)(2-) l(-1). Additionally, a simplified mathematical model was used to infer on metabolic pathways of the biomass involved in sulfate reduction. (C) 2009 Elsevier Ltd. All rights reserved.

A novel aerobic-anoxic biological filter for nitrogen removal from UASB effluent using biogas compounds as electron donors for denitrification

The performance of a new trickling filter (TF) configuration composed of an upper compartment for nitrification and a lower compartment for denitrification of effluent from a UASB reactor treating domestic sewage was evaluated. The TF was packed with new plastic material characterized by its durability and high percentage of void spaces. The feasibility of using the reduced compounds present in the biogas produced by a UASB reactor as electron donor for denitrification was also evaluated. Efficient nitrification and denitrification was achieved for the mean hydraulic (5.6 m(3) m(-2) d(-1)) organic (0.26 kg COD m(-3) d(-1)) and ammonia-N (0.08 kg m(-3) d(-1)) loading rates applied, resulting in ammonia-N removal ranging from 60 to 74%. The final effluent presented ammonia-N lower than 13 mg L(-1). Despite the presence of dissolved oxygen (DO) in the denitrification compartment, its performance was considered quite satisfactory and final nitrate concentrations were lower than 10 mg L(-1). The results indicate that methane was the main electron donor used for denitrification. Additionally, denitrification can probably be improved by avoiding high DO concentration in the denitrification compartment and by enhancing biogas transfer in the anoxic zone.

Nitrogen removal in a sequencing batch biofilm reactor with liquid circulation: Effect of feed strategy and carbon source in the denitrifying step

Ammonium nitrogen removal from a synthetic wastewater by nitrification and denitrification processes were performed in a sequencing batch biofilm reactor containing immobilized biomass on polyurethane foam with circulation of the liquid-phase. It was analyzed the effect of four external carbon sources (ethanol, acetate, carbon synthetic medium and methanol) acting as electron donors in the denitrifying process. The experiments were conducted with intermittent aeration and operated at 30+/-1 degrees C in 8-h cycles. The synthetic wastewater (100 mgCOD/L and 50 mgNH(4)(+)-N/L) was added batch-wise, while the external carbon sources were added fed-batch-wise during the periods where aeration was suspended. Ammonium nitrogen removal efficiencies obtained were 95.7, 94.3 and 97.5% for ethanol, acetate and carbon synthetic medium, respectively. As to nitrite, nitrate and ammonium nitrogen effluent concentrations, the results obtained were, respectively: 0.1, 5.7 and 1.4 mg/L for ethanol; 0.2, 4.1 and 1.8 mg/L for acetate and 0.2, 6.7 and 0.8 for carbon synthetic medium. On the other hand using methanol, even at low concentrations (50% of the stoichiometric value calculated for complete denitrification), resulted in increasing accumulation of nitrate and ammonium nitrogen in the effluent over time.

Toxicity and recalcitrant compound removal from bleaching pulp plant effluents by an integrated system: anaerobic packed-bed bioreactor and ozone

Effluents originated in cellulose pulp manufacturing processes are usually toxic and recalcitrant, specially the bleaching effluents, which exhibit high contents of aromatic compounds (e.g. residual lignin derivates). Although biological processes are normally used, their efficiency for the removal of toxic lignin derivates is low. The toxicity and recalcitrance of a bleached Kraft pulp mill were assessed through bioassays and ultraviolet absorption measurements, i.e. acid soluble lignin (ASL), UV(280), and specific ultraviolet absorption (SUVA), before and after treatment by an integrated system comprised of an anaerobic packed-bed bioreactor and oxidation step with ozone. Furthermore, adsorbable organic halides (AOX) were measured. The results demonstrated not only that the toxic recalcitrant compounds can be removed successfully using integrated system, but also the ultraviolet absorption measurements can be an interesting control-parameter in a wastewater treatment.

Pentachlorophenol (PCP) dechlorination in horizontal-flow anaerobic immobilized biomass (HAIB) reactors

This study verifies the potential applicability of horizontal-flow anaerobic immobilized biomass (HAIB) reactors to pentachlorophenol (PCP) dechlorination. Two bench-scale HAIB reactors (R1 and R2) were filled with cubic polyurethane foam matrices containing immobilized anaerobic sludge. The reactors were then continuously fed with synthetic wastewater consisting of PCP, glucose, acetic acid, and formic acid as co-substrates for PCP anaerobic degradation. Before being immobilized in polyurethane foam matrices, the biomass was exposed to wastewater containing PCP in reactors fed at a semi-continuous rate of 2.0 mu g PCP g(-1) VS. The applied PCP loading rate was increased from 0.05 to 2.59 mg PCP l(-1) day(-1) for RI, and from 0.06 to 4.15 mg PCP l(-1) day(-1) for R2. The organic loading rates (OLR) were 1.1 and 1.7 kg COD m(-3) day(-1) at hydraulic retention times (HRT) of 24 h for R1 and 18 In for R2. Under such conditions, chemical oxygen demand (COD) removal efficiencies of up to 98% were achieved in the HAIB reactors. Both reactors exhibited the ability to remove 97% of the loaded PCP. Dichlorophenol (DCP) was the primary chlorophenol detected in the effluent. The adsorption of PCP and metabolites formed during PCP degradation in the packed bed was negligible for PCP removal efficiency. (C) 2009 Elsevier Ltd. All rights reserved.

An upflow fixed-bed anaerobic-aerobic reactor for removal of organic matter and nitrogen from L-lysine plant wastewater

This paper reports on the design of a new reactor configuration - an upflow fixed-bed combined anaerobic-aerobic reactor - can operate as a single treatment unit for the removal of nitrogen (approximate to 150 mg N/L) and organic matter (approximate to 1300 mg COD/L) from Lysine plant wastewater. L-Lysine, an essential amino acid for animal nutrition, is produced by fermentation from natural raw materials of agricultural origin, thus generating wastewater with high contents of organic matter and nitrogen. The best operational condition of the reactor was obtained with a hydraulic retention time of 35 h (21 h in the anaerobic zone and 14 h in the aerobic zone) and a recycling ratio (R) of 3.5. In this condition, the COD, total Kjeldahl nitrogen (TKN), and total nitrogen (TN) removal efficiencies were 97%, 96%, and 77%, respectively, with average effluent concentrations of 10 +/- 36 mg COD/L, 2 +/- 1 mg NH(4)(+)-N/L, 8 +/- 3 mg Org-N/L, 1 +/- 1 mg NH(2)(-)-N/L, and 26 +/- 23 mg NH(3)(-)-N/L.

Post-treatment of effluents from the sulfate reduction process by anaerobic sequencing batch biofilm reactors

The main objective of this research was to evaluate the potential use of a bench-scale anaerobic sequencing batch biofilm reactor (ASBBR) containing mineral coal as inert support for removal Of Sulfide and organic matter effluents from an ASBBR (1.2 m(3)) utilized for treatment of sulfate-rich wastewater. The cycle time was 48 h, including the steps of feeding (2 h), reaction with continuous liquid recirculation (44 h) and discharge (2 h). COD removal efficiency was up to 90% and the effluents total sulfide concentrations (H(2)S, HS(-), S(2-)) remained in the range of 1.5 to 7.5 mg.l(-1) during the 50 days of operation (25 cycles). The un-ionized Sulfide and ionized sulfides were converted by biological process to elemental sulfur (S(0)) under oxygen limited conditions. The results obtained in the bench-scale reactor were used to design an ASBBR in pilot scale for use in post-treatment to achieve the emission standards (sulfide and COD) for sulfate reduction. The pilot-scale reactor, with a total volume of 0.43 m(3), the COD and total sulfide removal achieved 88% and 57%, respectively, for a cycle time of 48 h (70 days of operation or 35 cycles).

Removal of ammonium via simultaneous nitrification-denitrification nitrite-shortcut in a single packed-bed batch reactor

A polyurethane packed-bed-biofilm sequential batch reactor was fed with synthetic substrate simulating the composition of UASB reactor effluents. Two distinct ammonia nitrogen concentrations (125 and 250 mg l(-1)) were supplied during two sequential long-term experiments of 160 days each (320 total). Cycles of 24 h under intermittent aeration for periods of 1 h were applied, and ethanol was added as a carbon source at the beginning of each anoxic period. Nitrite was the main oxidized nitrogen compound which accumulated only during the aerated phases of the batch cycle. A consistent decrease of nitrite concentration started always immediately after the interruption of oxygen supply and addition of the electron donor. Removal to below detection limits of all nitrogen soluble forms was always observed at the end of the 24 h cycles for both initial concentrations. Polyurethane packed-bed matrices and ethanol amendments conferred high process stability. Microbial investigation by cloning suggested that nitrification was carried out by Nitrosomonas-like species whereas denitrification was mediated by unclassified species commonly observed in denitrifying environments. The packed-bed batch bioreactor favored the simultaneous colonization of distinct microbial groups within the immobilized microbial biomass. The biofilm was capable of actively oxidizing ammonium and denitrification at high ratios in intermittent intervals within 24 h cycles. (c) 2008 Elsevier Ltd. All rights reserved.

Influence of support material on the immobilization of biomass for the degradation of linear alkylbenzene sulfonate in anaerobic reactors

Two horizontal-flow anaerobic immobilized biomass reactors (HAIB) were used to study the degradation of the LAS surfactant: one filled with charcoal (HAIB1) and the other with a mixed bed of expanded clay and polyurethane foam (HAIB2). The reactors were fed with synthetic substrate supplemented with 14 mg l(-1) of LAS, kept at 30 +/- 2 degrees C and operated with a hydraulic retention time (HRT) of 12 h. The surfactant was quantified by HPLC. Spatial variation analyses were done to quantify organic matter and LAS consumption along the reactor length. The presence of the surfactant in the load did not affect the removal of organic matter (COD), which was close to 90% in both reactors for an influent COD of 550 ring l(-1). The results of a mass balance indicated that 28% of all LAS added to HAIB1 was removed by degradation. HAIB2 presented 27% degradation. Molecular biology techniques revealed microorgan isms belonging the uncultured Holophaga sp., uncultured delta Proteobacterium, uncultured Verrucomicrobium sp., Bacteroides sp. and uncultured gamma Proteobacterium sp. The reactor with biomass immobilized on charcoal presented lower adsorption and a higher kinetic degradation coefficient. So, it was the most suitable support for LAS anaerobic treatment. (c) 2008 Elsevier Ltd. All rights reserved.

Temperature and feed strategy effects on sulfate and organic matter removal in an AnSBB

The objective of this work was to analyze the interaction effects between temperature, feed strategy and COD/[SO(4)(2-)] levels, maintaining the same ratio, on sulfate and organic matter removal efficiency from a synthetic wastewater. This work is thus a continuation of Archilha et al. (2010) who studied the effect of feed strategy at 30 degrees C using different COD/[SO] ratios and levels. A 3.7-L anaerobic sequencing batch reactor with recirculation of the liquid phase and which contained immobilized biomass on polyurethane foam (AnSBBR) was used to treat 2.0 L synthetic wastewater in 8 h cycles. The temperatures of 15, 22.5 and 30 degrees C with two feed strategies were assessed: (a) batch and (b) batch followed by fed-batch. In strategy (a) the reactor was fed in 10 min with 2 L wastewater containing sulfate and carbon sources. In strategy (b) 1.2 L wastewater (containing only the sulfate source) was fed during the first 10 min of the cycle and the remaining 0.8 L (containing only the carbon source) in 240 min. Based on COD/[SO(4)(2-)] = 1 and on the organic matter (0.5 and 1.5 gCOD/L) and sulfate (0.5 and 1.5 gSO(4)(2-)/L) concentrations, the sulfate and organic matter loading rates applied were 1.5 and 4.5 g/L.d, i.e., same COD/[SO(4)(2-)] ratio (=1) but different levels (1.5/1.5 and 4.5/4.5 gCOD/gSO(4)(2-)). When reactor feed was 1.5 gCOD/L.d and 1.5 gSO(4)(2-)/L.d, gradual feeding (strategy b) showed to favor sulfate and organic matter removal in the investigated temperature range, indicating improved utilization of the electron donor for sulfate reduction. Sulfate removal efficiencies were 87.9; 86.3 and 84.4%, and organic matter removal efficiencies 95.2; 86.5 and 80.8% at operation temperatures of 30; 22.5 and 15 degrees C, respectively. On the other hand, when feeding was 4.5 gCOD/L.d and 4.5 gSO(4)(2-)/L.d, gradual feeding did not favor sulfate removal, indicating that gradual feeding of the electron donor did not improve sulfate reduction. (C) 2011 Elsevier Ltd. All rights reserved.