Continuous anaerobic treatment of wastewater from a kraft pulp mill

A pilot-scale study of the thermophilic anaerobic digestion of high-strength wastewater (evaporator condensate, EC) discharged from a kraft pulp production process was performed. The system consisted of a microfiltration (MF) membrane module for oily substances removal, a stripping system using evolved gas from the digester for sulfur compounds removal, an anaerobic fixed-bed bioreactor for methane fermentation, and an ultrafiltration (UF) membrane module for retention of a high density of bacterial cells. The bioreactor had a fixed-bed with an effective volume of 5 m³ packed with pumice stone. In a continuous run with only the MF membrane module for oily substances removal, the digester efficiency declined because of methanogenic inhibition by sulfur compounds. After fitting of the stripping system which used evolved gas from the digester, the inhibitive sulfur compounds in the EC were removed more than 80%, and high-loading and high-efficiency operation could be attained. The BOD loading and BOD removal of 35.5 kg BOD/m³/d and 93%, respectively were attained. By anaerobic treatment of the evaporator condensate waste before the conventional aerobic activated sludge method, the total costs would be reduced to ¥3.31/m³ wastewater compared with ¥4.53/m³-wastewater by the aerobic activated sludge method only. The stability of digester performance against interruption by feed stoppage was also examined.     

Impact of bleached kraft pulp mill effluent on benthic community structure in relation to environmental factors

In this study, we assessed the impact of bleachedkraft pulp mill effluent (BKME) on the distributionand composition of benthic communities at JackfishBay, Lake Superior. Sediment samples were collectedfrom 44 stations from which several environmentalvariables (extractable organic chlorine [EOCl],metals, organic carbon, particle size, secchi depth,and water depth) and benthic community compositionwere determined. Relationships between environmentalvariables and benthic community structure wereassessed using canonical correspondence analysis(CCA). CCA revealed two distinct biological gradientsat Jackfish Bay, the first associated with degradedbottom sediments and nutrient enrichment and thesecond associated with water depth. Both gradientsrevealed three distinct regions at Jackfish Bay: 1) anarea of highly degraded sediments, located 300–1200 mbelow the outfall, 2) a small, mesotrophic (nutrientenriched) area adjacent to this zone, and 3) remainingareas of Jackfish Bay, including the internalreference sites in Tunnel Bay. Sediments in theimpaired region contained high concentrations oforganic matter (7–21% as loss on ignition [LOI]) andEOCl (up to 5200 mg/kg dw); together these variablesaccounted for 73% of the variation associated withthe first canonical axis of the CCA. This region wasdominated by the oligochaetes Tubifex tubifexand Limnodrilus hoffmeisteri (64–100% of thebenthic community). Sediments in the second regionwere characterized by an abundant and diverse benthiccommunity comprised of benthic harpacticoids,Chironomidae, and oligochaetes. Stations outside ofthese two regions were characterized by a benthiccommunity similar in composition to that expected foroligotrophic Lake Superior waters, including Diporiea sp., Stylodrilus heringianus, Mysis relicta, Sphaerium, Pisidium and benthicharpacticoids. Based on a Monte Carlo significancetest, benthic community structure was significantly(p = 0.01) related to the environmental variablescomprising the first axis of the CCA. Water depth wasthe most important explanatory variable associatedwith the second axis of the CCA; both taxa richnessand abundance declined significantly with increasingdepth. The comprehensive approach employed in thisstudy clearly delineated the occurrence and degree ofimpact on the benthic environment and may be useful infuture risk assessments of sites affected byanthropogenic activity.     

Effect of bleached kraft pulp mill effluent on hepatic biotransformation reactions in vendace (Coregonus albula L.)

1. The effect of bleached kraft pulp mill effluent (BKME) on xenobiotic biotransformation enzyme activities in the liver of vendace (Coregonus albula L.) was studied by exposing some fish in field laboratory tanks at 0, 0.1, 0.2 and 0.5% (v/v) effluent concentrations of BKME corresponding to 0-0.08 toxic units and others in clean water as controls. 2. Slight increase (57%, 68%) in polysubstrate monooxygenase enzyme activities, measured as benzo(a)pyrene hydroxylase and 7-ethoxycoumarin O-deethylase activities, was observed in a dose related manner after 70 days of exposure to 0.5% concentration of BKME. 3. Highest increase was observed at 0.2% effluent concentration after 120 days of exposure, measured as benzo(a)pyrene hydroxylase activity. 4. BKME had an affect on UDPglucuronosyltransferase, at the beginning (14-70 days) by decreasing and in longer exposure (120 days) by slightly increasing the activity.     

CP/MAS 13C NMR analysis of cellulase treated bleached softwood kraft pulp

Fully bleached softwood kraft pulps were hydrolyzed with cellulase (1,4-(1,3:1,4)-beta-D-glucan 4-glucano-hydrolase, EC 3.2.1.4) from Trichoderma reesei. Supra-molecular structural features of cellulose during enzymatic hydrolysis were examined by using CP/MAS 13C NMR spectra in combination with line-fitting analysis. Different types of cellulose allomorphs (cellulose I(alpha), cellulose I(beta), para-crystalline) and amorphous regions were hydrolyzed to a different extent by the enzyme used. Also observed was a rapid initial phase for hydrolysis of regions followed by a slow hydrolysis phase. Cellulose I(alpha), para-crystalline, and non-crystalline regions of cellulose are more susceptible to enzymatic hydrolysis than cellulose I(beta) during the initial phase. After the initial phase, all the regions are then similarly susceptible to enzymatic hydrolysis.     

Long-term development in a Baltic fish community exposed to bleached pulp mill effluent

Observations near a Swedish pulp mill at the Bothnian Sea during 1982-1992 revealed low fish abundance and a disturbed community structure. The presence of endocrine disrupting or toxic substances in effluent water was indicated by biomarker responses, impaired reproduction and stimulated growth in perch (Perca fluviatilis). In 1992 the bleaching process was altered and a secondary treatment system was installed, improving the quality and decreasing the amount of effluent. This paper presents the results of follow-up studies during 1995-1998 with the objective to analyse any recovery of the fish community due to changes in mill operations. Although abundance and diversity of the fish community did recover, an effect of enrichment, indicated by high catches of cyprinids, was still visible in the vicinity of the mill outlet. Sexual maturation was delayed, gonad development was retarded, average growth rate was faster, and the condition factor was higher in perch caught in the vicinity of the effluent outlet, than in perch captured elsewhere. It is concluded that substances inhibiting reproduction and causing growth disturbance were still present in the effluents in effective concentrations.     

In vitro genotoxic evaluation of conventional bleached and biobleached softwood pulp mill effluents

The effluents of pulp and paper mills contain about 300 different chemical compounds; many of them are mutagens and clastogens. Genotoxic studies have shown that chlorination stage liquors are significantly more genotoxic, in the Ames Salmonella assay, than the other process of lignin extraction, and that lyophilized effluents are genotoxic in cultured mammalian cells. Since these effluents from conventional bleaching stages are genotoxic, Chilean industries are interested in changing this process to a less toxic one, such as biobleaching using enzymes. In this study, we tested the in vitro genotoxicity of two types of effluents: an effluent obtained from a conventional radiata pine kraft-bleaching process (effluent D) and one derived from a biobleaching process with hemicellulase (effluent B). Both effluents were tested without any concentration or purification steps in the Ames Salmonella assay (TA100) and in the micronuclei (MN) and sister chromatid exchange (SCE) tests in CHO cells. The results showed that neither effluent induced base pair substitution mutations in the Ames Salmonella assay, and neither increased the micronucleus frequency in CHO cells. But, both increased the SCE frequencies in CHO cells, showing that this assay is more sensitive than the other ones, and that the two effluents contained chemical compounds in amounts enough to induce in vitro genotoxicity measured by the SCE induction.     

Nitrification,denitrification and biological phosphorus removal in piggery wastewater using a sequencing batch reactor

Nutrients in piggery wastewater with high organic matter, nitrogen (N) and phosphorus (P) content were biologically removed in a sequencing batch reactor (SBR) with anaerobic, aerobic and anoxic stages. The SBR was operated with 3 cycles/day, temperature 30 degrees C, sludge retention time (SRT) 1 day and hydraulic retention time (HRT) 11 days. With a wastewater containing 1500 mg/l ammonium and 144 mg/l phosphate, a removal efficiency of 99.7% for nitrogen and 97.3% for phosphate was obtained. Experiments set up to evaluate the effect of temperature on the process showed that it should be run at temperatures higher than 16 degrees C to obtain good removals (> 95%). Batch tests (ammonia utilization rate, nitrogen utilization rate and oxygen utilization rate) proved to be good tools to evaluate heterotrophic and autotrophic biomass activity. The SBR proved to be a very flexible tool, and was particularly suitable for the treatment of piggery wastewater, characterized by high nutrient content and by frequent changes in composition and therefore affecting process conditions.     

A comparison of organochlorine removal from bleached kraft pulp and paper-mill effluents by dehalogenating Pseudomonas,Ancylobacter and Methylobacterium strains

The relative importance of each of three dechlorinating species to overall organochlorine removal from bleached kraft-mill effluents (BKME) was assessed. Ancylobacter aquaticus A7, Pseudomonas P1, and Methylobacterium CP13, strains indigenous to a BKME treatment system, were tested for growth on chlorinated acetic acids and alcohols, and for adsorbable organic halogen (AOX) reduction in batch cultures of sterile BKME from three sources. A. aquaticus A7 exhibited the broadest substrate range, but could only affect significant AOX reduction in softwood effluents. Methylobacterium CP13 exhibited a limited substrate range, but was capable of removing significant amounts of AOX from both hardwood and softwood effluents. By contrast, Pseudomonas sp. P1 exhibited a limited substrate range and poor to negligible reductions in AOX levels from both effluent types. Mixed inocula of all three species combined and inocula of sludge from mill treatment systems removed as much AOX from softwood effluents as did pure populations of Methylobacterium CP13. When BKME was hydrolysed prior to AOX analysis, the subsequent estimates of recalcitrant, or non-hydrolysable, AOX levels were far less variable than their counterpart total AOX measures. It is suggested that this is a relevant and useful measure of AOX for biodegradation studies.     

A survey of the composition and diversity of bacterial populations in bleached kraft pulp-mill wastewater secondary treatment systems

Bacterial community compositions from 10 pulp- and paper-mill treatment systems were compared using both traditional and molecular techniques. 16S-RFLP (Random Fragment Length Polymorphisms) analysis was used to examine the genotypic profiles of the whole bacterial community of each treatment system. Although all the communities shared approximately 60% of their DNA band pattern, as determined by computer-assisted cluster analysis, each community displayed a unique profile that was stable over time under normal operating parameters. Reverse Sample Genome Probing (RSGP) and 16S-RFLP were used to compare the culturable bacterial communities of several geographically separated pulp-mill biotreatment system communities. There was little overlap in the composition of the culturable community between mills at the genus level. Furthermore, RSGP variation was almost as high within a mill as between mills. Partial sequences of the 16S rRNA genes from culturable isolates identified Bacillus spp., Pseudomonas spp., and Xanthobacter as some of the dominant species. Finally, several 16S rRNA genes from two whole community 16S RNA gene libraries were partially sequenced and identified as similar to unknown alpha-, beta-, and gamma-Proteobacteria, Ralstonia, Alcaligenes, Nitrospira, Firmicutes, and clones representing the new Holophaga/Acidobacterium phylum. These findings suggest that although these pulp- and paper-mill biotreatment communities perform similar functions, they are populated by unique mixtures of species.     

Molecular weight distribution of Pinus radiata kraft mill wastewater treated by anaerobic digestion

Kraft mill is responsible for massive discharge of highly polluted effluents. The main characteristics of this effluent are high toxicity and low biodegradability due to tannin, lignin and chlorophenol compounds. The composition may vary dramatically depending, for instance, on the utilised feedstock and process. The purpose of this work was to investigate the molecular weight distribution of Pinus radiata kraft pulping wastewater treated by anaerobic digestion by using two types of anaerobic reactors: fixed bed and sludge blanket. Anaerobic sludge blanket (UASB) and anaerobic filter (AF) were operated. In both reactors, the total alkalinity ranged between 1.0 and 1.5 g CaCO3/l, while the organic load rate (OLR) was increasing during operation from 1.2 to 3.3 gCOD/l d. COD and total phenolic compounds (UV215) removal ranged between 30-50% and 13-20%, respectively, while the BOD5 removal ranged 60-90%. However only a partial biodegradation (10-43%) of tannin and lignin was observed. Results from ultrafiltration analyses indicated that the fraction with a molecular weight (MW) < 1000, COD and colour decreased after anaerobic treatment, but the total phenolic compounds increased. In the 1000 < MW < 10,000 fraction, there was no change in COD, UV215 and colour. In the > 10,000 MW fraction, colour and COD fraction increased by 14% and 5%, respectively, after anaerobic treatment. It can be concluded from this study, that treatment with UASB or AF reactors is not enough, under the conditions tested, for a large COD removal from Pinus radiata wastewater.     

Operational factors and nutrient effects on activated sludge treatment of Pinus radiata kraft mill wastewater

The biodegradability of Pinus radiata bleached kraft mill wastewater by an activated sludge treatment during a period of 280 days was evaluated. The effect of varying hydraulic retention time (HRT) in the range of 48 to 4.5 h and nitrogen (N) and phosphorus (P) addition on removal of biological oxygen demand (BOD5), chemical oxygen demand (COD), suspended solids (TSS and VSS), total phenolic compounds, tannin and lignin and reduction of toxicity was investigated. Removal of BOD5 was higher than 90% when HRT varied from 16 to 6 h, but decreased when HRT was less than 6 h. Similar performance was observed for COD removal, which was about 60% when HRT was varied from 16 to 6 h. Removal of total phenolic compounds and tannin and lignin was seriously affected by HRT. N and P addition to maintaining a ratio of 100:5:0.3 provided optimal BOD5, COD and suspended solids removal when HRT varied from 16 to 7 h, and no toxicity (using Daphnia) was detected in the treated effluent. When HRT was less than 6 h, the system showed destabilisation and pH, COD, BOD5 and suspended solids removal decreased.     

Composting of pulp and paper mill fly ash with wastewater treatment sludge

Wastewater treatment sludge and power boiler fly ash were combined and composted in mixed and static windrows 50 m long, 4 m high and 6 m wide. Moisture content was maintained above 50%. The final compost had a pH of 8.5, contained high concentrations of specific nutrients, and an average C:N ratio of 43:1. All metal, PCB, chlorophenol and PAH concentrations were below levels stipulated by local regulations. Over the first 8 weeks of the composting period dioxin concentration decreased by 45% to 41 pg/g TEQ. Leachate tests indicated minimal (<0.1 mg/l Cu and Pb; <50 mg/l Na, P, and SO₄⁻²) leaching of contaminants from the composted material. Application of compost (8 cubic yards/acre) at a sod farm improved soil characteristics as measured by a number of parameters. The dioxin concentration in the final soil/compost mixture was 3 pg/g TEQ, allowing the soil/compost mixture to be classified as agricultural soil. It was concluded that composting produced an acceptable soil conditioner attractive for large volume users of inexpensive soil material (sod farms, golf courses, land reclamation sites).     

Microwave, ultrasonic and chemo-mechanical pretreatments for enhancing methane potential of pulp mill wastewater treatment sludge

Microwave (2450 MHz, 1250 W), ultrasonic (20 kHz, 400 W) and chemo-mechanical (MicroSludge® with 900 mg/L NaOH followed by 83,000 kPa) pretreatments were applied to pulp mill waste sludge to enhance methane production and reduce digester sludge retention time. The effects of four variables (microwave temperature in a range of 50-175 °C) and sonication time (15-90 min), sludge type (primary or secondary) and digester temperature (mesophilic and thermophilic) were investigated. Microwave pretreatment proved to be the most effective, increasing specific methane yields of WAS samples by 90% compared to controls after 21 days of mesophilic digestion. Sonication solubilized the sludge samples better, but resulted in soluble non-biodegradable compounds. Based on the laboratory scale data, MicroSludge® was found the least energy intensive pretreatment followed by sonication for 15 min alternative with net energy profits of 1366 and 386 kWh/tonne of total solids (TS), respectively. Pretreatment benefits were smaller for thermophilic digesters.     

Methane production using a bio-reactor packed with pumice stone on an evaporator condensate of a kraft pulp mill

When an evaporator condensate stream from a kraft pulp mill was treated by anaerobic methane fermentation, the stream could not ferment continuously. Therefore, after the raw evaporator condensate was treated by various procedures, the treated samples were tested in a batch fermentation system. There seemed to be an inhibitor, an oily material, and the evaporator condensate could be fermented easily, after removal of the oily material, in a bio-reactor packed with pumice stone. In continuous operation, the minimum hydraulic retention time was 0.64 days, the maximum volumetric BOD removal rate was 11.47 kg/m³/d, and the maximum gas production rate for the theoretical volume was 97%. The efficiency of a bio-reactor using pumice stone was studied. The pumice stone has a large number of connected pores. The major pore sizes are 20–100 μm. The cell density of the pumice stone used in the bio-reactor was 18–19 g per liter.     

Nitrification and simultaneous denitrification byAzospirillum brasilense 12S

Azospirillum brasilense, an associative diazotrophs from sorghum roots grows autotrophically on NH ₄ ⁺ and CaCO₃. NH ₄ ⁺ a is also oxidized to NO ₂ ^- and then denitrified. Addition of malate to the autotrophic medium enhances both NH ₄ ⁺ oxidation as well as NONH ₂ ^- dissimilation. The incomplete nitrification linked denitrification results in a rapid loss of nitrogen from the growth medium. The bacterium also shows assimilatory NO ₃ ^- and NO ₂ ^- reductases and fixes nitrogen at 50 μg N/ml of NH ₄ ⁺ NO ₃ ^- or NO ₂ ^-     

Activity of laccase on unbleached and bleached thermomechanical pulp

The introduction of value-added properties to pulp fibres is an attractive proposition. One interesting option is targeted modification of fibre surfaces by enzymatic activation. In this work, the activity of laccase on pulp and pulp fractions from thermomechanical pulp (TMP) and peroxide bleached TMP was studied on the basis of consumption of the co-substrate oxygen in the reaction and by studying the formation of radicals in the pulp material as analysed by electron paramagnetic resonance spectroscopy (EPR). Laccases obtained from Trametes hirsuta and Myceliophthora thermophila were used in the study. Laccases were found to be active on pulp material of unbleached TMP, whereas only fines from bleached TMP reacted in laccase treatment. Dissolved and colloidal substances (DCS) were assumed to have a mediating role in the laccase-catalysed oxidation of the fibre-bound material.     

Nitrification and denitrification by Thiosphaera pantotropha in aerobic chemostat cultures

Abstract: Thiosphaera pantotropha has been reported to denitrify aerobically and nitrify heterotrophically. However, recent evidence has indicated that these properties (particularly aerobic denitrification) have been lost. The occurrence and levels of aerobic denitrification and heterotrophic nitrification by T. pantotropha in chemostat cultures have therefore been re-evaluated. Only low nitrate reduction rates were observed: the apparent nitrogen loss was of the same order of magnitude as the combined error in the calculated nitrogen consumption. However, ¹⁵N mass spectrometry revealed low aerobic denitrification rates (about 10% of the rates originally published by this group). Heterotrophic nitrification rates were about a third of previous observations. N₂ and N₂O were both produced from NH₄⁺, NO₃⁻ and NO₂⁻. Periplasmic nitrate reductase was present in aerobically grown cells.     

Nitrification and denitrification in a system of reciprocating jet bioreactor

Concept of separation of stages coupled with novel design of reciprocating jet bioreactor have been incorporated in this research for the development of high efficiency treatment system for contaminated wastewaters.Evaluation of pilot plant data reveals that a three stage reciprocating jet bioreactor system could be effectively employed for nitrification and denitrification of highly polluted wastewater obtained from Berlin wastewater treatment plant. Such a system with COD destruction stage (residence time 1–3 hours) followed by nitrification stage (residence time 3–4.5 hours) and denitrification stage (residence time 0.3 hours) gives COD destruction rate upto 58 kg COD/(m³ day), nitrification rate upto 3.2 NH ₄ ⁺ -N/(m³ day) and denitrification rate upto 28 kg NO ₃ ^– -N/(m³ day) while providing COD, NH ₄ ⁺ -N and NO ₃ ^– -N conversion of more than 90%.Nitrification and denitrification of wastewater at such a short residence time is possible mainly due to the employment of reciprocating jet bioreactor system.Paper presented at the Third Joint Schlesinger Seminar on Transport phenomena and processes in biological systems, Technion — Israel Institute of Technology, Haifa, Israel, May 8–9, 1990     

Trichoderma reesei cellulases in the bleaching of kraft pulp

In this work the effects of individual purified cellulases of Trichoderma reesei were studied in the enzyme-aided bleaching of kraft pulps. The cellobiohydrolases I and II, when used alone, had no positive effect on the bleachability of kraft pulps. The endoglucanase I (EG I), however, acted on pulp similarly to xylanases and with an enzyme dosage of 0.1 mg/g a clear increase in pulp brightness could be observed. Due to the unspecificity of this enzyme, the viscosity of the pulp was simultaneously decreased. Of the cellulases, EG II was clearly most detrimental in reducing the pulp viscosity. Hence, the action of purified cellulases of T. reesei on pulp as a substrate differs profoundly, and all cellulases are not detrimental to the pulp properties. Correspondence to: J. Buchert     

Acetylation and characterization of xylan from hardwood kraft pulp

Alkaline treatment of eucalyptus hardwood kraft pulp with 10% NaOH yielded 6-8% xylan. The acetylation of the extracted xylan was carried in DMAC/LiCl/pyridine system to obtain a series of xylan acetates with different degrees of substitution (DS). Structure elucidation of xylan and xylan acetate was obtained by ¹H and ¹³C NMR spectroscopy and other homonuclear and heteronuclear 2D-NMR techniques. Inverse-gated ¹³C NMR was employed to determine the DS of xylan acetate. Furthermore, results also revealed equal reactivities at the C-2 and C-3 positions of xylan towards acetylation. Thermal stability, solubility behavior and nanofiber formation of xylan acetate were influenced by its DS values. The mechanical properties of xylan acetate propionate were also investigated.