The formation of colour during biological treatment of pulp and paper wastewater.

Colour discharges are gaining renewed focus in the pulp and paper industry as increasingly strict regulatory limits are placed on wastewater quality and aesthetics. In-mill process improvements, such as ECF bleaching and oxygen delignification, have decreased wastewater colour loadings. However, a survey of 12 pulp and paper mill systems found that effluent treatment using aerated stabilisation basins (ASB) leads to average increases in colour of 20-40%. In some instances, this phenomenon may even double the influent colour levels. Activated sludge systems did not produce a colour increase. The measured increases that follow ASB secondary treatment may be sufficient for a mill to fail prescribed discharge standards. A detailed field survey focusing on sections of an integrated bleached kraft mill ASB treatment system was undertaken. The average increase in colour at the final point of discharge was 45%. The major changes in colour concentration occurred in the inlet to the main treatment pond, and in polishing ponds that followed the main treatment pond. Both of these areas receive little or no aeration. No significant change was observed in the highly aerated main pond. These results, along with literature reports, suggested that redox conditions play a major role in influencing colour behaviour. To test this, two series of paired continuously stirred reactors were used to treat whole mill effluent from two ECF bleached kraft mills in parallel. The first series initially treated under anaerobic conditions, followed by an aerobic reactor, while the second series reversed this order. With the initial anaerobic stage, effluent colour increased by 18% and 19% for the first and second series respectively. Subsequent treatment by aerobic bacteria further increased colour by 14% and 6%, for a total increase of 32% and 25%. Initial aerobic treatment, however, did not lead to any significant change in colour for either effluent. Further anaerobic treatment following aerobic conditions produced only small increases in colour. These results are consistent with the ASB and activated sludge system survey, suggesting that anaerobic conditions at the head of treatment systems initiate the observed increases in effluent colour in ASB treatment systems.     

Effect of phosphorus limitation on microbial floc structure and gene expression in activated sludge.

The effect of limiting phosphorus (P) in activated sludge was investigated in laboratory-scale sequencing batch reactors (SBRs). Correlative microscopy revealed that P-limitation (COD:N:P = 100:5:0.05) leads to morphological changes in floc structure and the composition of extracellular polymeric substances (EPS). This was found to be accompanied by expression of quorum-sensing in an acyl homoserine lactone bioassay. Differential gene expression in relation to P-limitation was examined in a global profile using the Affymetrix Escherichia coli antisense genomic microarray. Three separate experiments were conducted where the impact of P-limitation was examined under batch conditions and in SBRs at stable operating conditions and within 3-7 days following a down-shift in P. Significant changes in open reading frames (ORF) and intergenic regions based on the E. coli microarray were observed. Several genes associated with cell structure, including slt, wbbH, fimH, amB, rfaJ and slp were found to be expressed. Quorum regulated genes were also found to be expressed including psiF which is known to be induced by P-starvation (92% confidence level; 1.45 log ratio).     

Role of high molecular mass organics in colour formation during biological treatment of pulp and paper wastewater.

This paper forms part of series of biological treatment colour behaviour studies. Surveys across a range of mills have observed colour increases in aerated stabilisation basins of 20-45%. Much of the colour formation has been demonstrated to occur in high molecular mass effluent organic constituents (HMM) present in bleach plant effluents. Removing material greater than 3000 Da essentially eliminated the colour forming ability in both E and D stage wastewaters. We have also shown that pulp and paper sludges contain anaerobic bacteria capable of reducing humic like materials. Colour formation was correlated to the anoxic conditions and the availability of readily biodegradable organic constituents during the wastewater treatment process. Overall, these studies suggest that colour formation in pulp and paper biological treatment systems may be caused by anaerobic bacteria using HMM material from the bleaching effluents as an electron acceptor for growth. This leads to the reduction of the material, which in turn leads to non-reversible internal changes, such as intra-molecular polymerisation or formation of chromophoric functional groups.     

水解酸化-好氧生物工艺处理制浆造纸综合废水

介绍了一种以水解酸化-好氧生物工艺为核心的处理能力2万m3/d制浆造纸综合废水的工艺,对处理系统的启动和调试过程进行了总结,重点分析了污泥的培养和驯化、污泥负荷、调试中混凝剂的选择及浓度等因素对系统运行的影响.经过一个多月的调试,系统达到稳定,出水CODCr小于400 mg/L,SS小于80 mg/L,去除率均大于80%,达到了《造纸工业水污染物排放标准》(GB 3544-2001),表明该工艺设计合理、运行稳定可靠,具有处理效率高、投资省和运行费用少的特点.     

Effect of chemical and biological treatment on COD fingerprints of textile wastewaters.

Particle size distribution (PSD) via sequential filtration/ultrafiltration was used as the tool for COD fractionation and colour profiling of textile wastewaters before and after treatment. Profiles prior to treatment suggested PSD-based COD fingerprints characteristic for the influents. Treatment efficiencies were determined via comparing the profiles of the effluents from chemical- and biological-treatment to those of the corresponding influents. COD fingerprints of the wastewaters from the textile plants, applying different treatment alternatives, were different especially at the upper size range; yet profiles after treatment were similar, with the soluble fraction (< 2 nm) being almost the only apparent one. Half of the overall COD-removal via chemical treatment was at the particulate- and upper colloidal-ranges, revealing that this alternative was effective at higher ranges, but not at the soluble fraction. In contrast, biological treatment was effective at both ends of size distribution, with total removal at the particulate range and 50% elimination at the soluble portion. Overall colour content and PSD-based colour profiles of the influents were also different. Chemical treatment was successful in removing colour originating from the entire colloidal range, but was not efficient at the soluble fraction. Conversely, colour removal efficiency of biological treatment was moderate throughout the entire size spectrum.     

Anaerobic treatment of pulp and paper mill effluents--status quo and new developments.

Since the early 1980s, anaerobic treatment of industrial effluents has found widespread application in the pulp and paper industry. Over 200 installations are treating a large variety of different pulp and paper mill effluents. Amongst various anaerobic systems the UASB and IC are the most applied anaerobic reactor systems. Anaerobic treatment is well feasible for effluents originated from recycle paper mills, mechanical pulping (peroxide bleached), semi-chemical pulping and sulphite and kraft evaporator condensates. The advantages of anaerobic pre-treatment are (1) net production of renewable energy (biogas), (2) minimized bio-solids production, (3) minimal footprint and (4) reduced emission of greenhouse gases. Via in-line application of anaerobic treatment in closed circuits (paper kidney technology) further savings on cost of fresh water intake and effluent discharge levies are generated.     

Integrated biological treatment of recalcitrant effluents from pulp mills.

This work aimed at determining the degree of depuration of a recalcitrant effluent (weak black liquor, WBL) achieved in a series treatment consisting of a first stage methanogenic fluidised bed reactor followed by a second stage aerobic, upflow reactor packed with "biocubes" of Trametes versicolor immobilised onto small cubes of holm oak wood. The mesophilic, lab scale methanogenic fluidised bed reactor contained a microbial consortium immobilised onto granular activated carbon 500 microm average size. The process removed decreasing amounts of organic matter at decreasing hydraulic retention times (HRT), eventually reaching an average of 50% at 0.5 day HRT. Colour and ligninoid removals also decreased with decreasing HRT. Although the methanogenic fluidised bed reactor provided an effective treatment for the degradable organic matter, important concentrations of recalcitrant organic matter and colour still remained in the anaerobic effluent. This anaerobic effluent was fed to the aerobic packed bed reactor. Two HRT were tested in this unit, namely 5 and 2.5 days. The reactor averaged an organic matter removal in the range of 32% COD basis, during an experimental run of 95 days. Colour and ligninoid contents were removed in high percentages (69% and 54%, respectively). There was no significant difference in reactor performance at 5- and 2.5-day HRT. There was a positive correlation between pollutant removal efficiencies and Laccase activity in crude extracts of the reactor liquor. No supplemental soluble carbohydrate was required to sustain the fungus activity and the consistent reactor performance. Overall, the two-stage treatment achieved approximately a 78% removal of the original organic matter of the WBL (COD basis) and ca. 75% of colour and ligninoid contents.     

Combined chemical biological treatment of bleached eucalypt kraft pulp mill effluent.

Effectiveness of ozonation before and after biological treatment for removal of recalcitrant organic matter in bleached kraft pulp effluents was compared. Two industrial ECF bleached eucalypt kraft pulp effluents (E1 and E2) were pretreated with 100 mg O3/L. Raw and pretreated effluents were treated biologically in bench-scale sequencing batch reactors, under constant conditions. Following biological treatment, effluents were post-treated with 100 and 200 mg O3/L. Effluent pretreatment increased effluent biodegradability by 10% in E1 and 24% in E2. Combined O3-biological treated led to small but significant increases in COD, BOD and lignin removal over biological treatment alone, but pretreatment had no significant effect on effluent colour and carbohydrate removal. Ozone pretreatment did not affect biological activity during treatment of effluent E1 but resulted in a 38% lower specific oxygen uptake rate in effluent E2. At an equivalent dose of 100 mg/L, pre-ozonation produced better quality effluent than post-ozonation, especially with regard to COD and colour. Likewise, when an equivalent dose of 200 mg/L was applied, splitting the dose equally between pre- and post-treatments was more efficient than applying the entire dose in the post-treatment. The potential for combined chemical-biological treatment to improve effluent quality has been confirmed in this study.     

Bacterial composition of activated sludge--importance for floc and sludge properties.

Activated sludge flocs consist of numerous constituents which, together with other factors, are responsible for floc structure and floc properties. These properties largely determine the sludge properties such as flocculation, settling and dewaterability. In this paper we briefly review the present knowledge about the role of bacteria in relation to floc and sludge properties, and we present a new approach to investigate the identity and function of the bacteria in the activated sludge flocs. The approach includes identification of the important bacteria and a characterization of their physiological and functional properties. It is carried out by use of culture-independent molecular biological methods linked with other methods to study the physiology and function, maintaining a single cell resolution. Using this approach it was found that floc-forming properties differed among the various bacterial groups, e.g. that different microcolony-forming bacteria had very different sensitivities to shear and that some of them deflocculated under anaerobic conditions. In our opinion, the approach to combine identity with functional analysis of the dominant bacteria in activated sludge by in situ methods is a very promising way to investigate correlations between presence of specific bacteria, and floc and sludge properties that are of interest.     

Membrane filtration for tertiary treatment of biologically treated effluents from the pulp and paper industry.

Discharge waters from activated sludge processes in the pulp and paper industry and from a municipal wastewater treatment plant were filtered with various nanofiltration (NF) and low pressure reverse osmosis (RO) membranes. The purpose was to study flux, retention, and permeate quality after membrane filtration by using a high shear (CR-250/2) filter. The suitability of the achieved permeates for reuse at the industrial site is also discussed. The NF permeate was practically free from colour and organic compounds but contained significant amount of inorganic compounds e.g. chloride ions, especially when a high amount of sulphate containing discharge waters were filtered, in which case a low pressure RO membrane was needed to successfully remove monovalent anions. Organic compounds were almost completely retained by NF and RO membranes and organic carbon in the permeate was less than 10 mg/dm3 on average. The achieved permeate can easily be reused in paper production. Nanofiltration has a significantly higher flux and also a lower fouling tendency than reverse osmosis but it passes through monovalent ions when there is a high sulphate concentration in the water. Therefore, RO might be needed in such cases to produce excellent process water.     

Elimination of aromatic surfactants from municipal wastewaters: comparison of conventional activated sludge treatment and membrane biological reactor.

Behaviour of anionic surfactants of linear alkylbenzene sulphonates (LAS) type and non-ionic surfactants of nonylphenol polyethoxylate (NPnEO) type was studied in the conventional mechanical/biological sewage treatment plant (STP) as well as using a membrane biological reactor (MBR). LAS and NPnEO were determined using high performance liquid chromatography (HPLC) equipped with spectrofluorimetric detection. Liquid chromatography/tandem mass spectrometry (LC/MS/MS) was used for identification and quantification of stable metabolites, including nonylphenol (NP), nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO) and nonylphenoxy carboxylic acids (NPnEC). The study showed that aromatic surfactants belong to the most prominent constituents in the examined municipal wastewaters with typical LAS and NPnEO concentrations of 2-10 mg/L and 0.1-0.5 mg/L, respectively. The removal of aromatic surfactants in conventional STP showed well-known features reported in the literature, including an efficient microbial transformation of the parent molecules and formation of stable metabolic products. The elimination efficiency of aromatic surfactants using the MBR unit was higher than that in the conventional STP, while the composition of recalcitrant nonylphenolic residues in the effluent seems to be ecotoxicologically more favourable due to the lower contributions of the lipophilic metabolites.     

污水生物处理中微生物次级代谢产物的研究进展

就污水生物处理过程中微生物次级代谢产物的生成特性及其影响的研究进行了综述。溶解性微生物产物和胞外聚合物是污水生物处理工艺过程中微生物次级代谢的主要产物,其相对分子质量分布、生物可降解性、螯合性、毒性等能说明生物处理系统的整体运行状况;而进水浓度、SRT、HRT、OLR(有机负荷率)等系统运行参数也影响微生物次级代谢产物的生成与性质。目前,有关污水生物处理中微生物次级代谢产物的研究还很不完善,很多问题有待进一步研究。     

Semi-continuous treatment of recalcitrant anaerobic effluent from pulp and paper industry using hybrid pellets of Trametes versicolor.

The objective of this work was to evaluate the semi-continuous post-treatment of anaerobically-pre-treated weak black liquor (anaerobic effluent, AnE) by aerobic post-treatment using hybrid pellets of Trametes versicolor. The latter consisted of fungus immobilized onto holm oak sawdust (mixed or double pellets) or a mixture of holm oak sawdust and powdered activated carbon (triple pellets). First, a semicontinuous experiment was run to compare the effectiveness of triple and mixed pellets in agitated flasks for 15 cycles of 7 days each. A second extended batch test was implemented with 500 mL AnE and triple pellets to give 400 mg fungal biomass; some units were spiked with protease inhibitor. In the first experiment, triple pellets displayed consistently higher removal efficiencies of pollutant parameters than double pellets (10 to 15% higher), although overall averages were moderate and no statistical significance to the difference could be set because of the noise of fluctuations. Periodic fluctuations of removal were characterized by three periods of approximately six cycles each with maximum removals occurring at cycles 3-4, 7-9, 13, and 14. Evaluating pooled removals of the latter cycles showed that triple pellets were significantly more effective than double pellets, with removal efficiencies as high as 47% of COD, colour, and absorbance at 254 nm (A254). In general, protease activity seemed to increase in the third period (last six cycles), whereas activities of MnP, LiP and Lac significantly decreased. In the second experiment, pollutant removals and enzymatic activities of triple pellets with protease inhibitor were significantly higher than those of units without added protease inhibitor. These results indicate that protease could be the main cause of periodic falls of pollutant removal efficiencies found in the first experiment.     

The effect of polymeric flocculants on floc strength and filter performance.

Polymeric flocculants are widely used throughout the water industry as flocculant aids, they are known to increase floc density and aid settlement in the clarification stage of the water treatment process. In this research, polymeric flocculants were used to improve floc strength prior to filtration on a dissolved air flotation (DAF) plant in an attempt to prevent filter breakthrough. A modified jar test procedure using a PDA (photometric dispersion analyser) optical flocculation monitor was developed in order to evaluate the system floc strength. Filtration trials were carried out on a pilot filter rig situated on a surface water treatment works in Yorkshire. The filter feed originated from the main plant filter channel. Filter performance was assessed by continuous online monitoring of effluent particle counts, turbidity and headloss over the period of the filter run. Results indicated that low doses of polymeric flocculants had a beneficial effect on filtered water quality, as measured by particle counts, turbidity, UV254 absorption and dissolved organic carbon (DOC). Polymeric flocculants also had the effect of extending filter run length. The modified jar test results indicated that the flocculants used improved the floc strength and enhanced reflocculation of the micro flocs present after the flotation process.     

Degradation of wine distillery wastewaters by the combination of aerobic biological treatment with chemical oxidation by Fenton's reagent.

The degradation of wine distillery wastewaters by aerobic biological treatment has been investigated in a batch reactor. The evolution of the chemical oxygen demand, biomass and total contents of polyphenolic and aromatic compounds was followed through each experiment. According to the Contois model, a kinetic expression for the substrate utilization rate is derived, and its biokinetic constant is evaluated. The final effluents of the aerobic biological experiments were oxidized by Fenton's reagent. The evolution of chemical oxygen demand, hydrogen peroxide concentration and total contents of polyphenolic and aromatic compounds was followed through each experiment. A kinetic model to interpret the experimental data is proposed. The kinetic rate constant of the global reaction is determined.     

Evaluation of total phosphorus and total nitrogen methods in pulp mill effluents.

Under the Clean Water Action Plan, the US Environmental Protection Agency is requiring states to establish numeric criteria for phosphorus and nitrogen. In preparation for the development of nutrient criteria NCASI undertook a research project to conduct a comparative study of methods for the determination of total phosphorus and total nitrogen in pulp and paper mill matrices. This paper presents results of a single laboratory method evaluation and comparative study of digestion techniques and analytical methods for the determination of total phosphorus (TP) and total nitrogen (TN) in pulp and paper mill secondary treated effluents. Analytical methods included EPA Methods 365.2 and 365.4 for TP. TN and total kjeldahl nitrogen (TKN) methods included EPA Methods 351.2, 351.4, and 353.2. Examinations of sample preservation and storage stability were conducted. Substitution of mercuric sulfate with copper sulfate during block digestion resulted in higher blank levels and method detection limits. TP measurements using EPA Method 365.4 (autoanalyzer) were found to be accurate with a positive bias as determined using matrix spike experiments. Sample digestion by acidic persulfate oxidation or mercuric sulfate block digestion in conjunction with EPA Method 365.4 yielded low blank levels (averages of 0.01 and 0.02 mg/L, respectively), precision of 2.1 and 2.4% relative standard deviations, respectively, and accuracy expressed as an average recovery (%R) of 117% for both. EPA Method 351.2 (autoanalyzer) was more precise than EPA Method 351.4 (ammonia probe). Accuracy (%R) for EPA Method 351.2 ranged from 81 to 95%, depending on the digestion technique applied, and was 55% when EPA Method 351.4 was utilized. Investigation of a method utilizing basic to acidic persulfate oxidation for the simultaneous determination of TN and TP using only two analytical techniques was found to be effective at concentrations above 1 mg/L in pulp mill effluents.     

Influence of physico-chemical treatment on the subsequent biological process treating paper industry wastewater

The present paper presents the main results of the biodegradation study of paper industry wastewater through physico-chemical treatment. Indeed, around 60% of chemical oxygen demand (COD) removal can be achieved by electroflocculation treatment. Furthermore, a removal efficiency of the COD of almost 91% has been obtained by biological treatment, with activated amount of sludge for 24 h of culture. Concerning the physico-chemical pre-treatment of the untreated, filtered and electroflocculated rejection effluents, it has been investigated through the degradation curve of COD studies.     

Occurrence and significance of filamentous bacteria in pulp and paper activated sludge systems.

A microbial survey of 27 activated sludge (AS) systems included 16 conventional activated sludge (CAS) systems, five sequential batch reactors (SBR) and six oxygen-activated sludge (OAS) systems, all treating pulp and paper effluents. The most prevalent filaments observed were Thiothrix (26%) and Type 021N (22%). The designs of the activated sludge systems seemed to have an effect on the filament types. We found Thiothrix to be the most common filament associated with bulking. For CAS systems, a completely mixed mode of operation promoted Thiothrix and Type 021N growth. Type 021N was favoured in CAS systems with food to microorganism (F/M) ratios higher than 0.2, and with dissolved oxygen (DO) residuals higher than 2 ppm, while Thiothrix generally proliferated at lower F/M ratio and DO residuals. Nutrient deficiencies as well as nutrient dosage variations were suspected in most of the systems having Thiothrix and Type 021N as the most prevalent filaments. Thiothrix appeared to prefer polyphosphate and/or ammonia rather than urea/phosphoric acid as N and P sources. Systems with aerobic selectors showed the lowest filament counts, while systems with no selectors showed the highest filament counts.     

Modelling of biological nitrogen removal during treatment of piggery wastewater.

During this study, a mathematical model simulating piggery wastewater treatment was developed, with the objective of process optimisation. To achieve this, the effect of temperature and free ammonia concentration on the nitrification rate were experimentally studied using respirometry. The maximum growth rates obtained were higher for ammonium-oxidising biomass than for nitrite-oxidising biomass for the temperatures above 20 degrees C; values at 35 degrees C were equal to 1.9 and 1.35 day(-1), respectively. No inhibition of nitrification was observed for free ammonia concentrations up to 50 mgN/L. Using these data with others experimental data obtained from a pilot-scale reactor to treat piggery wastewater, a model based on a modified version of the ASM1 was developed and calibrated. In order to model the nitrite accumulation observed, the ASM1 model was extended with a two-step nitrification and denitrification including nitrite as intermediate. Finally, the produced model called PiWaT1 demonstrated a good fit with the experimental data. In addition to the temperature, oxygen concentration was identified as an important factor influencing the nitrite accumulation during nitrification. Even if some improvements of the model are still necessary, this model can already be used for process improvement.     

Effects of heat treatment on microbial communities of granular sludge for biological hydrogen production

Dark fermentation shares many features with anaerobic digestion with the exception that to maximize hydrogen production, methanogens and hydrogen-consuming bacteria should be inhibited. Heat treatment is widely applied as an inoculum pre-treatment due to its effectiveness in inhibiting methanogenic microflora but it may not exclusively select for hydrogen-producing bacteria. This work evaluated the effects of heat treatment on microbial viability and structure of anaerobic granular sludge. Heat treatment was carried out on granular sludge at 100 °C with four residence times (0.5, 1, 2 and 4 h). Hydrogen production of treated sludges was studied from glucose by means of batch test at different pH values. Results indicated that each heat treatment strongly influenced the granular sludge resulting in microbial communities having different hydrogen productions. The highest hydrogen yields (2.14 moles of hydrogen per mole of glucose) were obtained at pH 5.5 using the sludge treated for 4 h characterized by the lowest CFU concentration (2.3 × 10(3)CFU/g sludge). This study demonstrated that heat treatment should be carefully defined according to the structure of the sludge microbial community, allowing the selection of highly efficient hydrogen-producing microbes.