Lipophilic extractives in process waters during manufacturing of totally chlorine free kraft pulp from eucalypt wood

The chemical composition of lipophilic extractives from process waters throughout a totally chlorine free (TCF) bleaching sequence after kraft pulping of eucalypt wood has been studied. These compounds are among the most problematic wood constituents for both TCF and zero liquid effluent (ZLE) processes, since they tend to accumulate in circuits resulting in the formation of the so-called pitch deposits causing serious problems in the pulp and paper industry. Pitch deposits collected at different parts of the pulp mill were also characterized and their composition compared with that of lipophilic compounds in process waters and Eucalyptus globulus wood. The identification of these compounds from process waters, wood and pitch deposits was performed by gas chromatography and gas chromatography-mass spectrometry using short- and medium-length high temperature capillary columns. Sterols, sterol esters, steroid ketones and steroid hydrocarbons were the main compounds identified. These chemical species arise from eucalypt wood extractives that survive the pulping and are released from pulp into the process waters during the bleaching process. Finally, they can deposit in pulp and on different parts of the mill or remain suspended in process waters being discharged in effluents.     

Changes in character of organics in the receiving environment of effluent from a sulphite pulp mill

Purpose

The characteristics of organics in sulphite pulp mill effluent and in the receiving environment of effluent discharge were investigated to assess the basis for the persistence or attenuation of colour.

Methods

Characterization of organics was conducted through determination of SUVA, specific colour, and molecular weight distribution of organics using high performance size exclusion chromatography and by solid-state ¹³?C cross polarization (CP) NMR. The characteristics of organics from mill wastewater before and after secondary aerobic treatment, followed by lime treatment and from the receiving environment, an enclosed brackish lake were compared. Changes in the character of organics in lake water over a period of 14?years were studied in the context of changes in mill processing and climate impacts.

Results

High colour in mill effluent and in receiving waters correlated with high SUVA and specific colour levels, high molecular weight range and aromatic content. Conversely, lake waters with low colour had UV absorbing compounds of much lower molecular weight range and low relative abundance of aromatic compounds. Attenuation of colour and changes in the character of organics in the receiving environment coincided with increased concentrations of metal cations.

Conclusions

These increased concentrations appear to be due to the effects of climate change, lake management and their presence in mill effluent, with subsequent discharge to the lake. Attenuation of colour was found to be predominantly through removal of high molecular weight aromatic compounds where the removal processes could be through adsorption and co-precipitation with divalent metals, as well as through dilution processes.     

Molecular size distribution of natural organic matter in raw and drinking waters.

The purpose of this study was to compare the molecular size distribution (MSD) of natural organic matter (NOM) in raw waters (RW) and drinking waters (DW), and to find out the differences between MSD after different water treatment processes. The MSD of NOM of 34 RW and DW of Finnish waterworks were determined with high-performance size-exclusion chromatography (HPSEC). Six distinct fractions were generally separated from water samples with the TSK G3000SW column, using sodium acetate at pH 7 as an eluent. Large and intermediate humic fractions were the most dominant fractions in surface waters (lakes and rivers), while in artificially recharged groundwaters and natural groundwaters intermediate and small fractions predominated. Water treatment processes removed the two largest fractions almost completely shifting the MSD towards smaller molecular size in DW. Granular activated carbon (GAC) filtration, ozonation, and their combination reduced all humic fractions compared to the conventional treatment. Humic fractions correlated with total organic carbon (TOC) content and chemical oxygen demand, this being especially true in RW. The results demonstrate that the HPSEC method can be applied for a qualitative and also for rough estimate quantitative analyzes of NOM directly from RW and DW samples without sample pretreatment.     

Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV–Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.     

Comparative toxicity of effluents processed by different treatments in V79 fibroblasts and the algae Selenastrum capricornutum

The efficacy of ozonation and of photocatalysis processing in the treatment of pulp mill ECF (elementary chlorine free) bleaching and textile effluents was evaluated by determining total organic carbon reduction (TOC) and the toxicity. The chronic toxicity of the effluents was evaluated by the ability to inhibit the growth of algae Selenastrum capricornutum. Cultured hamster V79 fibroblasts were used to assess the cytotoxicity of effluents submitted to different detoxification processes. Two endpoints were measured in V79 cells: 3-(4,5-dimethylthiazole-2-yl)-2,5-biphenyl tetrazolium bromide (MTT) reduction and neutral red uptake (NRU). Both treatment processes were able to reduce the TOC, although ozonization was less effective for pulp mill ECF bleaching. The pulp mill ECF bleaching and textile effluents reduced the growth of S. capricornutum by 39% and 27%, respectively. However, at the highest concentration tested, the textile effluents treated by photochemical process for 60 min showed increased cytotoxicity in V79 cells compared to the untreated effluent when assessed by the NRU and MTT reduction assays (increases of 30% and 40%, respectively). Pulp mill ECF bleaching effluent treated by ozonization had a similar cytotoxicity to that of untreated effluent in the NRU assay. In contrast, the MTT reduction assay indicated that effluents treated with ozone were around 20% more cytotoxic than untreated effluents. These results show that cultured fibroblasts may be useful for studying cellular responses to pollutants and may be included in tests to monitor the efficiency of effluent detoxification processes.     

Conifer aphids in an air-polluted environment. II. Host plant quality

Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies (L.) Karst.) seedlings were transported to five forest sites at increasing distances from a pulp mill emitting mainly SO(2). Levels of compounds which may have nutritional or defensive value for aphids on pine and spruce seedlings were studied. Glucose and fructose concentrations were significantly increased in pine and spruce needles near the pulp mill. There were no changes in sucrose and starch concentrations. In pine shoots, total free amino acid concentration and the concentrations of ornithine, lysine, histidine and arginine were significantly negatively correlated with the distance from the pulp mill, while in spruce only the individual amino acids glycine, ornithine, lysine and histidine showed a significant negative correlation with distance. There were no changes in total phenolic, catechin, total monoterpene and total resin acid concentrations. However, in pine seedlings monoterpenes beta-pinene and sabinene and in spruce seedlings resin acid palustric acid were significantly correlated with the distance from the pulp mill. The results indicate that SO(2) disturbs carbohydrate metabolism in spruce and pine seedlings. The elevated concentrations of arginine may be the result of the combinations of SO(2), NO(3) and NH(3) emissions of the pulp mill. The emissions did not have any impact on total amounts of defensive substances in trees. Thus, the possible susceptibility of conifers to herbivores appears to be due to changes in nutritive value rather than to reduced chemical resistance.     

Effects of tertiary treatment by fungi on organic compounds in a kraft pulp mill effluent

Background, aim and scope  

Pulp and paper mills generate a plethora of pollutants depending upon the type of pulping process. Efforts to mitigate the environmental impact of such effluents have been made by developing more effective biological treatment systems in terms of biochemical oxygen demand, chemical oxygen demand, colour and lignin content. This study is the first that reports an evaluation of the effects of a tertiary treatment by fungi (Pleurotus sajor caju, Trametes versicolor and Phanerochaete chrysosporium and Rhizopus oryzae) on individual organic compounds of a Eucalyptus globulus bleached kraft pulp and paper mill final effluent after secondary treatment (final effluent).     

Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV–Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.     

Organic chlorine compounds in lake sediments. V. Bottom of Baikal near a pulp mill

Organically bound chlorine (OCl) together with inorganic chloride (Cl⁻) was measured from bottom surface samples of the Lake Baikal near a pulp mill and compared to organic matter contents (OM). Although total contents of OCl, Cl⁻ and OM were much lower than, the ratio of OCl to OM was of the same order of magnitude as in pulp mill recipients of Finland.     

Molecular size distribution of compost-derived humates as a function of concentration and different counterions

Conformational changes in the structures of humic acids (HA) extracted from compost with varying degrees of maturity were monitored by high performance size exclusion chromatography (HPSEC). The molecular size distribution of HA was compared in solutions containing sodium or ammonium counterions at pH 7 and pH 4.5. These findings indicate that the humates' molecular size depended not only on the nature of the counterions but also on their concentration in the solution. The physicochemical nature of sodium counterions determined smaller molecular sizes than those of the more hydrated ammonium counterions, at low concentrations of humates. Conversely, at higher humate concentrations, the more compact conformation of sodium humates produced larger molecular sizes than those of ammonium humates due to the aggregation of more hydrophobic surfaces in the sodium humates. Composting led to the degradation of labile microbial components with accumulation of hydrophobic constituents. This caused self-association of hydrophobic compounds into humic superstructures of larger molecular size over composting time. At lower pH, changes in conformational stability by the addition of acetic acid to humate solutions were explained by the supramolecular model of humified organic matter.     

Characterization of the humic material formed by composting of domestic and industrial biowastes Part 1. HPLC of the cupric oxide oxidation products from humic acids

The changes induced by humification of anaerobically digested sewage sludge, source separated biowaste, and pulp mill biosludge were determined by extracting the fractions of bitumen and humic and fulvic acids from the samples of fresh and humified composts. In all cases, a distinct decrease in the amount of bitumen could be detected during humification. The amount of humic acids increased in sewage sludge and biowaste samples, but decreased in pulp mill biosludge sample during humification. The humic acids were degraded by CuO oxidation and the phenolic degradation products were analysed by reversed-phase high-performance liquid chromatography. The yield of these aromatic degradation products was in the range 0.9–2.0 % for each sample. The main phenolic degradation products were 4-hydroxybenzoic acid, vanillic acid, 4-hydroxybenzaldehyde, vanillin, syringaldehyde, and acetovanillone. Two lignin dimers, dehydrodivanillin and dehydrodiacetovanillone, were also identified.     

A laboratory exposure procedure for screening pulp and paper mill effluents for the potential of causing increased mixed function oxidase activity in fish

To better understand the relationships between pulp manufacturing processes and mixed function oxidase (MFO) enzyme induction in fish, a practical and standardized exposure procedure is required. This study was undertaken to develop a laboratory-based exposure procedure to quantify the relative MFO induction potencies of different types of pulp and paper mill effluents. One major consideration in developing the procedure was to ensure that the protocol was practical so that tests could be performed in a short time, with small volumes of effluents and using simple experimental conditions. A series of concentration-response and time-course experiments were conducted to find the minimum time and effluent concentration which could distinguish the ability of different effluents to cause significant MFO induction in rainbow trout in the laboratory. Experiments were also conducted to determine the effects of biotic and abiotic factors such as loading density, fish size and feeding regime. This study showed that the exposure of rainbow trout in the laboratory to 10% concentration of secondary-treated effluent for 96 h caused significant increases in hepatic MFO activity. The magnitude of MFO induction was comparable to other field and laboratory observations. While fish size, loading density and feeding regime were found to affect the test results, consistent responses within a laboratory using this protocol are possible, provided that these factors are standardized. Therefore, the short-term exposure approach described in this paper could be a relevant tool for assessing the ability of different types of pulp and paper mill effluents to cause MFO induction in fish.     

Evaluation of the treatment efficiencies of paper mill whitewaters in terms of organic composition and toxicity

The efficiency of several lab scale treatments (aerobic, anaerobic and ozone or combination of these) was evaluated using two packaging board mill whitewaters. The effect of the different treatments on the elimination of the organic load, the chemical oxygen demand (COD) and the toxicity was tested as well as the relationship between these parameters. Biocides, phenolic compounds, surfactants, plasticiziers and wood extractives were identified in untreated and treated whitewaters by liquid chromatography coupled with mass spectrometry (LC-MS) or gas chromatography coupled with mass spectrometry (GC-MS). A strong dependency on the water type and treatment efficiency was observed, being the combination of anaerobic and aerobic treatments the best option to reduce the organic contaminants in these waters, although in some cases, the toxicity did not decrease. However, ozone as post-treatment permitted a further reduction of organic compounds, toxicity and COD.     

Odours from pulp mill effluent treatment ponds: the origin of significant levels of geosmin and 2-methylisoborneol (MIB)

Pulp and paper mills are well known for their sharp, sulphurous stack emissions, but the secondary treatment units also can be significant contributors to local odour. This study investigated the source(s) of earthy/musty emissions from a mixed hardwood pulp mill in response to a high local odour. Samples from five sites in the mill over five months were analyzed for earthy/musty volatile organic compounds (VOCs), examined microscopically, and plated for bacteria and moulds. In all cases, activated sludge showed substantial geosmin levels and to a lesser extent 2-methylisoborneol (MIB) at 2000-9000 times their odour threshold concentrations (OTCs). These VOCs were lower or absent upstream and downstream, suggesting that they were produced within the bioreactor. Geosmin and MIB were highest in late summer and declined over winter, and correlated with different operating parameters. Geosmin was most closely coupled with temperature and MIB with nitrogen uptake. Cyanobacteria were present in all sludge samples, but actinomycetes were not found. Gram-negative bacteria and one fungal species isolated from the bioreactor and secondary outfall tested negative for geosmin or MIB. We conclude: (i) geosmin and MIB contribute significantly to airborne odours from this mill, but are diluted below OTC levels at the river; (ii) these VOCs are generated by biota in the activated sludge; and (iii) cyanobacteria are likely primary source(s). The growth of cyanobacteria in activated sludge represents a loss of energy to the heterotrophic population; thus earthy/musty odours may represent a diagnostic for less than optimal conditions.     

An overview of the methods used in the characterisation of natural organic matter (NOM) in relation to drinking water treatment

Natural organic matter (NOM) is found in all surface, ground and soil waters. During recent decades, reports worldwide show a continuing increase in the color and NOM of the surface water, which has an adverse affect on drinking water purification. For several practical and hygienic reasons, the presence of NOM is undesirable in drinking water. Various technologies have been proposed for NOM removal with varying degrees of success. The properties and amount of NOM, however, can significantly affect the process efficiency. In order to improve and optimise these processes, the characterisation and quantification of NOM at different purification and treatment processes stages is important. It is also important to be able to understand and predict the reactivity of NOM or its fractions in different steps of the treatment. Methods used in the characterisation of NOM include resin adsorption, size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) spectroscopy, and fluorescence spectroscopy. The amount of NOM in water has been predicted with parameters including UV-Vis, total organic carbon (TOC), and specific UV-absorbance (SUVA). Recently, methods by which NOM structures can be more precisely determined have been developed; pyrolysis gas chromatography-mass spectrometry (Py-GC-MS), multidimensional NMR techniques, and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The present review focuses on the methods used for characterisation and quantification of NOM in relation to drinking water treatment.     

Particulate organic matter in the sea: the composition conundrum

As organic matter produced in the euphotic zone of the ocean sinks through the mesopelagic zone, its composition changes from one that is easily characterized by standard chromatographic techniques to one that is not. The material not identified at the molecular level is called "uncharacterized". Several processes account for this transformation of organic matter: aggregation/disaggregation of particles resulting in incorporation of older and more degraded material; recombination of organic compounds into geomacromolecules; and selective preservation of specific biomacromolecules. Furthermore, microbial activities may introduce new cell wall or other biomass material that is not easily characterized, or they may produce such material as a metabolic product. In addition, black carbon produced by combustion processes may compose a fraction of the uncharacterized organic matter, as it is not analyzed in standard biochemical techniques. Despite these poorly-defined compositional changes that hinder chemical identification, the vast majority of organic matter in sinking particles remains accessible to and is ultimately remineralized by marine microbes.     

Treatment of bleach pulp mill effluent by MF-MBR

The types of treatment most commonly used by pulp mills are biological treatments in combination with sedimentation or coagulation/flocculation as pretreatment. The main issues faced by these types of treatment are low efficiency in the removal of organic matter and the loss of aggregate value for the recovered fiber. Therefore, this study aims to evaluate the use of microfiltration (MF) combined with a membrane bioreactor (MBR) for the treatment of bleach pulp mill effluents. The results showed that the use of the MF-MBR system was an excellent alternative for the treatment of bleach pulp mill effluents with an average COD removal of 95%. The microfiltration allowed the recovery of fibers, which can be returned to the production process without losing economic value, and produced a better quality effluent for further treatment in the MBR. The MBR presented high efficiency removal of organic matter.     

Model compound synthesis for the structure determination of new unknown planar aromatic compounds originating from pulp mill

Several model compounds have been synthesized for verification of the structures of new unknown planar aromatic compounds (UPACs) observed in high-resolution gas chromatography/low-resolution mass spectrometry analyses of the polychlorodibenzodioxins (PCDDs) and polychlorodibenzofurans (PCDFs) in pulp mill products, effluents, sediments and mussels. The mass spectra of synthetic alkyl polychlorodibenzofurans (C₆-PCDFs) were different, but those of alkyl polychlorobibenzyls (C₅-PCBBs) were very similar compared to the spectra of UPACs.     

PCDTs in the environment

Polychlorinated dibenzothiophenes (PCDTs) are sulfur analogues of polychlorinated dibenzofurans. Recently, PCDTs have been found in stack gas and fly ash samples, pulp mill effluents, sediments and in some aquatic organisms. PCDTs have been analyzed by high resolution GC/MS and by other GC-MS techniques. Combustion is until now the major known source of PCDTs in the environment. Tri-, tetra- and pentaCDTs in concentrations approaching those of PCDTs have been analyzed in some samples from waste incineration and metal reclamation. Concentrations of PCDTs in pulp mill effluents have been found to be quite low. 2378-TeCDT was found to be the major TeCDT isomer in some pulp mill effluents. Preliminary toxicological investigations have shown that PCDTs possess some kind of dioxin type toxicity.