Effect of pH on toxicity of kraft pulp and paper mill effluent to salmonid fish in fresh and seawater

In freshwater bioassays with juvenile rainbow trout (Salmo gairdneri), at initial pH values from 4 to 11, kraft mill effluents were considerably less toxic at pH 9–10 than at neutrality. When pH of test solutions was controlled throughout the bioassay period, the least toxic range was 8.5–9.5. Toxicity at typical receiving-water pH values was 50–67% greater.The acute toxicity of effluent samples to yearling coho salmon (Oncorhynchus kisutch) was identical for these effluents in seawater and freshwater respectively, provided that the pH was adjusted and held at the same value, and that test fish were previously acclimated to the dilution water for several months. Thus seawater constituents other than pH did not affect the acute toxicity of pulp and paper mill effluents appreciably.     

Chlorinated phenolics of bleached kraft mill origin : An olfactory evaluation

Biologically treated effluent samples from 9 Canadian bleached softwood kraft mills were analyzed for chlorinated phenolics content. Odour thresholds were determined for selected chlorinated phenolics and for a synthetic mixture of these compounds at concentrations typical of a biologically-treated bleached kraft mill effluent. Results indicate that chlorinated phenolics present in effluent discharged from bleached kraft mills are not expected to contribute an off-odour to recipient waters.     

Disruption of precopulatory behavior in the amphipod Anisogammarus pugettensis upon exposure to bleached kraft pulpmill effluent

Marine amphipods in precopula, Anisogammarus pugettensis (Dana), were used in static 117 h bioassays with neutralized, filtered, bleached kraft pulp mill effluent (BKME) and daily solution replacement. The effluent interfered with precopula behavior; high concentrations (40% of full strength BKME) resulted in rapid release of paired amphipods. A concentration-related time to 50% release of paired individuals was observed. For one batch of BKME, the behavioral threshold concentration (EC₅₀) was estimated at 10–15% of full strength BKME. The estimated 96 h LC₅₀ for underyearling coho salmon (Oncorhynchus kisutch) for the same effluent tested in freshwater was 36% BKME—illustrating a greater sensitivity of the amphipod behavioral bioassay in comparison to the salmonid acute lethal toxicity test. The amphipod precopula bioassay for toxicity testing has some merit in that it is moderately quantitative under given test conditions and does not require elaborate equipment.     

Use of rat brain Na, K-ATPase assay to determine effectiveness of biological treatment to reduce toxicity of paper mill effluents

This work evaluates the toxicity of kraft mill wastewaters and the extent of detoxification attained after biological treatment of these effluents with the fungus Phanerochaete chrysosporium. The degree of inhibition of the enzyme Na⁺, K⁺-ATPase was used as an indicator of toxicity. The untreated alkali extraction stage effluent significantly inhibited the enzyme activity. When this effluent was treated biologically the degree of enzyme inhibition was practically reduced to zero. The inhibition of the enzyme Na⁺, K⁺-ATPase was found to be a suitable indicator of toxicity for bleached pulp and paper mill waste waters.     

Long term BOD determinations on biologically treated and untreated kraft mill effluent discharged to Lake Saimaa, Finland

Long-term BOD determinations have been carried out on kraft pulp mill effluent over a period of more than 200 days using the conventional dilution method and utilizing a special bottle sealing technique. Determinations were made at the temperatures 2, 5, 10 and 20°C on untreated effluent and on effluent treated by an experimental biological extended aeration treatment plant which treated effluent discharged to Lake Saimaa in eastern Finland.BOD curves have been constructed for up to a period of 200 days and the results indicate that untreated effluent exerts a two-stage BOD on receiving waters, the second stage commencing after approx. 28 days. Treated effluent was found to have a low BOD and showed no second stage of oxygen uptake.     

Acute toxicity of unbleached kraft mill effluent (UKME) to the opossum shrimp, Neomysis americana smith

Ninety-six hour TL₅₀ values of unbleached kraft mill effluent (UKME) for Neomysis americana were found to range from concentrations of 3.29–6.85 per cent at 26–28°C and 3.90–7.30 per cent at 16–18°C. Differences between batches of effluent proved insignificant in experiments at each temperature regime. Furthermore, UKME did not lose its toxicity when stored for 5–7 days at 4°C. A concentration of 20 per cent effluent killed 100 per cent of the organisms in 8 of the 12 bioassays. Slope functions and confidence limits of TL₅₀ were calculated. Toxicity did not appear to be correlated with the Biochemical Oxygen Demand (BOD) of individual batches of raw effluent.     

Effects of kraft mill effluents on juvenile salmon production in laboratory streams

Effects of effluents on juvenile chinook salmon Oncorhynchus tshawytscha were studied in six laboratory streams. Primary effluent (KME) from mill A reduced salmon production at a concentration of 1.5% by volume (0.2 × 96h TL50) but not at 0.5% (0.07 × 96 h TL50). Fall and spring exposure to stabilized kraft effluent (SKME) from mill A at 1.5% reduced salmon production, while in summer experiments, fish production was enhanced at concentrations of up to 4% for mill A and up to 7.5% for mill B. Thus, production values varied with the source and extent of treatment of effluent and perhaps with season. Fish growth was related to food density during some experiments.     

Leeches as in situ biomonitors of chlorinated phenolic compounds. Part 2: Pulp mill investigations

Leeches (Nephelopsis obscura Verrill) were evaluated as in situ biomonitors of chlorinated phenolic compounds in the Fraser River at Prince George, BC, downstream from three bleached kraft pulp mills practising chlorine dioxide (ClO₂) substitution. Five biomonitoring periods, of 7 days duration, were selected to cover a full range of seasonal river conditions.Leeches bioconcentrated tri- and tetrachlorinated phenolics (bioconcentration factors: 465–6000) in proportions similar to those present in both mill effluent and river water. Leeches showed 3,4,5-trichloroguaiacol (3,4,5-TCG) to be the most consistent tracer of bleached kraft mill discharge. Leeches provided direct evidence that increasing ClO₂ substitution reduces amounts of chlorinated phenolics accumulated by aquatic organisms, with sharp decreases observed at ClO₂ levels greater than 90%. This study suggests that leeches could be applied as routine biomonitors for environmental impact monitoring.     

An evaluation of the potential toxicity of treated bleached kraft mill effluent to striped bass (Morone saxatilis walbaum) larvae exposed through metamorphosis to the juvenile stage

Twenty-day-old striped bass (Morone saxatilis) larvae were exposed to a range of treated bleached kraft mill effluent (BKME) concentrations from 0 to 20% effluent by volume (v/v) under continuous flow test conditins. The experimental test concentrations in the 2–20% BKME test aquaria had a BOD₅ which ranged from < 1 to 5 mg l⁻¹, TSS 12–17 mg l⁻¹, and true color 35–416 mg l⁻¹. Bleached kraft mill effluent did not kill larvae exposed to it for 20 days through metamorphosis to the juvenile stage. The BKME did not alter growth in length, weight or condition factor in larvae over the 20-day exposure period as determined by multiple regression analysis. A linear regression analysis on the dry weight data at Day 20 only, however, indicated a trend of decreasing weight with increasing BKME concentration. Effluent-exposed larvae also developed normally during the 20-day study. All individuals examined completed the transformation from postlarvae to juveniles by the age of 40 days.     

Effects of lignin and chlorolignin in pulp mill effluents on the binding and bioavailability of hydrophobic organic pollutants

The partition coefficients (K_p) of benzo(a)pyrene (BaP), 3,3′,4,4′-tetrachlorobiphenyl (TCB) and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) to dissolved kraft lignin (Indulin AT), chlorolignin isolated from a bleached kraft mill effluent (BKME) and dissolved organic matter (DOM) in a lake receiving BKME were measured by equilibrium dialysis. The K_p values of kraft lignin were 28.2 × 10⁵, 6.5 × 10⁵ and 15.9 × 10⁵ and those of chlorolignin were 8.3 × 10⁵, 2.9 × 10⁵ and 2.2 × 10⁵ for BaP, TCB and TCDD, respectively. In addition, DOM in a series of lake water samples collected from the southern part of Lake Saimaa, SE Finland, receiving BKME revealed higher binding capacities to all of the three model compounds than natural DOM in water upstream from the pulp mill. An important phenomenon related to the environmental transport and fate of xenobiotics was almost the full reversibility of the binding between chlorolignin and model compounds. The obtained K_p values of chlorolignin after a 4 day dissociation period were 12.6 × 10⁵ and 4.6 × 10⁵ for BaP and TCDD, respectively.In short-term (24 h) accumulation experiments with Daphnia magna the effects of kraft lignin and chlorolignin on the bioavailability of three model compounds was very clear. The bioconcentration factors of the xenobiotics in the chlorolignin containing water (DOC = 10 mg C/l) were 20–30 and 25–35% of those organic-free control and upstream reference waters (DOC = 7.2 mg C/l), respectively. The effect of chlorolignin of BKME on the bioavailability of model compounds was also seen in the lake water series of Lake Saimaa.     

Coagulation and precipitation of a mechanical pulping effluent—I. Removal of carbon,colour and turbidity

This study examined the effects of metal coagulant concentration, effluent dilution and pH on the removal of total carbon, colour and turbidity from a combined bleached chemithermomechanical/thermomechanical (BCTMP/TMP) effluent. Both chloride and sulphate salts of iron and aluminum were effective in treating the mechanical pulping effluent in batch jar screening tests. pH had a pronounced affect on precipitation. In terms of minimizing the total carbon (TC), colour and turbidity levels, the optimum adjusted pH ranges were: 4.0–6.5 for ferric chloride, above 7.4 for ferrous sulphate, 5.0–6.0 for aluminum chloride and 5.8 to 6.8 for aluminum sulphate. Removal of TC, colour and turbidity of up to 88, 90 and 98%, respectively, were observed. The precipitation yielded a supernatant which was virtually clear and colourless.     

Fate of wood extractives in wastewater treatment plants at kraft pulp mills and mechanical pulp mills

Extensive environmental effects of the forest industry led to implementation of activated sludge treatment of effluents in the 1980s. Although the existence of chlorinated compounds in the effluents has decreased, a discussion about the possible environmental effects of elemental-chlorine-free (ECF) and total-chlorine-free (TCF) bleached pulp mill effluents has arisen, and chronic effects on aquatic organisms have still been found. Recently, studies have mainly focussed on wood extractives and their role in the effects of effluents. Resin acids and unsaturated fatty acids are found to be toxic, and plant sterols are reported to have adverse endocrine effects on water organisms already at low concentrations. In this study, Finnish wastewater treatment plants of an ECF kraft pulp mill, a paper mill, and an integrated TCF kraft pulp and paper mill were sampled in order to ascertain how wastewater treatment plants, and especially activated sludge treatments, remove wood extractives. Concentrations of extractives in discharged wastewaters varied between 0.4 and 11 g/t kraft or mechanical pulp, and the concentrations decreased over 95% during the treatment processes. Of the wood extractives, 1.1-64% were adsorbed to biosludge and 35-99% were degraded or transformed to other forms during the activated sludge treatment. A major part of these compounds were discharged in particles (74-99%). The removal of extractives was efficient even in the effluent treatment plant, which was highly loaded during the sampling period.     

A solid chemical oxygen demand (COD) method for determining biomass in waste waters

A method of biomass determination similar to volatile suspended solids (VSS) that used chemical oxygen demand (COD) as a detection method instead of gravimetric methods is described. The “solid COD” method has a strong correlation with VSS for biomass at different stages of growth on different wastewaters including municipal sewage and bleached kraft mill effluent. Soluble COD from the wastewaters did not interfere with the assay. However, non-biomass suspended solids in chemi-thermo-mechanical pulping effluent were found to have a different COD/VSS ratio and thus interfered with solid COD results. The ratio between COD and VSS for biomass was approx. 1.2–1.6 mg COD/mg VSS.     

MFO induction in fish by filtrates from chlorine dioxide bleaching of wood pulp

Spent bleaching liquors from pulp bleached with chlorine dioxide were assessed for their potency to induce hepatic mixed function oxygenase enzymes (MFO) in rainbow trout, as indicated by activity of ethoxyresorufin-o-deethyase (EROD). Filtrates were collected from two kraft mills in Central Canada to assess the potency of filtrates from hardwood and softwood bleaching. All mill-scale bleaching filtrates induced MFO activity, and filtrates from softwood pulp bleaching appeared more potent than filtrates from hardwood bleaching. Filtrates from the final bleaching stage were most potent, and filtrates from the first stage were the least potent. In laboratory bench-scale bleaching experiments, pulp from softwood and hardwood kraft mills in Eastern Canada was bleached via an industry-standard 5-stage chlorine dioxide bleaching sequence. The filtrates were collected and used in fish bioassays to assess EROD-inducing potency. Potency of bench-scale filtrates varied depending on wood furnish (i.e. softwood vs. hardwood) and the bleaching stage, with all bench-scale filtrates being much weaker EROD inducers than mill-scale filtrates. Recycled paper mill washwater is a possible source of compounds causing increased potency of the mill-scale filtrates.     

Effects of transient temperature conditions on the divergence of activated sludge bacterial community structure and function

The effect of temperature fluctuations on bacterial community structure and function in lab-scale sequencing batch reactors treating bleached kraft mill effluent was investigated. An increase in temperature from 30 to 45 degrees C caused shifts in both bacterial community structure and function. Triplicate reactors were highly similar for 40 days following startup. After the temperature shift, their community structure and function started to diverge from each other and from the control. A multi-response permutation procedure confirmed that the variability in community structure between transient and control reactors were greater than that among the triplicate transient reactors. The fact that these disturbances manifest themselves in different ways in apparently identical reactors suggests a high degree of variability between replicate systems.     

The interaction of treated bleached kraft mill effluent and dissolved oxygen concentration on the survival of the developmental stages of the sheepshead minnow (Cyprinodon variegatus)

The interactions of treated bleached kraft mill effluent (BKME) and dissolved oxygen concentration (DO) on the survival of the embryo, fry, juvenile and adult stages of the sheepshead minnow, Cyprinodon variegatus, were studied under continuous-flow 96 h bioassay conditions. Embryo survival was dependent on effluent concentration only and showed no interaction at nominal DO concentrations of 1.0, 3.0 and 5.0 mg l⁻¹. Survival of the fry was related solely to DO concentration with no interaction with BKME concentrations up to 100%. Juvenile sheepshead minnows showed increased sensitivity to BKME at a nominal DO concentration of 1.0 mg l⁻¹. Adult fish were not affected by BKME at any of the DO concentrations tested. This study shows that the acute toxicity of BKME effluent to sheepshead minnows is a function of the developmental stage of the organism and DO concentration in the receiving stream.     

Acute and early life stage toxicity of industrial effluent on Japanese medaka (Oryzias latipes)

To develop the whole effluent toxicity testing methods (WET), embryo larval stage toxicity test using Japanese medaka (Oryzias latipes) was conducted to evaluate an effluent from a banknote printing plant (BPP). The method is based on acute toxicity using endpoint of 96-h larval morality and on chronic toxicity using endpoints such as the time to hatch, hatching success, deformity, growth rate, swim-up failure, accumulative mortality and sexual ratio. In test for 96-h larval mortality, LC50 (the concentration was lethal to 50% of newly hatching medaka larvae) was 72.9%. In chronic toxicity test, newly fertilized embryos (<5-h old) were exposed to 1%, 6.25%, 12.5%, 25%, 50% effluent concentrations and to 200 mug/l BPA in a 24-h static renewal system at 25+/-1 degrees C until 15 day post-hatch. The results showed that all chronic endpoints were significantly different from the control at 50% dilution (p < 0.01). Embryos began to show lesions on 4th day at higher concentrations (12.5%, 25%, 50% BPP effluent concentrations). Treatment group of 25% dilution showed delayed time to hatch. A reduction in body weight was observed at 25% dilutions for males and females, respectively. Deformities were observed in newly hatched larvae at 25% and 50% BPP effluent concentrations. At 25% dilution, sex ratio of larvae was alternated and there was feminization phenomenon. We conclude that embryo larval stage test using medaka is feasible to evaluate both acute and chronic toxicities and potential endocrine disrupting activity of industrial effluents.     

The influence of the high and low molecular weight fractions of a bleach kraft mill effluent on the microbial activity of activated sludge

The high molecular weight (HMW) fraction (> 1000 Da) of bleached kraft mill effluent (BKME) is the principal source of adsorbable organic halide (AOX), colour and chemical oxygen demand in treated effluent. The influence of HMW material on the microbial activity of activated sludge microorganisms was studied in a series of batch growth experiments using fractionated effluent. The HMW material in the untreated effluent comprised 80% of the AOX but only 20% of the soluble COD. Multivalent metal ions had a greater affinity for this HMW fraction. The addition of HMW material to the LMW fraction had a stimulatory effect on microbial activity as measured by increases in biomass and substrate utilization. Chemical characterization and subsequent growth experiments revealed that nitrogen, which was deficient in the LMW effluent, was primarily associated with the HMW material. The association of nitrogen with the HMW fraction may have an important role on the behaviour of nitrogen within a biological treatment system and in the receiving environment.     

Development and application of a quasi-static Langmuir isotherm for modelling selected resin acid fate in pulp mill wastewater treatment

Resin acids are pulp mill effluent contaminants that exhibit significant solubility, diffusivity, and surfactancy changes with pH within the range typically used for biological treatment. Such physical-chemical property changes which can influence removal during biological wastewater treatment, can be characterized by dynamic surface tension measurements. Dynamic surface tension measurements were made by the maximum bubble pressure method during batch treatment of selected resin acids in pulp mill effluent. Interpretation of dynamic surface tension data was made through the framework of a quasi-static Langmuir isotherm model that was derived as part of this investigation. The results suggested that under acidic conditions, resin acids form associations with other dissolved organic matter contained in pulp mill effluent, while under alkaline conditions, they behave as relatively soluble surfactants. A resin acid residuum, or threshold concentration, has been found to increase under acidic growth conditions. This residuum increase corresponded to an inferred reduction in resin acid bioavailability that was suggested from the isotherm modelling. The development of quasi-static isotherm adsorption models has application in computer simulation for design of adsorption based unit processes, and could potentially be utilized as an informative treatment process monitor.     

Nanofiltration removal of chlorinated organic compounds from alkaline bleaching effluents in a pulp and paper plant

Three commercial nanofiltration membranes were used for the removal of chlorinated organic compounds from the first alkaline extraction effluent originated from a kraft mill, using eucalyptus wood as raw material. The assays were carried out at the following operating conditions: pressure = 20 bar, TEMPERATURE = 20°C and circulation VELOCITY = 2 m/s. The results show the nanofiltration feasibility. For the three membranes the rejection factors of chlorinated organic compounds are greater than 95% and two of them present permeate fluxes of approx. 42 kg/hm². Several reference solutes with a wide range of molecular weights and functional groups were also permeated. Their results compared with those of mill effluent allow us to conclude that the effluent tannic compounds are not in a fouling form and that the majority of the organochlorinated matter has a molecular weight greater than 500 Da.