Assessing the biological status of fish in a river receiving pulp and paper mill effluents

This study compared the use of sentinel species- and community-based field approaches for assessing the biological status of fish living in a river receiving pulp and paper mill effluents. Three approaches were compared. Two approaches used sentinel species. One of these involved an internal/external examination of the fish that leads to the calculation of a fish health assessment index (HAI) and the other involved biochemical measurements of hepatic mixed function oxidase (MFO) activity and plasma steroid levels. The third approach characterized the fish community structure according to an index of biotic integrity (IBI). The comparison focused on how the methods respond to the hypothesis that recent process modifications/effluent treatment changes, resulting in demonstrable improvements in effluent quality, have beneficial effects on fish. Neither of the approaches using sentinel fish indicated clear mill-related influences either before or after the process modifications/effluent treatment changes. There was no evidence of depressed plasma steroids and increased MFO activity in fish frequently associated with mill effluent exposure in previous studies. While the HAI was higher at stations downstream from two mills, this could not be linked to effluent exposure alone. In contrast, the study of community structure showed a substantial improvement in fish assemblages at all the mill sites.     

Determining algal-available phosphorus in pulp and paper mill effluents: algal assays vs routine phosphorus analyses

We determined the potentially algal-available P (P(aa)) in pulp and paper mill effluents by two bioassay techniques (a dual-culture assay and a batch approach) and compared it with chemically analysed P (total P, total dissolved P, reactive P, dissolved reactive P and dissolved hydrolysable P). The mean P(aa) given by the dual-culture assay was within a 40% range of that given by the batch approach. The P(aa) obtained by both bioassays differed from total P. Dissolved reactive P appeared to be the most readily available chemical P fraction, but other P fractions also contributed to P(aa). The analysis of reactive P, which involves direct staining of an unfiltered sample, best approximated the P(aa) given by the dual-culture assay (relative error 9%). The results suggest that assessment of eutrophying effluent P can be improved by analysing simple chemical P fractions in wastewater. The fractions to be analysed, however, may be site specific.     

Fish community responses to pulp and paper mill effluents at the southern Lake Saimaa, Finland.

The fish community in sublittoral and profundal waters, at stony shores, and densities of vendace larvae were studied in the southern Lake Saimaa, Finland. The objective was to investigate the possible recovery of fish populations after modernizations at the pulp and paper mills discharging into the lake. Sublittoral and profundal waters were studied by gill net trial fishings, stony shores by electrofishing, and vendace larvae by beach seine. The research area was divided in a polluted (0.5-4.0% effluent), an intermediate (0.1-0.5%) and a 'clean' reference area. The fish community in sublittoral and profundal waters in the lake was dominated (> 60%) by perch and roach. Relative abundance of fish was highest in the polluted area, and lowest in the reference area. The number of species caught was similar among areas. The abundance of bleak and ruffe was highest in the polluted area, while the abundance of vendace and whitefish was highest in the intermediate and reference area. The fish fauna of stony shores in the lake was dominated by bullhead, stone loach and minnow, densities were lowest at polluted shores and highest in the intermediate area. Minnow, apparently a more sensitive species to pulp mill effluents, were not caught at the most polluted shores. The catch of vendace larvae was similar among areas, larvae were also caught in the vicinity of the mills. Compared with before the modernization at the mills, the relative abundance of perch in the polluted area was increased, ruffe decreased, while populations of whitefish and vendace showed signs of recovery. These changes may be explained by the reduced nutrient load and toxicicity of pulp mill effluents. At present, the fish community in the polluted area can be considered typical for a moderate eutrophication.     

Betulinol and wood sterols in sediments contaminated by pulp and paper mill effluents: dissolution and spatial distribution

The goal was to determine dissolution potency of betulinol and wood sterols (WSs) from pulp and paper mill-contaminated sediments and the current stratification for assessment the load due to potential erosion in the river-like watercourse. Both compounds are wood extractives, which may be toxic to benthos and fish. This research continues a study in which other wood extractives, resin acids and their derivative, retene, were analysed. Sediments were collected from 1, 3.5, 12, 15, and 33 km downstream from the pulp and paper mills, and from 2 upstream reference sites. The dissolution potency into sediment–water elutriates (1?+?4?v/v) was studied by two agitation times and temperatures. The vertical amounts of extractives were determined from the uppermost 20 cm of sediment. The amounts of extractives potentially released were estimated from the sediment layers 0–2 and 2–5 cm by using spatial interpolation. According to the interpolation, the total amount of betulinol and β-sitosterol was calculated as kg/ha in the whole sediment area. Significant concentrations of betulinol (1,666 μg/g, dw) and WSs (2,886 μg/g, dw) were measured from the sediments. According spatial interpolation, the highest calculated amount of betulinol (4,726 kg/ha) and that of the most abundant WS, β-sitosterol (3,571 kg/ha), were in the lake where the effluents were discharged. In the dissolution experiment, the highest concentration of betulinol in sediment (0–10 cm) and elutriate was 412 μg/g (dw) and 165 μg/l, respectively. For WSs, concentrations were 768 μg/g (dw) in sediment and 273 μg/l in elutriate. In a worst-case scenario, betulinol may be desorbed to water in concentrations which are hazardous to aquatic animals. Instead WSs are not a risk in this study area. The amount of desorption varied depending on the concentration of contaminants in sediment, the nature of disturbance, and the sediment organic carbon content.     

Assessing potential risks to wildlife and sportsmen from exposure to dioxin in pulp and paper mill sludge spread on managed woodlands

Potential human and wildlife exposures to TCDD in landspread pulp and paper mill sludge in the State of Maine were evaluated by means of a human health and an ecological risk assessment methodology. The highest historical concentrations of TCDD reported for these sludges do not present a risk to American woodcock, selected as an indicator species for this analysis. Concentrations of TCDD as high as 50 ppt in soil are not likely to produce adverse effects in the embryonic/hatchling stage of the woodcock. This soil concentration of TCDD does not present a significant risk to sportsmen and their families that may consume birds which inhabit these sites.     

Toxicity to Microtox, micro-algae and duckweed of effluents from the Bai Bang paper company (BAPACO), a Vietnamese bleached kraft pulp and paper mill

Toxicity of the combined effluent as well as effluents from different production units of BAPACO, a Vietnamese bleached kraft integrated pulp and paper mill, was studied using three ecotoxicological tests: Microtox, the micro-alga, Selenastrum capricornutum, and the duckweed, Lemna aequinoctialis. Physico-chemical characteristics of the effluents were also analyzed. Due to unstable operating conditions of the mill, a number of samples taken at different monitoring periods from each effluent were tested, in order to get statistically reliable ranges and averages of toxicity characteristics. For the mill combined effluent, it was found that the micro-algae were the most sensitive followed by Microtox bacteria, while duckweed was not sensitive. Microtox tests showed that the bleaching filtrate from the chlorination stage (C-stage) was the most toxic among all effluents in the mill. The combined effluent from the bleaching plant contributed the largest TEF (Toxicity Emission Factor) to the toxicity balance of the whole BAPACO combined effluent. A less-than-additive mode of toxicity was obtained. In spite of high pollution loads, e.g. BOD, COD, SS, to the Red River, the toxicity of the effluent was considered to be low. However, during periods of low river water sublethal toxic effects on the biota may be expected.     

Determination of dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) in paper pulp mill defoamer additives and in paper pulp samples

An analytical procedure has been developed for quantitatively measuring dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) present at part-per-billion levels in paper mill defoamers and paper pulp using gas chromatography coupled with either low resolution mass spectrometry (GC-LRMS) or high resolution mass spectrometry (GC-HRMS).     

Investigation of pathogenic Escherichia coli and microbial pathogens in pulp and paper mill biosolids.

Biosolids produced from pulp and paper mill wastewater treatment have excellent properties as soil conditioners, but often contain high levels of Escherichia coli. E. coli are commonly used as indicators of fecal contamination and health hazard; therefore, their presence in biosolids causes concern and has lead to restrictions in land-spreading. The objectives of this study were to determine the following: (1) if E. coli from the biosolids of a wastewater-free pulp and paper mill were enteric pathogens, and (2) if other waterborne microbial pathogens were present. E. coli were screened for heat-labile and heat-stable enterotoxin and verocytotoxin virulence genes using a polymerase chain reaction. Ten isolates were also screened for invasion-associated locus and invasion plasmid antigen H genes. None of the 120 isolates carried these genes. Tests for seven other microbial pathogens were negative. Effluents and biosolids from this mill do not contain common microbial pathogens and are unlikely to pose a health hazard.     

Effects of solar radiation on the fluorescence properties and molecular weight of fulvic acids from pulp mill effluents

The pulp and paper industry generates large volume of wastewater that adversely affects water resources. Lignin derived macromolecular compounds, similar to natural humic substances, are the main waste products in the pulp mill effluents. The UV-Vis and fluorescence spectroscopies were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. Solar irradiation of the solutions of these fulvic acids caused solution acidification and decay both in the UV-Vis absorbance and in the fluorescence. This decay was not the same for the whole spectra but pointed to the selective photodegradation of lignin typical structures. Furthermore, by sequential ultrafiltration it was found that during irradiation, the high-molecular weight fractions were destroyed and low-molecular-weight constituents, potentially more able to penetrate the cell membranes of living organisms were formed. Photodegradation of macromolecular organic matter from a kraft pulp mill effluent may be a key process occurring in natural waters that modifies the physicochemical properties of such effluents.     

Catalytic wet oxidation of the pretreated synthetic pulp and paper mill effluent under moderate conditions

In the present study, catalytic wet oxidation (CWO) was investigated for the destruction of organic pollutants in the thermally pretreated effluent from a pulp and paper mill under moderate temperature and pressure conditions. The thermal pretreatment studies were conducted at atmospheric pressure and 368K using copper sulfate as a catalyst. The thermal pretreatment reduced COD by about 61%. The filtrate of the thermal pretreatment step was used at pH 8.0 for CWO at 383-443K temperature and a total pressure of 0.85MPa for 4h. Catalysts used for the reaction include copper sulfate, 5% CuO/95% activated carbon, 60% CuO/40% MnO(2), and 60% CuO/40% CeO(2). Maximum COD reduction was found to be 89% during CWO step using 5% CuO/95% activated carbon with a catalyst loading of 8gl(-1) at 443K and 0.85MPa total pressure. Overall COD reduction for the pretreatment and the CWO was found to be 96%. Besides this, 60% CuO/40% CeO(2) catalyst also exhibited the similar activity as that of obtained with 5% CuO/95% activated carbon catalyst at 423K temperature and 0.85MPa total pressure. The pH of the solution during the experimental runs decreases initially due to the formation of carboxylic acid and then increases due to the decomposition of acids.     

Some factors influencing EROD activity in winter flounder (Pleuronectes americanus) exposed to effluent from a pulp and paper mill

EROD (ethoxyresorufin-O-deethylase) activity was determined in winter flounder, a sediment-inhabiting and non-migratory fish species, living near a pulp and paper mill in Newfoundland in relation to temperature, gender, sexual maturity, and lesions in the liver. Samples of liver were taken from fish captured by SCUBA divers at 0 degrees C, 5 degrees C and 16 degrees C. Enzymic activity was detected in fish living only above 0 degrees C. Adult males and juvenile fish had higher levels of EROD activity than prespawning females at 5 degrees C. Macrophage aggregates only or occurring simultaneously with bile ductule hyperplasia and clear cell foci in the liver, did not impair EROD activity but necrosis had a negative effect. Results from this study indicate the importance of water temperature, gender, sexual maturity and liver pathology in assessing EROD activity of fish in biomonitoring programs.     

Identification and level estimation of chlorinated neutral aromatic sulfur compounds and their alkylated derivatives in pulp mill effluents and sediments

Seven effluent samples from a modern pulp mill, in which chlorine and chlorine dioxide bleaching is used, and five sediment samples from the recipient watercourse were investigated for polychlorinated dibenzothiophenes (PCDBTs), polychlorinated thianthrenes (PCTAs), polychlorinated diphenylsulfides (PCDPSs) and for alkylated derivatives of these. Mainly di-, tri-, tetra- and pentachlorinated congeners were studied. Particles and filtrates from the effluents were analyzed separately. The concentration levels of the nonalkylated compounds were found to be higher in the filtrates than in the particles. Trichlorinated dibenzothiophenes and thianthrenes were found as the major congeners. Pentachlorinated derivatives were not found. Alkylated di- and trichlorodibenzothiophenes were detected in some samples, while alkylated chlorinated thianthrenes and diphenylsulfides were nondetectable. The estimated concentration levels of the compounds detected were in the range of 40–2700 pg/L in the pulp mill effluents and in the range of 2–40 pg/g dry weight in the sediments. Mixtures of methylated di- and trichlorodibenzothiophenes used as references in analyses were prepared from methylchlorobiphenyls. Some new pure model compounds were obtained by HPLC fractionation of the chlorination mixture of dibenzothiophene. Structures of these were determined by ¹H NMR.     

Characterisation and optimisation of three potential aerobic bacterial strains for kraft lignin degradation from pulp paper waste

Eight aerobic bacterial strains were isolated from pulp paper mill effluent sludge. Out of eight through nutrient enrichment technique three potential aerobic bacterial strains ITRC S(6), ITRC S(7) and ITRC S(8) were found capable to effectively degrade the kraft lignin (KL), a major byproduct of the chemical pulping process and main contributor to the colour and toxicity of effluent. Further, these potential strains (ITRC S(6), ITRC S(7) and ITRC S(8)) were biochemically characterised as Gram variable small rod, Gram negative rod and Gram positive rod respectively. Subsequently, 16S rRNA sequencing showed 95% base sequence homology and it was identified as Paenibacillus sp. (AY952466), Aneurinibacillus aneurinilyticus (AY856831), Bacillus sp. (AY952465) for ITRC S(6), IITRC S(7) and ITRC S(8), respectively. In batch decolourization experiments Bacillus sp. ITRC S(8) reduced the colour of lignin amended mineral salt medium, pH 7.6 by 65% after 6th d, at 30 degrees C, A. aneurinilyticus ITRC S(7) by 56% and Paenibacillus ITRC S(6) 43%. Under these conditions the three strains degraded the KL by 37%, 33% and 30%, respectively while the mixed culture of these three bacteria reduced colour by 69%, lignin by 40% and total substrate by 50% under same conditions. Biodegradation of the KL was not affected by low (<0.2 mg l(-1)) dissolved oxygen content; thus oxygen inhibition is more likely to be a metabolism-dependent event. Initially with 48 h incubation the decolourization was slow with decreased pH. Further incubation there was rapid decolourization with slight increase in pH at 6d compared with initial pH by increasing culture optical density. The lignin analysis from medium with HPLC indicated complete degradation rather than biotransformation with complete loss of absorbance peak at 280 nm.     

Effect of long term exposure to petroleum on mixed function oxygenases in fish: Further support for use of the enzyme system in biological monitoring

A number of long term, low level petroleum hydrocarbon exposures were carried out from 1978 to 1981 in order to further evaluate use of the mixed function oxygenase (MFO) system in biological monitoring. The studies involved exposure, at ambient temperatures, of fish from three separate families including (a) spawning codfish ($\text{Gadus morhua}$), (b) post-spawned sculpins ($\text{Myoxocephalus octodecemspinosus}$), and (c) gonadally maturing flounder ($\text{Pseudopleuronectes americanus}$). MFO activity remained elevated approximately four-fold in the liver, and three-fold in the gills of codfish exposed for four months to water concentrations of 0.30–0.60 ppm petroleum, at ?1-1°C. Similarly, liver enzyme activity remained elevated approximately three-fold in sculpins exposed to very low levels (0.15–0.20 ppm) of petroleum for three months, at 4–12°C. Results indicate that several years may be required before hydrocarbon concentrations are reduced in petroleum contaminated sediments, such as those heavily impacted by oil spills, to non-inducing threshold levels. Oil contaminated sediment was, even after a year of weathering, quite effective in inducing a high level of MFO activity (seven-fold) in flounder, at 11-6°C. A number of factors that might detract from use of the mixed function oxygenase system in biological monitoring were not realized in these long term studies with petroleum hydrocarbons.     

Nonylphenolic compounds in drinking and surface waters downstream of treated textile and pulp and paper effluents: a survey and preliminary assessment of their potential effects on public health and aquatic life

Eleven drinking water treatment plants, located downstream of textile plants or pulp and paper mills, have been sampled monthly during a year for the analysis of 17 nonylphenol ethoxylates (NP1-17EO) and two nonylphenoxycarboxylic acids (NP1-2EC). At all but one plant, results in the drinking water, for the sum of these 19 substances, range between below detection levels and 6.7 microg/l. Annual means are between 0.02 and 2.8 microg/l. At the other plant, the yearly average concentration is 10.4 microg/l and the monthly maximum is 43.3 microg/l. In the surface (pre-treatment) water, the annual mean concentrations of the 11 plants range between 0.14 and 17.8 microg/l and the recorded instantaneous maximum is 55.3 microg/l. According to Canadian health authorities, drinking water is a negligible route of human exposure to nonylphenolic compounds, even at the highest concentrations found in this study. After transformation of the data into nonylphenol equivalents, about 20% of the surface water samples exceed the Canadian 1 microg/l nonylphenol water quality guideline for the protection of aquatic life. Some results also exceed Québec's 6 microg/l nonylphenol guideline. The efficiency of the plants in removing nonylphenolic compounds from drinking water is highly variable, ranging from 11% to 99%.     

Extractability of trace elements in precipitated calcium carbonate (PCC) waste from an integrated pulp and paper mill complex

From the utilization point of view, it is notable that the total element concentrations in the precipitated calcium carbonate (PCC) waste were significantly lower than the maximal allowable heavy metal concentrations for fertilizers used in agriculture and in forestry, set on the basis of the EU and Finnish legislation. The easily soluble Ca concentration of 168.5g kg(-1) (d.w.) in PCC waste was 105 times higher than the typical value of 1.6g kg(-1) (d.w.) in the coarse mineral soil in Finland indicates that the PCC waste is a potential agent for soil remediation and for improving soil fertility if it is used as fertilizer. According to a five-stage sequential extraction procedure, the highest concentrations of most of the elements occurred either in HF+HNO3+HCl or H2O2+CH3COONH4 fraction. This means that the major part of the elements retained in the PCC waste are not easy to extract (leach) under conditions normally found in nature. This is beneficial since, if inorganic materials and by-products are utilized in earth construction, the content of harmful compounds must be low and the harmful components must be tightly bound to the matrix.     

The effects of sludge burning on the PCDD/PCDF content of ashes from pulp and paper mill hog fuel boilers

The results of a study designed to quantify the levels of PCDD/Fs in boiler and control device ashes resulting from burning sludge of bleached mill origin, admixed with bark, are summarized.     

Interspecies differences in mixed function oxidase activity in birds: Relationship between feeding habits, detoxication activities and organochlorine accumulation

The relationship between feeding habits and interspecies differences in the detoxication ability of the mixed function oxidase (MFO) system was investigated in birds. The role of MFO (particularly aldrin epoxidase activity) in the detoxication/bioaccumulation of organochlorines was also investigated. Euriphagic (yellow-legged herring gull (Larus cachinnans), black-headed gull (Larus ridibundus), jackdaw (Corvus monedula), magpie (Pica pica) and stenophagic (cormorant (Phalacrocorax carbo), coot (Fulica atra) and sparrow (Passer italiae)) species were collected in northern and central Italy. The following liver microsomal monooxygenase activities were measured: aldrin epoxidase, ethoxyresorufin dealkylation (EROD), benzyloxyresorufin dealkylation (BROD) and pentoxyresorufin dealkylation (PROD). NADPH-and NADH-cytochrome c reductase (NAD(P)H-CYT-CRED) and NADH-ferricyanide reductase (NADH-FERRIRED) activities were also measured in the liver microsomal fraction. Glutathione concentration (GSH) was measured in the liver cytosolic fraction. As a marker of liver damage gamma-glutamyl transpeptidase (GGTP) activity was assayed in the serum. The residues of organochlorines (HCB, pp'DDTs and PCBs) were determined in muscle samples. Omnivorous species, particularly the yellow-legged herring gull, had the highest aldrin epoxidase activities. In the yellow-legged herring gull the activity was approximately twice as high as in the jackdaw (p < 0.05), black-headed gull (p < 0.05) and coot (p < 0.05). Values five times lower were detected in the specialist fish-eater, the cormorant (p < 0.001). The lowest values of aldrin epoxidase activity were detected in the sparrow. Feeding habits were found to be related to evolutionary interspecies differences in MFO activity. A significant statistical correlation (r = 0.656) was found between the 'omnivore index' and MFO detoxication activity expressed as aldrin epoxidation. Organochlorines, and particularly PCBs, were higher in cormorants and yellow-legged herring gulls from a polluted lagoon than in the other species analysed (black-headed gull p < 0.01; sparrow p < 0.001; jackdaw p < 0.01; coot p < 0.001). Levels of pp'DDE were much higher in the cormorant and sparrow than in the other birds. Knowledge of the different species-specific detoxication abilities was found to be a useful tool for the identification of species potentially at risk in environments with high pollution by chlorinated hydrocarbons, or in general contaminants metabolized by the MFO system.     

The use of a sequential leaching procedure for heavy metal fractionation in green liquor dregs from a causticizing process at a pulp mill

A five-stage sequential leaching procedure was used to fractionate heavy metals (Cd, Cu, Pb, Cr, Zn, Fe, Mn, Ni, Co, As, V, Ba and Ti) in green liquor dregs into the following fractions: (1) water-soluble fraction (H2O), (2) exchangeable fraction (CH3COOH), (3) easily reduced fraction (HONH3Cl), (4) oxidizable fraction (H2O2 + CH3COONH4), and (5) residual fraction (HF + HNO3 + HCl). The green liquor dregs were derived from a causticizing process at a pulp mill at Kemi, Northern Finland. According to the leaching studies, the leachability of heavy metals in the water-soluble fraction varied between 0.5 and 2 mg kg(-1) expressed on a dry weight (d.w.) basis, indicating relatively low bioavailability of the metals. However, the concentration of Mn (2065 mg kg(-1); d.w.) showed a strong and of Zn (17.6 mg kg(-1); d.w.), Ni (39.7 mg kg(-1); d.w.) and Ba (32.0 mg kg(-1); d.w.) slightly tendency to be extracted in the exchangeable fraction. In addition, Zn, Mn, Ni, Co, V and Ba showed clear leachability in the easily reduced fraction, as well as Cd, Cu, Cr, Zn, Mn, As and Ba in the oxidizable fraction. For Cd, Cu, Cr, Zn, Mn, Ni, Co, Ba and Ti, the sum of leachable heavy metal concentrations in fractions 1-5 agreed relatively well with the "total" heavy metal concentrations. Recoveries of the sum of fractions 1-5 were 84-56% of those obtained by the US EPA method 3052 (i.e. concentrations obtained after microwave oven digestion with a mixture of HF and HNO3).     

脱木素工艺处理造纸废水的实践与机理

脱木素工艺为中小制浆企业的黑液治理提供了新的方法。系统中酸化纤维污泥减小碱木素胶粒间的斥力 ,吸附废水中已析出的木质素和细小纤维 ;酸破坏了系统中胶体的水化膜 ,增大了胶体的粒径 ;混凝剂中和胶体表面电荷 ,增加颗粒间的接触机会 ,同时发挥了絮凝沉降的作用。该工艺与传统工艺相比 ,减少了酸及混凝剂的用量 ,木素沉降速度快。当试验废水pH =5、绝干纤维污泥与进水CODCr质量之比为 1.1、硫酸铝投加量为 160mg/L时 ,CODCr去除率高于 63 %。