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.     

Chemically coupled microwave and ultrasonic pre-hydrolysis of pulp and paper mill waste-activated sludge: effect on sludge solubilisation and anaerobic digestion

The effects of alkali-enhanced microwave (MW; 50–175 °C) and ultrasonic (US) (0.75 W/mL, 15–60 min) pretreatments, on solubilisation and subsequent anaerobic digestion efficiency of pulp and paper mill waste-activated sludge, were investigated. Improvements in total chemical oxygen demand and volatile suspended solids (VSS) solubilisation were limited to 33 and 39 % in MW pretreatment only (175 °C). It reached 78 and 66 % in combined MW–alkali pretreatment (pH 12?+?175 °C), respectively. Similarly, chemical oxygen demand and VSS solubilisation were 58 and 37 % in US pretreatment alone (60 min) and it improved by 66 and 49 % after US–alkali pretreatment (pH 12?+?60 min), respectively. The biogas yield for US 60 min–alkali (pH 12)-pretreated sludge was significantly improved by 47 and 20 % over the control and US 60 reactors, respectively. The biogas generation for MW (150 °C)–alkali (pH 12)-pretreated sludge was only 6.3 % higher than control; however, it was 8.3 % lower than the MW (150 °C) reactor, which was due to the inhibition of anaerobic activity under harsh thermal–alkali treatment condition.     

Metal ion removal from water by sorption on paper mill sludge

Chromatographic columns packed with paper mill sludge are employed for metal ion recovery from water. The breakthrough curves show that cadmium, copper, lead and silver are removed from acid solutions (pH 2, 4); the affinity series is Pb(II)>Cu(II)>Ag(I)>Cd(II). Both the amount of metal retained and the metal-matrix interaction are pH dependent; the sorptive capacity increases with increasing pH. When the metals are present together at the same initial concentrations a competition among the different ions occurs although the affinity order remains unchanged. In metal recovery from the paper mill sludge column, the total amount of the cadmium and copper is displaced by HCl 1.0 M, 65% of the lead by HCl 0.1 M and 75% of the silver by HNO(3) 0.1 M. More than 95% of copper and lead and less than 20% of cadmium were recovered with HCl 0.1 M when the metals were present at the same time.     

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.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in paper making from a pulp mill in China

An extensive investigation on the input, formation and fate of PCDD/Fs in a pulp mill using reeds as raw materials in China was carried out. The main PCDD/Fs input in the production process came from reeds, which may be contaminated by PCDD/Fs from sodium pentachlorophenate to control snailborne schistosomiasis. High levels of I-TEQ in the products were observed.     

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.     

Production and characterization of sintered ceramics from paper mill sludge and glass cullet

Three different types of paper mill sludge were first incinerated and then attrition milled separately or mixed with glass cullet in varying proportions to obtain powders of different compositions. These powders were then dried, sieved, uniaxially pressed into samples and air sintered. Fired samples were characterized by density, water absorption, shrinkage on firing, strength, hardness and fracture toughness measurements; SEM and X-ray diffractions were also carried out to investigate microstructure and phase composition. Some sintered samples displayed fairly good physical and mechanical properties as a consequence of their low residual porosity and fine microstructure.     

造纸污泥生物干化特性及其影响因素实验研究

采用自主设计的污泥生物干化实验装置,研究了造纸污泥生物干化特性及其影响因素。重点研究了物料配比和评价参数（温度、pH值、含水率、挥发性固体、ATP含量和淀粉分解菌数量等）的变化规律。结果表明：通过正交实验获得生物干化的最优物料配比为：淀粉（25g／500g）、锯末（40g／500g）、接种量（15mL／500g）和磷酸二氢钾（5g／500g）。造纸污泥生物干化过程中,物料温度、pH值、含水率、挥发性固体、ATP含量和淀粉分解菌数量等指标变化规律性强,效果指示性明显,均可作为污泥干化效果的表征参数。在最优工艺条件下,污泥温度达到47．8℃,经过7d生物反应后,含水率降低到50．3％,挥发性固体降低到49．5％,生物干化效果显著。     

制浆造纸废水生化出水的混凝处理研究

研究了硫酸铝和三氯化铁对制浆造纸废水生化出水的处理效果.研究发现,不调节原水pH值,硫酸铝投加量为600 mg/L或三氯化铁投加量为300mg/L时,混凝后废水的COD＜150 mg/L,色度＜50倍,出水均符合现阶段排放标准.混凝剂比较发现,在最佳反应条件下,2种混凝剂的处理效果相当,但硫酸铝混凝的成本低于三氯化铁....     

造纸工业污泥燃烧特性及动力学实验研究

在不同升温速率及与其他污泥不同混合比例条件下,利用热重法对造纸污泥和含工业污水污泥进行了实验研究。结果表明,造纸污泥与含工业污水污泥表现出不同的DTG曲线形式,其中造纸污泥固定碳燃烧峰失重较为明显。随着升温速率的提高,造纸污泥的燃烧速率加大,燃尽时间缩短,提高了其综合燃烧特性;加入含工业污水污泥后,造纸着火性能及燃尽性能均得到改善。采用积分法（Coats-Redfern方程）计算得到各阶段燃烧反应的机理方程及相应的活化能参数,表明活化能的大小与试样的燃烧阶段是相对应的。     

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).     

添加造纸污泥对土壤-白萝卜系统中镉迁移的影响

采用盆栽实验方法研究了红壤、紫色土母质发育的水稻土（红壤、紫色土）添加不同量的造纸污泥对土壤-白萝卜系统Cd迁移的影响。结果表明：添加造纸污泥能提高土壤的pH、有机质、N、CEC,降低紫色土有效态Cd含量;添加造纸污泥显著降低了白萝卜叶、地下茎中Cd含量,显著降低土壤-白萝卜系统中Cd的转运系数及富集系数;Cd的转运系数和富集系数与土壤pH、有机质存在显著负相关关系;红壤和紫色土中造纸污泥最适添加量分别为5%、10%时,白萝卜根茎中Cd含量以及Cd的转运系数和富集系数可达到相对最低值。造纸污泥农用能够在一定程度上降低重金属有效性,阻止其在土壤-作物系统中的迁移,可以为造纸污泥资源化和安全利用提供新途径。     

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.     

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.     

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.     

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.     

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.     

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.     

造纸白泥和粉煤灰的添加对污泥消化液中氮磷回收的影响

污泥厌氧消化液中含有丰富的氮磷,若直接排放到环境中,将会对附近水体造成严重污染。由于消化液中Mg^2＋和Ca^2＋的含量很低,严重影响了氮磷的回收效果。把造纸白泥和粉煤灰引入到污泥厌氧消化液氮磷的回收当中,可以明显地提升消化液pH和提高PO4^3-P和NH3-N回收率。实验结果表明：当造纸白泥添加量为4g／（L·h）时,曝气12h后,pH可达10．19,此时PO4^3-P和NH3-N回收率分别达到64％和45％;而当粉煤灰添加量为4g／（L·h）时,曝气12h后,pH达到9．63,PO4^3-P和NH3-N回收率分别为46％和41％。但仅用曝气方式处理,12h后,pH值仅为8．52,PO4^3-P和NH3-N回收率分别只有20％和18％。实验结果还表明,水力停留时间（HRT）越大,pH上升速度越快,幅度越大,氮磷的回收效果就越好。     

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.