Search

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.

Paper sludges were traditionally landfilled or burned. Over the years, the use of paper sludges on soils has increased, as well as the concerns about their environmental effects. Therefore, the chemical characterization of paper sludges and their young (immature) compost needed to be investigated, and over 150 inorganic and organic chemicals were analyzed in de-inking paper sludge (DPS). In general, nitrogen, phosphorus and potassium contents were low but variable in raw DPS and its young compost. The contents of arsenic, boron, cadmium, cobalt, chromium, manganese, mercury, molybdenum, nickel, lead, selenium, and zinc were also low and showed low variability. However, the copper contents were above the Canadian compost regulation for unrestricted use and required a follow-up. The fatty- and resin acids, and polycyclic aromatic hydrocarbons were the organic chemicals measured at the highest concentrations. For resinic acids, care should be taken to avoid that leachates reach aquatic life. For polycyclic aromatic hydrocarbons, naphthalene should be followed until soil content reaches 0.1 microg g(-1), the maximum allowed for soil use for agricultural purposes according to Canadian Environmental Quality Guidelines. In young compost, the concentration of these chemical families decreased over time and most compounds were below the detection limits after 24 weeks of composting. In raw DPS, among the phenol, halogenated and monoaromatic hydrocarbons, dioxin and furan, and polychlorinated biphenyl families, most compounds were below the detection limits. The raw DPS and its young compost do not represent a major threat for the environment but can require an environmental follow-up.

Due to the regulation on bisphenol A (BPA) in several industrialized countries, the demand for other bisphenol analogues (BPs) as substitutes for BPA is growing. Eight BPs were determined in sludge from 40 representative wastewater treatment plants (WWTPs) in Korea. Total concentrations of BPs (ΣBP) in sludge ranged from

Bleached kraft pulp and paper mill effluents (BKMEs) are known to have adverse effects on aquatic organisms. One of the effects of BKMEs is its ability to induce cytochrome P4501A activity in exposed fish. 7-Ethoxyresorufin O-deethylase (EROD) activity is the most common biomarker used to measure the mixed-function monooxygenase activity. In this study, Tilapia were exposed to BKMEs using different exposure systems and their hepatic EROD activity, as well as liver/somatic index (LSI), were determined. In the Phase I study, Tilapia treated with betaNF and a whole (100%) BKME using a static, non-renewal system exhibited statistically significant EROD induction, but LSI values were not altered. In the Phase II study, fish were either caged in the mill's fishpond with the whole effluent passing through or cultured in tanks receiving 100% of the BKME continuously using a flow-through system in the laboratory. Their EROD activities were then compared with the non-exposed fish (control). The EROD activities in both groups of fish were elevated significantly with the greatest induction being observed in the field-exposed group. The LSI values in all of the field-exposed fish were significantly greater than the control Tilapia. The EROD assay was sensitive in detecting biological changes in fish exposed to the BKME. Further studies are warranted to better understand the impacts of BKMEs on aquatic organisms in Taiwan.

A dioxin mass balance in an Spanish municipal waste incinerator (MWI) is presented. Input and output inventories from two sampling collection episodes including the analysis of PCDD/PCDF in urban solid waste (USW), stack gas emissions, fly ash and slag are reported. In one collection the levels of USW were around 8 pg I-TEQ/g and non-thermal destruction was observed overall. In the other collection the levels of USW were higher (around 64 pg I-TEQ/g) and the dioxin balance revealed a thermal destruction. Analysis of the different waste materials (textile, organic, plastic, wood and paper) was performed separately and the textile samples presented the highest levels.

High molecular mass fractions of lignin and humic compounds in sediments and waters downstream of a pulp mill were characterized applying pyrolysis-gas chromatography-mass spectrometry. The results were compared to those obtained using reversed phase HPLC on the cupric oxide oxidation products. The chromatographic data of both pyrolysis and cupric oxide oxidation were also subjected to the principal component analysis (PCA). The sediment samples and fractions obtained by ultrafiltration of river water samples were freeze dried prior to characterization. The sediment samples were also extracted using 2 M sodium hydroxide solution. The extracts were ultrafiltrated, freeze dried and compared to the freeze dried original sediments using the procedures mentioned above. The amounts of HMMs obtained from the sediments ranged from 62 mg to 97 mg per one gram of sediment. Gel permeation chromatography was applied to samples obtained from sediments by extraction with tetrahydrofuran. The weight average molecular weights of these fractions were in the range of 1500–2300 amu.

The use of waste wood as an energy carrier has increased during the last decade. However, the higher levels of alkali metals and chlorine in waste wood compared to virgin biomass can promote the formation of deposits and organic pollutants. Here, the effect of fuel composition and the inhibitory effects of ammonium sulfate, (NH4)2SO4, on the concentrations of persistent organic pollutants (POPs) in the flue gas of a lab-scale combustor was investigated. Ammonium sulfate is often used as a corrosion-preventing additive and may also inhibit formation of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). In addition to PCDDs and PCDFs, polychlorinated naphthalenes (PCN) and biphenyls (PCB) were also analyzed. It was found that the flue gas composition changed dramatically when (NH4)2SO4 was added: CO, SO2, and NH3 levels increased, while those of HCl decreased to almost zero. However, the additive's effects on POP formation were less pronounced. When (NH4)2SO4 was added to give an S:Cl ratio of 3, only the PCDF concentration was reduced, indicating that this ratio was not sufficient to achieve a general reduction in POP emissions. Conversely, at an S:Cl ratio of 6, significant reductions in the WHO-TEQ value and the PCDD and PCDF contents of the flue gas were observed. The effect on the PCDF concentration was especially pronounced. PCN formation seemed to be promoted by the elevated CO concentrations caused by adding (NH4)2SO4.

A laboratory method is presented for investigating the biodegradation of an organic test material in an aerobic composting system based on the evolution of carbon dioxide. In addition to carbon conversion, biodegradation can also be monitored through weight loss and physical disintegration. The test method is different from other biodegradation tests, especially aquatic tests, because of the elevated temperature representative for real composting conditions and also because of enhanced fungal degradation activities. A ring test was run using paper and poly-beta-hydroxybutyrate/valerate as test materials and cellulose powder as a reference material. The test results and the experience gained by the participants showed that the method is suitable and practicable. Experience with real technical-scale composting facilities confirms that the method provides test results of high predictive value. The test is designed to become a European Standard in connection with determining the compostability of packagings and packaging materials.

Blood samples from 34 workers at a pulp and paper mill and from 14 control persons were analysed for 2,3,7,8-substituted PCDDs and PCDFs. There were no statistically significant differences in total lipid-adjusted PCDD/PCDF concentrations, expressed as toxic equivalents, in blood plasma between the potentially exposed bleaching plant or paper mill workers and the controls. The mean level was 61 pg/g I-TEQ in bleaching plant workers, 60 pg/g I-TEQ in paper mill workers and 49 I-TEQ pg/g in controls. Regarding the concentrations of individual isomers, however, there was an indication that the blood plasma concentrations might be affected by the living and working environment.

Current study presents the effect of irrigation with different compositions (0%, 20%, 40%, 60%, 80% and 100%) of PBM effluent on growth and antioxidant potential of Brassica rapa var. rapa L. plants. Seeds were exposed to different PBM effluent compositions, which resulted in significant decrease in their germination potential with elevated delay index. Significant changes in growth parameters (plant height, number of leaves and leaf area) were recorded for turnip plants at regular intervals (25, 50 and 75 d) as function of PBM effluent proportion. Response of biochemical and antioxidant constituents in different parts of turnip, against stress induced by PBM effluent, was assessed by estimating the contents of chlorophyll (a + b), carotenoids, protein, phenolics, flavonoids, ascorbic acid and malondialdehyde. Antioxidant activity was evaluated by measuring DPPH radical scavenging potential. The results of this study suggest that the impact of PBM effluent irrigation is dependent on concentration of effluent in irrigation mixture and is very clear on plant growth and antioxidant attributes. Maximum benefits were secured at 40% PBM effluent to irrigate turnip plants till maturity while higher concentrations were found useful for shorter period (25–50 d).

The removal of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) from solid matrices has received considerable attention because of the environmental persistence, bioaccumulation, and potential toxicity of these compounds. This study presents a simple method using concentrated HNO(3) as a suppression agent, and methanol-modified supercritical carbon dioxide (Sc-CO(2)) extraction for removing PFOS and PFOA from solid matrices. The optimal conditions were 16 M HNO(3) and 20% (v/v) methanol containing Sc-CO(2), under a pressure of 20.3 MPa and a temperature of 50 °C. Extraction time was set at 70 min (40 min for static and 30 min for dynamic extraction). PFOA and PFOS were identified and quantitated by liquid chromatography/mass spectrometry. The extraction efficiencies (with double extractions) were close to 100% for PFOA and 80% for PFOS for both paper and fabric matrices. The extraction efficiencies for sand were approximately 77% for PFOA and 59% for PFOS. The results show that this method is accurate, and effective, and that it provides a promising and convenient approach to remediate the environment of hazardous PFOA and PFOS contamination.

One of the chemical breakdown products of nonylphenol ethoxylates, 4-nonylphenol (4-NP), accumulates in organisms and is of concern as an environmental pollutant due to its endocrine disrupting effects. We measured 4-NP levels in the seawater, sediment, and twelve organisms within the California estuary, Morro Bay, and examined biomagnification of 4-NP using stable isotope abundances (δ(15)N and δ(13)C) to quantify trophic position. 4-NP concentrations in organisms from Morro Bay included 25000±8600 ng g(-1) lw in liver of California sea lion, 14000±5600 ng g(-1) lw in liver of harbor porpoise, 138000±55000 ng g(-1) lw in liver of sea otters, 15700±3600 ng g(-1) lw in liver of seabirds, 36100±6100 ng g(-1) lw in arrow goby fish, 62800±28400 ng g(-1) lw in oysters, and 12700±1300 ng g(-1) lw in mussels. 4-NP levels generally showed a pattern of trophic dilution among organisms in Morro Bay, with exceptions of biomagnification observed between three trophic links: mussel to sea otter (BMF 10.9), oyster to sea otter (BMF 2.2), and arrow goby to staghorn sculpin (BMF 2.7). Our examination of other west coast estuaries of USA and Canada revealed that mean 4-NP concentrations in gobies and mussels from Morro Bay were significantly higher than those from a more urbanized estuary, San Francisco Bay (goby: 11100±3800 ng g(-1) lw) and from a remote estuary, Bamfield Inlet, Canada (goby: 9000±900 ng g(-1) lw, mussel: 6100±700 ng g(-1) lw). Relative to other estuaries worldwide, 4-NP levels in seawater (0.42±0.16 μg L(-1)) and sediment (53±14 ng g(-1) dw) of Morro Bay are low, but gobies and oysters have higher 4-NP levels than comparable fauna.

The potential health and environmental hazards of carbon nanotubes (CNTs) have been a concerned issue. However, in contrast to the wide recognition of the toxicity of CNTs, little attention has been paid to the decontamination/remediation of CNT pollution. In this study, we report that CNTs can be removed from aqueous environment. In the presence of Ca²(+), CNTs aggregate quickly to micron size and then enable easy and effective removal via normal filtration. After filtration, CNT suspension becomes colorless with the remnant CNT concentration less than 0.5 μg mL⁻¹, a safe dose based on the published data. The filtration approach also works well in the presence of typical surfactant and dissolved organic matter. The removal efficiency is Ca²(+) concentration-dependent and regulated by the initial pH value and ionic strength. Our study is helpful for future decontamination of CNTs from aqueous environment.

Aroclor 1242 contains a high percentage of lightly chlorinated congeners, which makes it susceptible to congener profile alterations as a result of physical-chemical environmental weathering by water washing, evaporation, and volatilization. The analysis of the variability of congener profiles in paper sludge samples using PCA, mixing models, and correlation (R(2)) analysis, provided an integrated description of the behavior of Aroclor 1242 after its release in the environment. The results showed that the total PCB concentration decreased as the sample experienced weathering, with the congener profile of Aroclor 1242 shifting towards resembling heavier Aroclors as lighter congeners were lost. Mixing model analysis confirmed that a sample containing weathered Aroclor 1242 could easily be misidentified by laboratories as containing a mix of heavier Aroclors. The R(2) analysis showed that the profile of the congeners within a homologue group remained the same after weathering. This analysis showed that congeners that belong to the same level of chlorination behave similarly in such a manner that retains their overall profile when exposed to physical weathering.

Paper recycling is an environmental important activity that is carried out in all the countries, but during the recycling process a paper waste is produced. Generally these wastes are placed in landfill sites but it is possible to profit it as secondary fuel and raw material in manufacture furnaces. In this work the combustion of the waste papers with cement and ceramic raw material has been studied with the objective to analyse the interaction of these substances with the emitted pollutants like PAHs and PCDD/Fs. The results of the study show that the presence of inorganic material produces an increment in the lighter PAH emission but chlorinated compounds are not affected. The PCDD/F emission level found in the combustion of this waste is quite low compared with other wastes subjected to similar conditions.

Tetrabromobisphenol-A (TBBA) is the most common brominated fire retardant. In this study, a TBBA containing paper laminated printed circuit board (PCB) prepared from novolac was pyrolysed by both TGA and in a quartz glass reactor between 40 and 1,000 degrees C. The products were online detected by MS. It was found that the PCB degraded in three steps. Step one (

Iminodiacetic acid was immobilized on waste paper by chemical modification in order to develop a new type of adsorption gel for heavy metal ions. Adsorption behavior of the gel was investigated for a number of metal ions, specifically Cu(II), Pb(II), Fe(III), Ni(II), Cd(II), and Co(II) at acidic pH. From batch adsorption tests, the order of selectivity was found to be as follows: Cu(II) ≫ Fe(III) > Pb(II) > Ni(II) ≫ Co(II) > Cd(II). Column tests were carried out for pairs of metal ions to understand the separation and pre-concentration behavior of the gel. It was found that mutual separation of Ni(II) from Co(II) and that of Pb(II) from Cd(II) can be achieved at pH 3. Similarly, selective separation of Cu(II) from Cu(II)–Fe(III) and Cu(II)–Pb(II) mixtures at pH 1.5 and 2, respectively, was observed by using this new adsorption gel. In all cases, almost complete recovery of the adsorbed metal was confirmed by elution tests with HCl.

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 168.5 g kg −1 (d.w.) in PCC waste was 105 times higher than the typical value of 1.6 g 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 + HNO 3 + HCl or H 2 O 2 + CH 3 COONH 4 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.

Denitrification is applied in the tertiary treatment of wastewater to reduce nitrogen pollution. Fluorescence in situ hybridization (FISH), catalyzed reporter deposition (CARD)-FISH, cloning, and scanning electron microscopy (SEM) were applied to follow the evolution of the microbial composition and structure of granular sludge in chemolithotrophic denitrifying bioreactors fed with nitrate and thiosulfate. FISH oligonucleotide probes for the chemolitoautotrophic denitrifiers Thiobacillus denitrificans and Thiomicrospira denitrificans were designed and their utility tested. CARD-FISH and cloning data showed that bacterial diversity in the biofilms changed during the reactor operation. Chemoorganotrophic fermentative Gram-positive strains in the phyla, Actinobacteria and Firmicutes, were dominant in the methanogenic inoculum, both in terms of biodiversity and in number. Other significant phyla were Bacteroidetes and Chloroflexi. After 6 months of operation, Proteobacteria became dominant (83% of the clones). The diversity of Gram-positive bacteria was partially maintained although their abundance decreased notably. After 110 d of operation, the abundance of Tb. denitrificans cells increased considerably, from 1% to 35% of total DAPI-stained cells and from no isolated clones to 15% of the total clones. Tm. denitrificans only represented a minor fraction of the microorganisms in the sludge (1-4% of the DAPI-stained cells). These findings confirm that Tb. denitrificans was the dominant chemolitoautotrophic denitrifying microorganism in the bioreactors. The Archaeal diversity remained almost unchanged and it was represented mostly by Methanosaeta soehngenii. SEM results indicated a considerable loss in the integrity of the sludge granules during the operation, with risk of sludge buoyancy.

An efficient sequential, biological and photocatalytic treatment to reduce the pollutant levels in wastewater due to the bleaching process during paper production is reported. For a biological pre-treatment, 800 ml of non-sterilized effluent was inoculated with Trametes versicolor immobilized in polyurethane foam, with 25 g l(-1) glucose, 6.75 mM CuSO(4), and 0.22 mM MnSO(4) added, and cultured at 25 degrees C with an air flow of 800 ml min(-1) for 8d. The fungus did not inhibit growth of the heterotropic populations of the effluent. After 4d of culture, the chemical oxygen demand (COD) reduction and colour removal (CR) were 82% and 80%, respectively, with laccase (LAC) and manganese peroxidase (MnP) activities of 345 U l(-1) and 78 U l(-1), respectively. The COD reduction and CR correlated positively (p

TiO2 powder-containing paper composites, called TiO2 paper, were prepared by a papermaking technique, and their photocatalytic efficiency was investigated. The TiO2 paper has a porous structure originating from the layered pulp fiber network, with TiO2 powders scattered on the fiber matrix. Under UV irradiation, the TiO2 paper decomposed gaseous acetaldehyde more effectively than powdery TiO2 and a pulp/TiO2 mixture not in paper form. Scanning electron microscopy and mercury intrusion analysis revealed that the TiO2 paper had characteristic unique voids ca. 10 μm in diameter, which might have contributed to the improved photocatalytic performance. TiO2 paper composites having different void structures were prepared by using beaten pulp fibers with different degrees of freeness and/or ceramic fibers. The photodecomposition efficiency was affected by the void structure of the photocatalyst paper, and the initial degradation rate of acetaldehyde increased with an increase in the total pore volume of TiO2 paper. The paper voids presumably provided suitable conditions for TiO2 catalysis, resulting in higher photocatalytic performance by TiO2 paper than by TiO2 powder and a pulp/TiO2 mixture not in paper form.

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.

The dissolution potency of hydrophobic resin acids (RAs), retene and wood sterols from sediments was studied. These wood extractives and their metabolites are sorbed from pulp and paper mill effluents to downstream sediments. With harmful components like these, sediments can pose a hazard to the aquatic environment. Therefore, sediment elutriates with water were produced under variable conditions (agitation rate and efficiency, time), and concentrations of the dissoluted compounds were analyzed. Both naturally contaminated field sediments and artificially spiked sediments were studied. By vigorous agitation RAs can be released fast from the sediment matrix and equilibrium reached within 3 days. Compared to RAs, desorption of retene from lake sediment was slower and did not completely reach equilibrium in 23 days. Sterols spiked to pristine sediment with a 33-day contact time desorbed faster than those associated authentically with industrial sediment of from a contaminated lake. Simulating the water turbulence adjacent to a sediment surface by low and high rate of agitation in the laboratory, an increase in the mixing rate after 43-day elutriation suddenly released a high amount of wood sterols. The results indicate wide variation between hazardous chemicals in their tendency to dissolution from sediment solids. Erosion and hydrology adjacent to the sediment surface, as well as risks from dredging activities of sediments, may expose lake biota to bioactive chemicals.

An irrigation process through volcanic soil columns was evaluated for bleached Kraft mill effluent pollutants retention. The system was designed to remove color and phenolic compounds and a simple kinetic model for determining the global mass transfer coefficient and the adsorption rate constant was used. The results clearly indicate that the global mass transfer coefficient values ( K c a ) and the adsorption rate constants are higher for the irrigation processes onto acidified soil. This means that the pretreatment of washing the volcanic soil with an acid solution has a positive effect on the adsorption rate for both pollutant groups. The enhanced adsorption capacity is partially explained by the activation of the metal oxides present in the soil matrix during the acid washing process. Increasing the flow rate from 1.5 to 2.5 ml/min yielded higher ( K c a ) values and adsorption rate constants for both pollutant groups. For instance, regarding color adsorption onto acidified soil, there is an increment of 43% in the ( K c a ) value for the experiment with a flow rate of 2.5 ml/min. Increasing the porosity of the column from 0.55 to 0.59, yielded a decrease in the ( K c a ) values for color and phenolic compounds adsorption processes. Onto natural soil for example, these decreases reached 21% and 24%, respectively. Therefore, the ( K c a ) value is dependent on both the liquid-phase velocity (external resistance) and the soil fraction in the column (internal resistance); making forced convection and diffusion to be the main transport mechanisms involved in the adsorption process. Analyzing the adsorption rate constants ( K c a )/ m , phenolic compounds and color adsorption rates onto acidified soil of 2.25 × 10 −6 and 2.62 × 10 −6 l/mg min were achieved for experiment 1. These adsorption rates are comparable with other adsorption systems and adsorbent materials.

The aim of this work has been to study the viability of ozone and/or UV in the treatment of cardboard industry effluents. Several model compounds have been chosen for the experiments: guaicol, eugenol, glucose, acetate and butyrate. Significant differences in the ozonisation rates are observed between phenolic products coming from lignin (eugenol and guaiacol) and aliphatic compounds. Reactions fit in all cases a pseudo-first order kinetics and are influenced by the pH of the solution. Real effluents have also been tested, and the COD decrease has been found to depend on the fatty acids/phenols ratio. Finally, respirometric studies have shown an increase in the BODst in effluents subjected to a mild oxidation, while under stronger conditions a BODst decrease is observed.

The purpose of this study was to evaluate photodegradabilities of the following new low-nitrogen chelating agents: N-bis[(carboxymethoxy)ethyl]glycine (compound 1), N-bis[(1,2-dicarboxyethoxy)ethyl]glycine (compound 2) and N-bis[(1,2-dicarboxyethoxy)ethyl]aspartic acid (compound 3). At first photodegradation of these chelating agents as uncomplexed Na-compound 1–3 and Cu(II) complexes were tested, both in lake and distilled water, by exposing them to near-UV region radiation at the range of 315–400 nm. Uncomplexed Na-compounds 2 and 3 were selected to sunlight exposure experiments carried out in lake and distilled water. Compound 3 was also tested in sunlight as Cu and Ca complexes in both solutions. Photodegradation of Na6-compound 3 in distilled water was studied by exposing it to radiation at the wavelength of 253.7 nm. Photodegradation products were analysed by means of GC-MS (gas chromatography with mass selective detector). The results demonstrated that compound 1 was quite photostable even as Cu complex while compounds 2 and 3 were found to be photodegradable. Over 90% reduction of compound 3 was achieved during one week and 80% reduction of compound 2 in two weeks' time when they were added as Na salt to lake water and exposed to sunlight. Compound 3 as Cu complex degraded totally in the sunlight in less than one week. In the case of compound 3, the degradation rate decreased depending on the counter cation in the order Cu > Na ⩾ Ca. The study demonstrated that photodegradation of Na6-compound 3 does not result in total mineralization of the compound. A photodegradation pathway for Na6-compound 3 is proposed.

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 PbðIIÞ > CuðIIÞ > AgðIÞ > CdðIIÞ. 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 HNO3 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. 2003 Elsevier Science Ltd. All rights reserved.

Toluene and formaldehyde are malodorous and cause indoor pollution. These materials have received much attention as hazardous and malodorous substances. It is well known that long-term exposure to even fairly low levels of toluene and formaldehyde brings about the risk of asthma and eczema. In this study, a composite TiO2–zeolite (ZE) sheet prepared using a papermaking technique was applied to remove toluene and formaldehyde under UV irradiation. The optimum composition of the TiO2 (Ti)–ZE sheet was studied in detail with regard to the effective removal of various indoor pollutants. Gaseous toluene and formaldehyde were removed by a composite TiO2–ZE sheet with different efficiencies depending upon the ratio of Ti/ZE in the composite sheet. The composite sheets could decompose formaldehyde and toluene repeatedly after being recharged. It was shown that the sheets are potentially applicable as highly functional materials to be placed on walls and ceilings of houses for the removal of various indoor pollutants.

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.

The effects of UV radiation on the acute toxicity of retene (7-isopropyl-1-methylphenanthrene) to Daphnia magna Straus were studied. Dehydroabietic acid (DHAA) from which retene is formed in the vicinity of pulp and paper industry was also studied. Pyrene, anthracene, and phenanthrene were used as model PAH compounds. The time taken for immobilization (ET50) was monitored under biologically effective UV-B dose rates of 240, 365, 565, and 650 mW m−2 (UV-A and visible light also present). Median effective concentrations (EC50) were determined after a 15-min UV exposure (565 mW m−2) followed by 24 h in the dark. Retene ( 10–320 μg l −1 ) was not acutely toxic in the dark. The induction of phototoxicity was in agreement with the absorption properties of the compounds (absorption peak of retene at around 300 nm). Photoinduced toxicity followed an order pyrene>anthracene>retene. Phenanthrene and DHAA were not acutely phototoxic. Accumulation of the compound in Daphnia before UV exposure was essential. Some changes in the absorption spectra of the compounds were seen after a 5-h UV irradiation (565 mW m −2 ) , but none of the irradiated compounds were acutely toxic without further UV exposure. Therefore, the enhanced acute toxicity was primarily due to internal photosensitization reactions rather than photomodification. The dissolved fraction of 25% pulp and paper mill effluent reduced phototoxicity by attenuating UV radiation. The phototoxicity of retene was a function of both the exposure concentration and the UV-B dose rate, but relatively high UV-B dose rates and concentrations were needed for the acute photoinduced toxicity.

A variety of chlorinated catechols and guaiacols relevant to pulp bleaching were synthesized by employing fundamental differences in the acidities of phenolic hydroxyl groups in chlorinated catechols, and directive effects in guaiacols.

This paper describes work performed on the sampling and analysis of non-condensable gases (NCG) emitted from diffuse sources of a Portuguese Kraft pulp mill, which is the background information for a NCG collection, treatment and disposal system. The variability found in the composition of the gaseous compounds showed the existence of gaseous streams other than typical total reduced sulphur (TRS) compounds as usually described. From the measured TRS concentrations and the gas flow rate from each source it was possible to calculate the emission flow rate, E, of each source. These emission flow rates were then divided into three categories which are quite useful to identify significant sources and to choose abatement techniques. The methodology presented allows for a precise quantification of sources so that similar emissions can be grouped for treatment purposes. Sources with an emission flow rate bigger than 1 kg/h have a marked effect on the overall TRS emissions of the mill, as they are major contributors. It was also found that a new analytical procedure using Restek columns is more easy to use and overcomes operational problems noticed previously, namely a run time of 20-25 min instead of 50-60 min.

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.

Chlorinated derivatives of bisphenol A were detected in the final effluents of eight paper manufacturing plants in Shizuoka, Japan, where thermal paper and/or other printed paper is used as the raw material. Their amounts were determined by gas chromatography/mass spectrometry (GC/MS) after treatment with N, O-bis(trimethylsilyl)trifluoroacetamide, and ranged from traces to 2.0 microg/l. They are likely produced by chlorination of bisphenol A, which was released into the effluents from the pulping process of wastepaper, during or after bleaching with chlorine.

A cellulose bleaching effluent (E1) was degraded in batch conditions by photocatalysis using TiO2 and ZnO supported on glass Raschig rings. The effluent was completely decolourised and the total phenol content was reduced by 85% after 120 min treatment with both catalysts. Partial mineralization of the organic matter was confirmed by total organic carbon (TOC) reduction, approximately 50%. The residual organic matter shows a low acute toxicity as compared to the initial values and AOX values are strongly reduced after the photocatalytic oxidation. Molecular mass distribution showed that high molecular mass compounds were almost completely degraded.

Diffuse reflectance spectroscopy can be successfully used for the quantitative determination of small amounts of pollutants like metals. The remission function was found to be linearly proportional to the concentration, when we applied the Kubelka-Munk equation. The color reactions of Cu(II), Co(II), and Ni(II) with dithiooxamide, were realised on filter paper. Reaction between Fe(III) and ammonium thiocyanate was realized on filter paper and gelatine matrix. All measurements were accomplished with a laboratory-constructed reflectometer. We have obtained a calibration curve by plotting the optical density of reflectance A(R) vs log of the mol l(-1) concentration. Limits of detection at the 10(-4) M level were estimated for all the compounds. Linear dynamic range extend over one order of magnitude and shows the potential of device for the quantitative analysis of environmental pollutants.

In 1997, we collected nine river sediment samples, including one duplicate, from above and below three pulp and paper mills on the Wisconsin River in Wisconsin, USA, and one mill on Beaver Dam Creek in Ontario, Canada. We also obtained twenty split sediment samples from the Wisconsin River that were collected by the US EPA in collaboration with Indiana University. Finally, we collected influent and effluent samples from eight pulp and paper related industries in the US and Canada. We analyzed all sediment and water samples for hexa- through decachlorobornanes. We did not detect any chlorobornanes in most of the sediments. When chlorobornanes were detected, the concentration in sediments below pulp mills were similar to or less than in those from above the same mills. Chlorobornanes could not be detected in any of the influent or effluent samples. Thus, pulp and paper mills and relate facilities are not a source of chlorobornanes.

Alkylphenol ethoxylates (APEOs) are a group of non-ionic surfactants that are degraded microbially into more lipophilic degradation products with estrogenic potential, including nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO), octylphenol (4-tOP) and nonylphenol (4-NP). Nonylphenol ethoxylates are used in paper recycling plants for de-inking paper and have the potential to be released into the environment through spreading of wastewater treatment sludge for soil amendment. Three samples of recycled paper sludge were collected from farmers' fields and analyzed for concentrations of NP1EO, NP2EO, 4-NP and 4-tOP. Each sample differed in the amount of time elapsed since the sludge was placed on farmers' fields. Primary degradation products of APEOs were present at low micrograms/g concentrations in the sludge samples. Differences in the concentrations of these analytes in sludge samples indicated that APEO concentrations declined by 84% over a period of 14 weeks on farmers' fields. Changes in the chromatographic patterns of acetylated 4-NP indicated that there is a group of recalcitrant nonylphenol isomers that degrades more slowly than other isomers. These data indicate that microbial degradation may reduce the risk of environmental contamination by these compounds, but more work is required to assess the toxic potential of APEOs in sludges used for soil amendment.

Liquid packaging board (LPB) collected in Germany is processed in Finland as recycled fibre and as plastic reject for incineration. The chemical, biological and physical changes occurring in recycled LPB bales were monitored during storage of six and 18 months. The moisture content in the core of the bales ranged from 7% to 53%, and pH values varied from 6.0 to 8.5. The average amount of mesophilic bacteria per container was 1.5 x 10(7) - 5 x 10(8), which means that recycled LPB pulp cannot be recommended for sanitary use. The concentration of CO2 inside the bale is an indicator of the activity of aerobic microorganisms and might be suitable for identifying deteriorated bales and removing them from the production line. Insects were found in some bales and the more deteriorated the bale was the more species of insects were found. The results showed the conversion of cellulose into humic acids to be clearly underway in some recycled LPB bales. The bale samples were extracted into hot water and into fulvic acids and humic acid (HA) fractions. The concentration of the humic acid fraction varied in the range 0.3-0.6% of the organic matter in fresh bales and 2.2% in one old bale. During aging nitrogen was enriched in all fractions.

Lipophilic organic compounds originating from kraft pulping and papermaking were identified by straight gas chromatography/mass spectrometry (GC/MS) analyses. Samples analyzed included a primary clarifier effluent (PE) and a secondary clarifier effluent (SE) from the activated sludge treatment plant of a Finnish ECF-bleached (Elementally Chlorine Free) kraft pulp and paper mill. Liquid-liquid extraction composition of PE was compared with solid phase extraction (SPE) and dialysis of a semipermeable membrane device (SPMD) exposed to PE. Dichloromethane extracts of particulate material isolated from PE, sludges from both the primary and secondary clarifier, a sediment collected in the vicinity of the mill and whitefish subacutely exposed to the secondary treatment effluent were also investigated. Typical pulp mill-related compounds such as terpenes, terpenoids and aromatic compounds were identified in PE whereas these were non-detectable in SE. For example, thunbergene, thunbergol, squalene, longifolene and derivatives of abietic acid were observed in PE. Alkylated polycyclic aromatics were major compounds identified in the sediment sample with retene (C4-alkyl phenanthrene) as a predominant component.

Serum levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) among 46 long-term workers at a pulp and paper mill were compared to the levels in 16 community residents who never worked at the mill. Overall, there were no appreciable differences among the three exposure groups (community resident, low-exposure-potential worker, high-exposure-potential worker) for specific PCDDs or PCDFs. Neither exposure group nor duration in high-exposure-potential-jobs was related to total toxic equivalents (I-TEQ). Serum levels of PCDDs and PCDFs in this study generally were within the range previously reported for persons with no known occupational exposure.