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Industrial processes and municipal wastes largely contribute to the fluctuations in iron (Fe) content in soils. Fe, when present in unfavorable amount, causes harmful effects on human, flora, and fauna. The present study is an attempt to evaluate the composition of Fe in surface soils from paper mill and municipal landfill sites and assess their potential ecological and human health risks. Geochemical fractionation was conducted to explore the chemical bonding of Fe across different fractions, i.e., water-soluble (F1) to residual (F6). Different contamination factors and pollution indices were evaluated to comprehend Fe contamination extent across the study area. Results indicated the preference for less mobile forms in the paper mill and landfill, with 26.66% and 43.46% of Fe associated with the Fe-Mn oxide bound fraction (F4), and 57.22% and 24.78% in the residual fraction (F6). Maximum mobility factor (MF) of 30.65% was observed in the paper mill, and 80.37% in the landfill. The enrichment factor (EF) varied within the range of 20 < EF < 40, signifying a high level of enrichment in the soil. The individual contamination factor (ICF) ranged from 0 to >6, highlighting low to high contamination. Adults were found to be more vulnerable towards Fe associated health risks compared to children. The Hazard Quotient (HQ) index showed the highest risk potential pathways as dermal contact > ingestion > inhalation. The study offers insights into potential Fe contamination risks in comparable environments, underscoring the crucial role of thorough soil assessments in shaping land use and waste management policies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Fly ash (FA) from biomass combustion and biological sludge (S), both wastes from the pulp and paper industry, were granulated in different proportions (90% FA+10% S, and 70% FA+30% S w/w, dry weight basis, dw) and used to recover the functionality of soils affected by mining activities (Aljustrel, Iberian Pyrite Belt), with and without the application of municipal solid waste compost (MSWC). Application doses of both mixtures were 2.5, 5.0 and 10% (w/w, dw). These materials corrected soil acidity to circumneutral values and increased extractable P and K concentrations. A significant increase in soil organic matter (from 0.6 to 0.8-1.5% w/w, dw) and N content (from 0.04 to 0.09-0.12% w/w, dw) was also observed, but only when MSWC was applied. The soil was already heavily contaminated with Cu, Pb and Zn and the application of amendments did not increase their pseudo-total concentrations. The CaCl 2 extractable fractions of both Cu and Zn decreased to very low values. The improvement in soil quality, compared to fertilizer only treatment, was further evidenced by the increase in some soil enzymatic activities (dehydrogenase, β-glucosidase and cellulase), with a better response for the granules with the higher proportion of biological sludge, as well as by the decrease in the soil-water extract toxicity towards different organisms (Daphnia magna, Thamnocephalus platyurus, and Pseudokirchneriella subcapitata). Agrostis tenuis germinated and grew during the first month only in the amended pots, but, after that, a considerable phytotoxic effect was evident. This was mainly attributed to salt stress or to some specific ionic toxicity. In conclusion, to establish a long-term plant cover in mining soils amended with biomass ash-based materials, the selection of plants with higher resistance to salinity and/or the stabilization of the amendments, to reduce their soluble salt content, is recommended., (Copyright © 2019. Published by Elsevier B.V.)

In recent years, increasing efforts have focused on production of organic-inorganic compound fertilizers using ammonium sulfite pulping waste liquor. However, their ecological effects on soil have not been studied. In this study, earthworm Eisenia fetida was exposed to various doses (0, 0.13, 0.26 and 0.52 kg/m 2 ) for different time (7, 14, 21, and 28 d) to evaluate the effects of fertilizers made from pulping waste liquor, including reactive oxygen species (ROS) generation, antioxidant enzymes activities, glutathione S-transferase enzyme (GST) activity, malondialdehyde (MDA) content and DNA damage. Results showed that there were significant increase of ROS and MDA levels after 14 d, inducing production of antioxidant enzymes (superoxide dismutase (SOD), peroxidase (POD) and catalase (CAT)) as well as GST. Before 14 d, excess ROS and MDA caused damage to the DNA of earthworms, leading to gradual increase of Olive tail moment (OTM) in the comet assay. With the exposure time extended to 28 d, owing to the combined effects of elimination of free radicals by antioxidant enzymes and detoxification enzymes as well as self-repairing function of cells, ROS and MDA levels declined slightly and OTM gradually decreased. In summary, this study indicated that there was a toxicological effect on earthworms when fertilizers made from pulping waste liquor were applied to soil, which needs more attention., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Aided phytostabilisation uses metal-tolerant plants, together with organic or inorganic amendments, to reduce metal bioavailability in soil while improving soil quality. The long-term effects of the following organic amendments were examined as part of an aided phytostabilisation field study in an abandoned Pb/Zn mining area: cow slurry, sheep manure and paper mill sludge mixed with poultry manure. In the mining area, two heavily contaminated vegetated sites, showing different levels of soil metal contamination (LESS and MORE contaminated site), were selected for this study. Five years after amendment application, metal bioavailability (CaCl 2 extractability) along with a variety of indicators of soil microbial activity, biomass and diversity were analysed. Paper mill sludge mixed with poultry manure treatment resulted in the highest reduction of Cd, Pb and Zn bioavailability, as well as in stimulation of soil microbial activity and diversity, especially at the LESS contaminated site. In contrast, cow slurry was the least successful treatment. Our results emphasise the importance of the (i) long-term monitoring of soil quality at sites subjected to aided phytostabilisation and (ii) selection of the most efficient amendments and plants in terms of both reduction of metal bioavailability and improvement of soil quality., (© FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

The efficiency of combining iron sulfate and organic amendments (paper mill sludge, olive mill waste compost and olive tree pruning biochar) for the remediation of an As- and Cu-contaminated soil was evaluated. Changes in As and Cu fractionation and solubility due to the application of the amendments was explored by leachate analysis, single and sequential extractions. Also, the effects on Arrhenatherum elatius growth, germination of Lactuca sativa and toxicity to the bacteria Vibrio fischeri were assessed. The combination of iron sulfate and the organic amendments efficiently reduced As solubility and availability through the formation of amorphous iron oxides, while organic matter did not seem to mobilize As. At the same time, copper fractionation was strongly affected by soil pH and organic matter addition. The soil pH significantly influenced both As and Cu mobility. Within all the amendments tested, FeSO 4 in combination with compost showed to be the most suitable treatment for the overall remediation process, as it reduced As and Cu availability andenhanced soil nutrient concentrations and plant growth. In sipte of contradictory trends between chemical analyses and ecotoxicity tests, we can still conclude that the application of organic amendments in combination with reactive iron salts is a suitable approach for the remediation of soils contaminated by Cu and As., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The probabilistic ecological risk assessment using terrestrial toxicity data has been mainly based on microfauna or mesofauna. Soil algae, which are food source for microfauna and mesofauna, may be alternatively used for assessing soil toxicity. However, there are no internationally recommended guidelines for soil algal bioassays, and the collection of algae from the test soils has some limitations. In this study, we suggested the paper-disc method as an easy-to-use alternative. This method has been widely used for testing the antibacterial toxicity of various chemicals in agar media by measuring the diameter of the inhibition zone around the disc. We adapted the paper-disc method for screening the toxicity of copper (Cu) and nickel (Ni) to the soil alga Chlorococcum infusionum using various evaluation endpoints, such as growth zone, chlorophyll fluorescence, and photosynthetic activity. Chlorophyll fluorescence and photosynthetic activity decreased with the increasing concentrations of Cu(+2) or Ni(+2) contaminated soils. Algal growth zone was analyzed visually and showed similar results to those of chlorophyll fluorescence. The direct ethanol extraction method and indirect culture medium extraction method were similarly effective; however, the former was easier to perform, while the latter might facilitate the analysis of additional endpoints in future studies. Overall, the results suggested that the paper-disc method was not only a user-friendly assay for screening soil toxicity, but also effective due to its association with indirect soil quality indicators., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The goal of this research was to assess the potential of several industrial wastes to immobilise metals in two polluted soils deriving from an old Pb/Zn mine. Two different approaches were used to assess the performance of different amendments: a chemical one, using extraction by ethylenediaminetetraacetic acid (EDTA), and a biological one, using Lupinus albus as a bio-indicator. Four amendments were used: inorganic sugar production waste (named 'sugar foam', SF), sludge from a drinking water treatment sludge (DWS), organic waste from olive mill waste (OMW) and paper mill sludge (PMS). Amendment to soil ratios ranged from 0.1 to 0.3 (w/w). All the amendments were capable of significantly decreasing (p < 0.05) EDTA-extractable Pb, Zn and Cu concentrations in the two soils used, with decreases in ranges 21-100, 25-100 and 2-100 % for Pb, Zn and Cu, respectively. The amendments tested were also effective in reducing the bioavailability of Pb and Zn for L. albus, which gave rise to a decrease in shoot metal accumulation by the lupine plants compared to that found in the control soil. That decrease reached up to 5.6 and 2.8 times for Pb and Zn, respectively, being statistically significant in most cases. Moreover, application of the OMW, DWS and SF amendments led to higher average values of plant biomass (up to 71%) than those obtained in the control soil. The results obtained showed the technology put forward to be a viable means of remediating mine soils as it led to a decrease in the availability and toxicity of metals and, thus, facilitated the growth of a vegetation layer.

In order to assess the potential of wetland plants to remediate metals from a paper mill effluent contaminated wetland site in Northeast India, 25 abundant plant species belonging to 15 different families, soil, and water samples from the sites were tested for Pb, Zn, Mg, and Fe by atomic absorption spectrophotometer. The results showed that metal accumulation by wetland plants differed among species and tissues. Plants thrived in high Pb, Zn, Mg, and Fe which indicated their tolerance. According to the criteria used for selecting plants for phytoremediation such as high metal tolerance, short life cycle, wide distribution, large shoot biomass and translocation factor (TF) >1; five species each were Mg and Fe accumulators, nine species were Pb accumulators and, eight species were Zn accumulators and the rest were excluders. Alternanthera sessilis was the only plant species that had TF > 1 for all the four metals. The study indicated great promise for phytoremediation, as these accumulators could be used in future for practical phytoremediation approaches and reduction of the risk from harmful metals to human health.

Increased ethoxyresorufin-O-deethylase (EROD) activity is a sensitive biomarker of exposure to the chemicals which activate the aryl hydrocarbon receptor (AhR) and induce the cytochrome P450 system, such as many polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs). Pulp bleaching was one of the main sources of PCDDs and PCDFs until elemental chlorine free (ECF) and total chlorine free bleaching processes since 1990s have remarkably decreased but not completely eliminate discharges of these chemicals. In addition, historically contaminated sediments may act as a source of these persistent contaminants. In this study, the contamination history and recovery of a watercourse heavily loaded by the chemical wood industry were studied by analyzing PCDDs, PCDFs and PCBs from vertical sediment samples and by measuring hepatic EROD activity from rainbow trout intraperitoneally dosed with the sediment extracts. No PCDDs or PCDFs were found above the chromatographic limit of detection from the study area and only small amounts of PCB congeners 101, 138, 153, and 180 were present. No increased EROD activity was observed in fish indicating the absence of any AhR-activating compounds in the surface sediment, to about 15 cm depth, representing about the last 20 years when kraft pulping and ECF bleaching with activated wastewater treatment have been used. It can be concluded that nowadays organochlorines and other AhR-ligands do not harm the previously heavily polluted watercourse., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Organic pollutants present in the soil of a microcosm containing pulp and paper mill black liquor were extracted with hexane/acetone (1:1 v/v) to study the biodegradation and detoxification potential of a Bacillus sp. gas chromatography-mass spectroscopic (GC-MS) analysis performed after biodegradation showed formation of simpler compounds like p-hydroxyhydrocinnamic acid (retention time [RT] 19.3 min), homovanillic acid methyl ester (RT 21.6 min) and 3,5-dimethoxy-p-coumaric alcohol (RT 24.7 min). The methyltetrazolium (MTT) assay for cytotoxicity, 7-ethoxyresorufin-O-deethylase (EROD) assay for dioxin-like behavior and alkaline comet assay for genotoxicity were carried out in the human hepatocarcinoma cell line HuH-7 before and after bacterial treatment. Bioremediation for 15 days reduced toxicity, as shown by a 139-fold increase in black liquor's LC50 value, a 343-fold reduction in benzo(a)pyrene equivalent value and a 5-fold reduction in olive tail moment. The EROD assay positively correlated with both the MTT and comet assays in post biodegradation toxicity evaluation.

The present study on heavy metal contamination in soil and their accumulation in edible part (leaves) and roots of Spinacia oleracea (Spinach) on irrigation with paper mill effluent (PME)/sewage revealed that there was significant increase in the nickel (Ni, +227.17 %) content of the soil irrigated with PME, whereas in the soil irrigated with sewage chromium (Cr, +274.84 %), iron (Fe, +149.56 %), and cadmium (Cd, +133.39 %), contents were increased appreciably. The value of enrichment factor (EF) for Ni (3.27) indicated moderate enrichment in PME-irrigated soil. The EF of Fe, zinc (Zn), Cd, and Cr were <2 in PME effluent-irrigated soil which showed deficiency of minimal enrichment. In sewage irrigated soil, EF value for Cr, Fe, and Cd indicated moderate enrichment, while the values for Zn and Ni indicated deficiency of minimal enrichment. Among various metallic concentrations, the maximum concentration of Fe was observed in leaves (400.12 ± 11.47 mg/kg) and root (301.41 ± 13.14 mg/kg) of S. oleracea after irrigation with PME, whereas the maximum concentrations of Fe was found in leaves (400.49 ± 5.97 mg/kg) and root (363.94 ± 11.37 mg/kg) of S. oleracea after irrigation with sewage for 60 days. The bioaccumulation factor value was found maximum for Cd (2.23) in the plants irrigated with PME while that of Fe (0.90) in the plants irrigated with sewage. The undiluted use of PME/sewage for irrigation increased the concentration of Cr, Cd, Zn, Ni, and Fe metals which were accumulated in S. oleracea, posing a potential threat to human health from this practice of irrigation.

Industrial residue application to soil was investigated by integrating granulated blast furnace or converter steel slag with residues from the pulp and paper industry in various formulations. Specimen analysis included relevant physicochemical properties, total element concentrations (HCl+HNO3 digestion, USEPA 3051) and chemical speciation of chosen heavy metals (CH3COOH, NH2OH·HCl and H2O2+H2O2+CH3COONH4, the BCR method). Produced matrices showed liming effects comparable to commercial ground limestone and included significant quantities of soluble vital nutrients. The use of converter steel slag, however, led to significant increases in the total concentrations of Cr and V. Subsequently, total Cr was attested to occur as Cr(III) by Na2CO3+NaOH digestion followed by IC UV/VIS-PCR (USEPA 3060A). Additionally, 80.6% of the total concentration of Cr (370 mg kg(-1), d.w.) occurred in the residual fraction. However, 46.0% of the total concentration of V (2470 mg kg(-1), d.w.) occurred in the easily reduced fraction indicating potential bioavailability., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The mean concentrations of Zn, Cu, Cd, Cr and Fe in mosses around Webuye Pan Paper factory were found to be significantly higher than in controls taken from Kakamega, indicating atmospheric contribution from the anthropogenic activities within the factory, shown within a radius of 1 km around the factory. The mean concentrations (μg/g dry weight) in the mosses ranged from 60.9-124.5, 22.6-34.2, 13.3-14.7, 20.1-33.3 and 1,822.4-2,079.2, respectively. The mean concentrations of Pb in mosses sampled from the eastern and western side of the factory were also significantly higher than in controls. The mean concentrations of Zn, Cu, Cd, Cr, Pb and Fe in topsoil samples ranged from 7 (Pb)-2,310 (Fe) mg/kg dry wt, depending on sample means based on site direction, distance from the factory and season. There was no clear variation in metal concentrations in mosses and topsoils with direction from the factory which was consistent with the observed fluctuations in wind direction which changed from south-west in the mornings to north and south-west in the afternoons during sampling.

The possibility of amending Pb2+ contaminated soil (S) with paper sludge (P) was investigated through adsorption and desorption experiments. The adsorption process of Pb2+ in soil containing paper sludge (SP) could be well described by pseudo second-order kinetic model and the Langmuir isotherm model. After P addition, the equilibrium time decreased greatly (from 28 to 8 hr) and the Pb2+ maximum adsorbed amount (Qmax) increased by a factor of more than three to 102.04 mg/g. Qmax reached its maximum as S:P was 9:1 (m/m) after 10 days contact between S and P. Moreover, Pb2+ adsorbed amount increased with the rise of pH during the adsorption process. Desorption experiments indicated that Pb2+ adsorption in SP was irreversible. The metal ion fraction was analyzed with Energy Dispersive Spectrometer and Environmental Scan Electron Microscope. As a result, the addition of P to soil was found to induce a decrease in the mobile forms. The Pb2+ complexes formation in the presence of carbonates was the main adsorption mechanism. Overall, the paper sludge could be one of the promising soil amendments for the remediation of soil with Pb2+ contamination.

This study examined the potential biological hazard of pulp and paper waste solids. The solids examined were chosen on the basis of the range of wood-related organic extractives and were either primary solids screened from the effluent stream before secondary treatment, or biosolids from aerated stabilisation lagoons. Acute effects were tested at the level of plants, invertebrates and soil microbes using an oat germination and growth test, earthworm survival and reproduction test, an enchytraeid worm survival and reproduction test, and standard measures of microbial respiration. This was further benchmarked against a marine bacteria toxicity test using extract of the waste solids. Resin acids and resin acid neutrals made up the greatest proportion of organic extractives measured in biosolids whereas resin acids and fatty acids were the main constituents detected in primary solids. Examination of the tissue of earthworms from the tests revealed no net bioconcentration of the organic extractives. The waste solids were not acutely toxic to any of the soil organisms as tested without any dilution. Conversely, extracts of the waste solids demonstrated toxicity in the marine bacteria. In some cases, the solid waste material enhanced the growth of plants, earthworm reproduction and microbial respiration. The only adverse affect was that reproduction of enchytraeids was reduced by some of the waste solid treatments. However these effects did not appear to be associated with concentrations of resin acid neutrals and resin acids in these materials. Overall pulp and paper wastes were relatively benign in terms of toxicity to the soil organisms tested.

The effect of irrigation by the effluent of paper industry versus well water on properties of soils in three seasons was studied in Nagpur district, Maharashtra. The effluent had high total dissolved salts and biological oxygen demand than well water. pH, EC and availability of N, P, K, Zn, Cu, Fe, Mn, Cd, Co, Cr, Ni, Pb, particularly in surface layer of paper industry effluent irrigated soil at different seasons found to increase compared to well water irrigated soils, but heavy metals (non-essential nutrients) were within the permissible limits.

Two basidiomycetous fungi (Merulius aureus syn. Phlebia sp. and an unidentified genus) and a deuteromycetous fungus (Fusarium sambucinum Fuckel MTCC 3788) were isolated from soils affected with effluents of a pulp and paper mill over several years. These isolates were immobilized on nylon mesh and the consortium was used for bioremediation of pulp and paper mill effluent in a continuously aerated bench-top bioreactor. The treatment resulted in the reduction of color, lignin and COD of the effluent in the order of 78.6%, 79.0% and 89.4% in 4 days. A major part of reductions in these parameters occurred within first 24h of the treatment, which was also characterized by a steep decline in the pH of the effluent. During this period, total dissolved solids, electrical conductivity and salinity of the effluent also registered marked decline. It is pertinent to note that this is the first report of bioremediation of pulp and paper mill effluent by an immobilized fungal consortium.

In the last few years solidification/stabilisation of acidic soils polluted by heavy metals with low-cost sorbents has been investigated. Paper mill sludges are produced in large amounts and their disposal is a serious environmental problem. The possibility was therefore studied of using paper mill sludge as a stabilizer to reduce the bioavailable metal forms in polluted soils and thus the transferability of metals to plants (barley). We first investigated the sorbing properties of paper mill sludge for Zn(II) and Pb(II) and then their fractionation both in a polluted soil and in the same soil amended with paper mill sludge in order to check the decrease in mobile forms. Finally in both soils we tested the uptake of two metals by common barley in order to assess the performance of soil remediation from an ecological point of view. The addition of paper mill sludge to a soil contaminated by lead and zinc induces a decrease in the mobile forms of both metals, probably due to the presence in sludge of organic matter and kaolinite, which are able to bind the metals very strongly. The decrease in the mobile forms, which are the most readily available for uptake by plants, corresponds to a decrease in plant uptake.

Metal pollution of soils is a great environmental problem. The major risks due to metal pollution of soil consist of leaching to groundwater and potential toxicity to plants and/or animals. The objective of this study is to evaluate by means of chemical and ecotoxicological approach the effects of paper mill sludge addition on the mobile metal fraction of polluted metal soils. The study was carried out on acidic soil derived from mining activities and thus polluted with heavy metals, and on two paper mill sludges having different chemical features. The results obtained by leaching experiments showed that the addition of a paper mill sludge, consisting mainly of carbonates, silicates and organic matter, to a heavy-metal polluted soil produces a decrease of available metal forms. The carbonate content seems to play a key role in the chemical stabilisation of metals and consequently in a decrease of toxicity of soil. The leached solutions have a non-toxic effect. The mild remediation by addition of sludge has moreover a lasting effect.

The potential impact on a variety of bioassay organisms when pulp-mill biosolids from a thermomechanical pulp mill (western Canada) were applied to a reference soil has been investigated in a laboratory setup. The current research assessed acute, chronic, and reproductive impacts using a battery of terrestrial and aquatic organisms. Terrestrial organisms were exposed to soil amended with different concentrations of biosolids, while aquatic organisms were used to assess the impact of biosolids' runoff into receiving waters. The former bioassays showed that an application rate of 20 tonneshectare(-1) (tha(-1)) "bone-dry" biosolids applied to reference soil produced no observable adverse impact on the terrestrial organisms. In the latter assays, undiluted (100%) and 50% diluted biosolids' runoff into receiving water had a detrimental impact on the aquatic organisms. However, concentrations not exceeding 25% (environmentally relevant concentrations) had neither an acute nor chronic impact compared to reference populations. The organisms' abilities to reproduce were also unaltered. While this study only examined the biosolids from one mill, there is the potential that land-application of characteristically well-defined pulp mill biosolids may constitute an acceptable way of disposing of pulp and paper mill biosolid residues. However, the biosolids coming from different mills, with differing processes, must be dealt with on a case-by-case situation. Each series of biosolids must be rigorously tested for toxicological impact in the laboratory under tightly controlled conditions. Subsequently, field experimentation must be conducted before definitive conclusions can be made.

An examination of the relative breakdown rates of unused toilet paper, facial tissues and tampons was undertaken in nine different environments typical of Tasmanian natural areas. Bags of the paper products (toilet paper, facial tissues, tampons) were buried for periods of 6, 12 and 24 months at depths of 5 and 15 cm. A nutrient solution simulating human body wastes was added to half of the samples, to test the hypothesis that the addition of nutrients would enhance the breakdown of paper products buried in the soil. Mean annual rainfall was the most important measured variable determining mean breakdown in the nutrient addition treatment between sites, with high rainfall sites (mean annual rainfall of greater than 650 mm) recording less decayed products than the drier sites (mean annual rainfall of 500-650 mm). Temperature and soil organic content were important influences on the breakdown of the unfertilised products. Toilet paper and tissues decayed more readily than tampons. Nutrient addition enhanced decay for all products across all sites. Depth of burial was not important in determining the degree to which products decayed. In alpine environments, burial under rocks at the surface did not increase the speed of decay of any product. The Western Alpine site, typical of alpine sites in the Tasmanian Wilderness World Heritage Area, showed very little decay over the two-year period, even for nutrient enhanced products. Management prescriptions should be amended to dissuade people from depositing human toilet waste in the extreme (montane to alpine) environments in western Tasmania. Tampons should continue to be carried out as currently prescribed.

Newsprint samples collected from 12-16 ft (top layer (TNP)), 20-24 ft (middle layer (MNP)), and 32-36 ft (bottom layer (BNP)) below the surface of the Norman Landfill (NLF) were characterized by infrared (IR) spectroscopy, cross-polarization, magic-angle spinning 13C nuclear magnetic resonance (CP-MAS 13C NMR) spectroscopy, and tetramethylammonium hydroxide (TMAH) thermochemolysis gas chromatography/mass spectrometry (GC/MS). The extent of NLF newsprint degradation was evaluated by comparing the chemical composition of NLF newsprint to that of fresh newsprint (FNP) and newsprint degraded in the laboratory under methanogenic conditions (DNP). The O-alkyl/alkyl, cellulose/lignin, and lignin/resin acid ratios showed that BNP was the most degraded, and that all three NLF newsprint samples were more degraded than DNP. 13C NMR and TMAH thermochemolysis data demonstrated selective enrichment of lignin over cellulose, and TMAH thermochemolysis further exhibited selective enrichment of resin acids over lignin. In addition, the crystallinity of cellulose in NLF newsprint samples was significantly lower relative to that of FNP and DNP as shown by 13C NMR spectra. The yield of lignin monomers from TMAH thermochemolysis suggested that hydroxyl groups were removed from the propyl side chain of lignin during the anaerobic decomposition of newsprint in the NLF. Moreover, the vanillyl acid/aldehyde ratio, which successfully describes aerobic lignin degradation, was not a good indicator of the anaerobic degradation of lignin on the basis of the TMAH data. The toluene sorption capacity increased as the degree of newsprint degradation increased or as the O-alkyl/alkyl ratio of newsprint decreased. The results of this study further verified that the sorbent O-alkyl/ alkyl ratio is useful for predicting sorption capacities of natural organic materials for hydrophobic organic contaminants.

A method has been developed for the analysis of (14)CO(2) evolution from the mineralization of (14)C-labelled organic compounds in soil samples. The new method is less space demanding and substantially cuts down laborious manual work compared to the traditional incubation bottle method used. Furthermore, the use of scintillation cocktail is largely reduced with the new method. In the new method, (14)CO(2) is trapped in filter paper held in the lid of a 20 ml glass vial by surface tension. The trapping solution used is Ca(OH)(2), which fixates CO(2) in the filter paper and the analysis of trapped (14)CO(2) is done using the Cyclone trade mark Storage Phosphor system. The lids are placed in a 32 well holder and exposed to a phosphor screen prior to scanning in a Cyclone trade mark scanner. The new filter method has been tested and compared to results obtained using the traditional method. The results show good agreement but due to a smaller capacity for CO(2) with the filter method compared to the traditional method, the interval between sampling has to be shorter using the filter method when the CO(2) development is high. The detection limits for the filter method is higher compared to the traditional method. With the filter method, the level of radioactivity has to exceed 300 dpm before detection is possible, while the same limit for the traditional method is around 30 dpm. On the other hand, the gas trapping faster and the efficiency is higher with the filter method.

River Kymijoki, the fourth largest river in Finland, has been heavily polluted by pulp mill effluents as well as by chemical industry. Loading has been reduced considerably, although remains of past emissions still exist in river sediments. The sediments are highly contaminated with polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated diphenyl ethers (PCDEs), and mercury originating from production of the chlorophenolic wood preservative (Ky-5) and other sources. The objective of this study was to simulate the transport of these PCDD/F compounds with a one-dimensional flow and transport model and to assess the impact of restoration dredging. Using the estimated trend in PCDD/F loading, downstream concentrations were calculated until 2020. If contaminated sediments are removed by dredging, the temporary increase of PCDD/F concentrations in downstream water and surface sediments will be within acceptable limits. Long-term predictions indicated only a minor decrease in surface sediment concentrations but a major decrease if the most contaminated sediments close to the emission source were removed. A more detailed assessment of the effects is suggested.

An approach based on the number of extractions performed over time was applied to study the time necessary to attain equilibrium conditions between the different chemical forms present in two natural soils laboratory-loaded with heavy metals (Cu(II), Pb(II), Zn(II)). The influence of some soil parameters, such as pH value, cation exchange capacity and organic matter content, on the equilibrium time was evidenced both by the different nature of the soils and by the treatment of soils with paper mill sludge. Equilibrium conditions were determined by studying the metal partitioning in the soil on a case by case basis. The behaviour of the three metals was not the same, and the conditions of equilibrium among the different chemical forms were the result of the amount of heavy metals added as well as of the nature of the soil.

13C NMR analyses of hydrophobic dissolved organic matter (DOM) fractions isolated from a landfill leachate contaminated groundwater near Norman, OK; the Colorado River aqueduct near Los Angeles, CA; Anaheim Lake, an infiltration basin for the Santa Ana River in Orange County, CA; and groundwater from the Tomago Sand Beds, near Sydney, Australia, found branched methyl groups and quaternary aliphatic carbon structures that are indicative of terpenoid hydrocarbon precursors. Significant amounts of lignin precursors, commonly postulated to be the major source of DOM, were found only in trace quantities by thermochemolysis/gas chromatography/mass spectrometry of the Norman Landfill and Tomago Sand Bed hydrophobic DOM fractions. Electrospray/tandem mass spectrometry of the Tomago Sand Bed hydrophobic acid DOM found an ion series differing by 14 daltons, which is indicative of aliphatic and aryl-aliphatic polycarboxylic acids. The product obtained from ozonation of the resin acid, abietic acid, gave a similar ion series. Terpenoid precursors of DOM are postulated to be derived from resin acid paper sizing agents in the Norman Landfill, algal and bacterial terpenoids in the Colorado River and Anaheim Lake, and terrestrial plant terpenoids in the Tomago Sand Beds.

Eggs of double-crested and pelagic cormorants were collected between 1973 and 1998 from colonies in the Strait of Georgia, BC, Canada, and assayed for concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and non-ortho- and mono-ortho-biphenyls (PCBs). Double-crested cormorant eggs contained (on average) up to 433 ng kg(-1) wet weight 1,2,3,6,7,8-HxCDD, 151 ng kg(-1) 1,2,3,7,8-PnCDD, and 74 ng kg(-1) 2,3,7,8-TCDD, whereas pelagic cormorant eggs contained up to 300, 99, and 28 ng kg(-1) wet weight of these respective congeners. The dominant non-ortho-PCB was CB-126, which ranged as high as 2263 ng kg(-1) in double-crested cormorant eggs. Concentrations of PCDDs and PCDFs fell dramatically in the early 1990s, following both severe restrictions on the use of chlorophenolic wood preservatives and antisapstains and a switch from molecular chlorine bleaching to alternative bleaching technologies at pulp mills in the region. Concentrations of PCBs did not show similar marked declines over time. On the basis of total TEQs > or = 148 ng kg(-1) and previously published documentation of effects in siblings of the cormorant eggs analyzed here, double-crested cormorant young may have exhibited significantly elevated EROD activity and/or brain asymmetries at all colonies from 1973 to 1989 and even at some colonies during the 1990s. Pelagic cormorant eggs collected from a few colonies in 1988-1989 also contained total TEQs greater than the threshold value estimated for double-crested cormorants.

Food supply and contaminants were investigated as possible causes of low bald eagle productivity near a bleached kraft pulp and paper mill at Crofton on Vancouver Island, British Columbia. Over a seven year period, 1992-1998, average productivity of five eagle territories situated south of the pulp mill at Crofton was significantly lower (0.43 young/occupied territory) than six territories north of the mill (1.04 young/occupied territory). A reference population of 32 territories located in Barkley Sound on the west coast of Vancouver Island demonstrated intermediary mean productivity (0.75 young/occupied territory). Measures of prey biomass delivered to nests were lowest south of the mill, and correlated significantly with nesting success. On average, measures of energy delivered to nests and a parameter determined to be related to prey availability, adult nest attendance time, accounted for about 70% of variability in nest success. Contaminant concentrations, including pulp mill derived polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), as well as dichlorodiphenyldichloroethane (DDE), polychlorinated biphenyls (PCBs), and calculated tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs) were significantly greater in plasma samples of nestlings from south of the mill compared to the other two sites, but did not correlate significantly with individual nest success data. Nests south of the mill concentrate around Maple Bay, which appears to be a deposition area for contaminants transported by tides and currents from sources such as the pulp mill. Concentrations of DDE and PCBs in plasma of nestling eagles from south of the mill were less than the critical values estimated to affect production of young. For TEQs, there are no published critical values for plasma by which to compare our results. We conclude that less than adequate energy provisioning to nests, presumably related to low prey availability, was likely the main cause of poor nest success south of the mill site at Crofton. However, higher concentrations of both DDE and PCDD/F derived TEQs may have acted in concert with food stress to further reduce bald eagle productivity.

In continuation of their studies on Biodegradation of cellulosic waste materials, the authors have presented their experimental data on biodegradation on waste paper pulp. Greater efficiency in the cow dung and M3 culture experimental setups have been pointed out and discussed. Necessity of detailed data evaluation of temperature, pH, dry weight, cellulose, protein, carbohydrate, Nitrate, Phosphate & Potassium levels is suggested. Derivation of %, absolute and increase/decrease % of BOO, COD and VS have been pointed out for the first time in solid waste Biodegradation. Further data evaluation and derivation of critical reaction rate kinetics have been recommended for further studies in solid waste-degradation to achieve quicker Bioconversion of cellulosic wastes into compost.

Mill process changes and source controls instituted in the late 1980s at pulp and paper mills along the British Columbia (BC) coast produced dramatic reductions in both the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and the TEQ (2,3,7,8-TCDD toxic equivalents). Nevertheless, questions remained as to whether the sediments were acting as contaminant sources or sinks, whether crab uptake pathways have stayed the same since the mills ceased producing PCDD/Fs, and whether improvement was faster at some sites than others. To examine the processes governing the changes in PCDD/F composition, PCDD/F sources and compositional trends for the coastal BC sites were interpreted using sediment and crab PCA (principal components analysis) models and two indices based on the three main groups of PCDD/Fs that covary in all PCA models. One index measured the relative inputs of chlorine bleaching PCDFs and PCP (pentachlorophenol)-related PCDDs at each mill and harbor site whereas the other measured the relative inputs of PCP wood preservatives and pulp mill effluents. Results indicated that PCDFs produced during chlorine bleaching accumulate from sediments to crabs more readily than the PCDDs but that the chlorine bleaching TCDFs have generally decreased in importance at all mill sites. In the years just before 1995, little change was observed in either the proportion of toxic 2,3,7,8-chlorinated congeners or the PCDD/F concentrations, and the improvements seemed to have largely ceased by 1995. The lack of change in PCA composition for the harbors provided a further, disturbing indication that ecosystem recovery may have stalled. Results also implied that the main route of PCDD/Fs into crabs shifted from uptake via a pelagic food web incorporating effluent-borne PCDD/Fs associated with suspended particulate matter to uptake via a benthic food web.

Drinking water is supplied by individual roof-catchment systems for homes and businesses near a dissolving sulfite pulp mill (now closed) located just north of Ketchikan in southeast Alaska. This study was conducted to determine if polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) found in the sediments of the roof-catchment cisterns resulted from historical deposition of stack emissions from the pulp mill's multi-fuel power boilers. Fly ash from the power boilers had maximum total PCDD/F concentrations of 3.08 x 10(5)-3.10 x 10(6) ng/kg, which resulted from combustion of bleach plant wastewater sludge and saltwater-soaked wood waste. Cistern sediments had maximum total PCDD/F concentrations of 7.71 x 10(4) ng/kg. Potential sources of PCDDs/Fs in the cistern sediments were considered to be automobile exhaust, heating oil combustion, and private trash burning as well as pulp mill boiler emissions. Discriminant analysis was used to analyze differences between profiles of tetra through octa homologue classes of PCDDs/ Fs (defined as proportional contributions to total concentration) from different source terms. Homologue profiles of potential sources from Ketchikan included in this analysis were fly ash collected from the mill's power boilers and soils collected from background areas (areas with similar PCDD/F sources as the residences [e.g., auto exhaust and burn barrels] near the mill but beyond the zone of aerial deposition of emissions from the mill). Profiles for emissions from automobile exhaust, fertilizers, oil heating, residential trash burning, and residential wood heating were also included in the source "training" data set (for the discriminant analysis) using data from published literature. The classification rules developed from the discriminant analysis were applied to the following test media sampled at Ketchikan: roof-catchment cistern sediments and soils collected from areas in the vicinity of the mill's power boilers (i.e., nearby residential or commercial [developed] areas, on the mill property, and nearby forestlands). The homologue profiles of cistern sediment and nearby developed area soil samples were similar to background soils, whereas the profiles for the forestland soil samples (influenced by emissions from the mill but not other anthropogenic sources) closely matched the fly ash pattern. The homologue profiles of the emission sources from published data were more similar to one another than either background soils or fly ash. Soil samples from the mill property were classified as members of all source groups. On the basis of these analyses, the composition of PCDDs/Fs detected in the cistern sediments is typical of Ketchikan background conditions and not reflective of mill emissions.

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.

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 total concentration of mercury was determined in samples of water, soil and sludge from the Mediterranean coastal area of Southeast Spain (Motril), where Hg contamination is produced primarily by a local paper mill. Samples were taken at surface level in a 5 Km radius from the factory. The total Hg concentrations varied from 0.117 to 0.760 microgram/g in soil and sludge, and from ND to 2.088 micrograms/L in water. A negative correlation was observed between the distance of the sampling station from the mill and the concentration of Hg in the soil and sludge samples. Similarly, an increase in Hg concentration was observed in the freshwater and wastewater after passing close to the factory.

Sanitary-chemical, bacteriological and toxicological characterization of sediments in the regions of the pulp and paper mills sewage letting out are given. Methods of the analytical control are offered.