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Metal-contaminated soil remediation by means of paper mill sludges addition: chemical and ecotoxicological evaluation.

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.

Carbonates↗

STR genotyping and mtDNA sequencing of latent fingerprint on paper.

A systematic study was conducted to investigate whether DNA can be successfully extracted from latent fingerprints deposited on ordinary paper and analysed using short tandem repeat profiling and mitochondrial DNA sequencing. In order to evaluate the performance of latent fingerprint analysis in a criminal case, experiments with varying conditions were carried out to improve our understanding of low copy number (LCN) DNA typing. After optimising the extraction methods to achieve increased sensitivity, the examination of touched paper can routinely yield the STR profile of the individual who has touched it. A fingerprint can therefore be considered as a potential source of DNA for genetic identification. Nevertheless, the findings of our "after enhancement experiment" (using chemically or physically pre-treated fingerprints), and our "mixture experiment" (using fingerprints from three to four people on the same sheet of paper) help to define the limitations of the low copy number PCR technique in forensic casework.

Alleles↗

Photofading of ballpoint dyes studied on paper by LDI and MALDI MS.

The determination of the age of an ink entry from a questioned document is often a major problem and a controversial issue in forensic sciences. Therefore, it is important to understand the aging process of the different components found in ink. The aim of this work is to characterize the degradation processes of methyl violet and ethyl violet, two typical ballpoint dyes by using laser desorption/ionization (LDI) and matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS), and to evaluate the possible application of the method to forensic examination of documents. The mass spectrometric methods were first tested and were found to be adequate for the purpose of this work. Moreover, it is possible to analyze the dye from a stroke directly from the paper (LDI-MS), so the sample preparation is minimized. The degradation of the dyes methyl violet and ethyl violet in strokes from a ballpoint pen was studied under laboratory conditions influenced by different factors such as light, wavelength of light, heat, and humidity. Then, strokes from the same ballpoint were aged naturally in the dark or under the influence of light over one year and then analyzed. The results show that the degradation of these dyes strongly depends on light fluence. Humidity also increases degradation, which can be explained by the basicity of the paper. The influence of heat on the degradation process was found to be rather weak. It was also observed that the dyes from the ink strokes did not show significant degradation after one year of storage in the dark. In conclusion, the storage conditions of a questioned document and the initial composition of the dyes in the ink have to be known for correct interpretation of the age of an ink entry. Measurements over longer periods of time are necessary to follow the degradation of dyes exempt from light exposure. LDI was found adequate and very useful for the analysis of ballpoint dyes directly from paper without further pretreatment.

Coloring Agents↗

Enzymatic versus chemical deinking of non-impact ink printed paper.

Enzymatic versus chemical deinking is examined for MOW and photocopy prints. Several enzymatic preparations and two fibre/ink particle separation methods are tested. Deinking was monitored by image analysis and standard pulp and paper characterisation procedures. The effectiveness of the fibre/ink particle separation method depends on the ink particle's size: for smaller particles a washing step is recommended whereas for larger particles, the use of flotation is necessary. The enzymatic treatment is a competitive alternative for MOW and photocopy paper deinking. However, the process requires the selection of an adequate enzymatic preparation for each paper grade.

Biodegradation, Environmental↗

Environmental quality of primary paper sludge.

The reuse and recycling of waste paper sludge is increasing rapidly as far as the economical and positive environmental benefits are realised. In this study, primary sludge coming from a large production plant, located in the centre of Italy, was collected and the environmental quality of the sludge was assessed through geotechnical, physical and chemical analysis and leaching tests, as required by the Italian regulation on solid waste recovery. The results suggest that primary sludge from paper industry do not represent a major threat for the environment in regard to the heavy metal content. The use of this sludge for in situ applications appears an interesting avenue for an integrated management of waste from the paper industry.

Conservation of Natural Resources↗

Zeolite synthesis from paper sludge ash at low temperature (90 degrees C) with addition of diatomite.

Paper sludge ash was partially converted into zeolites by reaction with 3M NaOH solution at 90 degrees C for 24 h. The paper sludge ash had a low abundance of Si and significant Ca content, due to the presence of calcite that was used as a paper filler. Diatomite was added to the NaOH solution to increase its Si content in order to synthesize zeolites with high cation exchange capacity. Diatomite residue was filtered from solution before addition of ash. The original ash without addition of diatomite yielded hydroxysodalite with a cation exchange capacity ca. 50 cmol/kg. Addition of Si to the solution yielded Na-P1 (zeolite-P) with a higher cation exchange capacity (ca. 130 cmol/kg). The observed concentrations of Si and Al in the solution during the reaction explain the crystallization of these two phases. The reaction products were tested for their capacity for PO(4)(3-) removal from solution as a function of Ca(2+) content, suggesting the formation of an insoluble Ca-phosphate salt. The product with Na-P1 exhibits the ability to remove NH(4)(+) as well as PO(4)(3-) from solution in concentrations sufficient for application in water purification. Both NH(4)(+) and PO(4)(3-) removal showed little variation with pH between 5 and 9. Alternative processing methods of zeolite synthesis, including the addition of ash to an unfiltered Si-NaOH solution and addition of a dry ash/diatomite mixture to NaOH solution, were tested. The third process yielded materials with lower cation exchange capacity due to formation of hydroxysodalite. The second process results in a product with relatively high cation exchange capacity, and reduces the number of processing steps necessary for zeolite synthesis.

Adsorption↗

Treatment of pulp and paper mill wastewater by polyacrylamide (PAM) in polymer induced flocculation.

The flocculation performances of nine cationic and anionic polyacrylamides with different molecular weights and different charge densities in the treatment of pulp and paper mill wastewater have been studied. The experiments were carried out in jar tests with the polyacrylamide dosages range of 0.5-15 mg l(-1), rapid mixing at 200 rpm for 2 min, followed by slow mixing at 40 rpm for 15 min and settling time of 30 min. The effectiveness of the polyacrylamides was measured based on the reduction of turbidity, the removal of total suspended solids (TSS) and the reduction of chemical oxygen demand (COD). Cationic polyacrlyamide Organopol 5415 with very high molecular weight and low charge density is found to give the highest flocculation efficiency in the treatment of the paper mill wastewater. It can achieve 95% of turbidity reduction, 98% of TSS removal, 93% of COD reduction and sludge volume index (SVI) of 14 ml g(-1) at the optimum dosage of 5 mg l(-1). SVI values of less than 70 m lg(-1) are found for all polyacrylamide at their respective optimum dosage. Based on the cost evaluation, the use of the polyacrylamides is economically feasible to treat the pulp and paper mill wastewaters. This result suggests that single-polymer system can be used alone in the coagulation-flocculation process due to the efficiency of the polyacrylamide. Sedimentation of the sludge by gravity thickening with settling time of 30 min is possible based on the settling characteristics of the sludge produced by Organopol 5415 that can achieve 91% water recovery and 99% TSS removal after 30 min settling.

Acrylic Resins↗

Application of molybdenum and phosphate modified kaolin in electrochemical treatment of paper mill wastewater.

Pulp and paper mill wastewater is characterized by very high chemical oxygen demand (COD) values that inhibit the activity of microorganisms during biological oxidations. The electrochemical degradation of pulp and paper mill wastewater catalyzed by molybdenum and phosphate (Mo-P) modified kaolin with graphite as anode and cathode was investigated. The catalyst was characterized by XRD, XPS and SEM spectra and the effects of pH, metal ion and introduction of NaCl on the efficiency of the electrochemical degradation process were also studied. It was found out that the modified kaolin loaded with Fe(3+) had higher electrochemical catalytic activity in the electrochemical degradation of paper mill wastewater at pH 4. A 96% COD removal efficiency was obtained in 40min of electrochemical treatment of the wastewater at current density 30mAcm(-2). A possible mechanism for degradation of the mill wastewater constituents was also proposed.

Catalysis↗

Gene expression fingerprints of largemouth bass (Micropterus salmoides) exposed to pulp and paper mill effluents.

Effluents from pulp and paper mills that historically have used elemental chlorine in the bleaching process have been implicated in inhibiting reproduction in fish. Compounds with estrogenic and androgenic binding affinities have been found in these effluents, suggesting that the impairment of reproduction is through an endocrine-related mode of action. To date, a great deal of attention has been paid to phytoestrogens and resin acids that are present in mill process streams as a result of pulping trees. Estrogen and estrogen mimics interact directly with the estrogen receptor and have near immediate effects on gene transcription by turning on the expression of a unique set of genes. Using differential display (DD) RT-PCR, we examined changes in gene expression induced by exposure to paper mill effluents. Largemouth bass were exposed to 0, 10, 20, 40, and 80% paper mill effluent concentrations in large flow-through tanks for varied periods of time including 7, 28 or 56 days. Plasma hormone levels in males and females and plasma vitellogenin (Vtg) in females decreased with dose and time. Measurements of changes in gene expression using DD RT-PCR suggest that the gene expression patterns of male fish do not change much with exposure, except for the induction of a few genes including CYP 1A, a protein that is induced through the action of the Ah receptor in response to dioxin and similar polyaromatic hydrocarbons. However, in the case of females, exposure to these effluents resulted in an up-regulation of CYP 1A that was accompanied by a generalized down-regulation of genes normally expressed during the reproductive season. These antiestrogenic changes are in agreement with previous studies in bass exposed to these effluents, and could result in decreased reproductive success in affected populations.

Amino Acid Sequence↗

Treatment of pulp and paper mill wastewater--a review.

Pulp and paper mills generate varieties of pollutants depending upon the type of the pulping process. This paper is the state of the art review of treatability of the pulp and paper mill wastewater and performance of available treatment processes. A comparison of all treatment processes is presented. Combinations of anaerobic and aerobic treatment processes are found to be efficient in the removal of soluble biodegradable organic pollutants. Color can be removed effectively by fungal treatment, coagulation, chemical oxidation, and ozonation. Chlorinated phenolic compounds and adsorable organic halides (AOX) can be efficiently reduced by adsorption, ozonation and membrane filtration techniques.

Adsorption↗

Effects of pulp and paper mill effluents on the microplankton and microbial self-purification capabilities of the Biobío River, Chile.

Most studies focus on the ecotoxicity of pulp and paper mill effluents, rather than on how they affect the physicochemical and biological structure and the intrinsic ecological capabilities of the receiving watercourses. We investigated the impact of such effluents on the water quality, microplankton system and microbial self-purification capacity (degradation of polymeric organic compounds via extracellular enzymes) of the Biobío River in Chile. The physicochemical impact on the water quality was indicated by raised conductivity, by the pollution of the water body with nitrate, nitrite and soluble reactive phosphorus, by the appearance of tannin and lignin, and by the steady accumulation of inorganic and organic suspended matter (SPM) along the river. From the biological structure of the microplankton system, very low and declining concentrations of chlorophyll a and heterotrophic flagellate densities were determined. The pulp and paper mill effluents introduced high bacterial abundances and biomass concentrations into the river water. This reflects the effective use made of the abundantly available inorganic and organic nutrients within this industrial and municipal process water by bacteria adapted to these extreme environments, additionally supported by concomitant low grazing pressure derivable from low heterotrophic flagellate abundances. Indeed, in one section of the river affected by a pulp mill, the plant was found to significantly contribute to the self-cleaning capacity of the river. However, this elevated degradation capacity was not enough to compensate for the additionally discharged organic material which, together with the toxic effects of the paper plant effluents, significantly interferes with the ecological status of the Biobío River.

Animals↗

Accuracy of digital panoramic images displayed on monitor, glossy paper, and film for assessment of mandibular third molars.

OBJECTIVE: The aim of this study was to compare the accuracy of 3 modalities of digital panoramic radiographs-monitor-displayed images and printed copies on glossy paper and on blue transparent film-for assessment of position and morphology of mandibular third molars. STUDY DESIGN: 164 third molars were recorded with one of 2 digital panoramic systems (Digora and Orthophos Plus) and assessed by 4 observers on 3 radiographic modalities: monitor display, glossy paper, and transparent film. The assessments were compared with surgeons' findings at the time of the operation ("gold standard"). RESULTS: Overall, the observer variation was larger than the variation between methods. A detailed paired analysis revealed some differences between the modalities for some diagnostic categories, but these were few and inconsistent. CONCLUSION: Printed images from the Kodak 1200 ink-jet printer on glossy paper and blue transparent film may be as accurate as the original monitor-displayed digital panoramic images from the Digora and Orthophos Plus systems for assessment of position and morphology of mandibular third molars.

Adolescent↗

Life cycle assessment of the waste hierarchy--a Danish case study on waste paper.

The waste hierarchy is being widely discussed these days, not only by cost-benefit analysts, but a growing number of life cycle assessments (LCA) have also begun to question it. In this article, we investigate the handling of waste paper in Denmark and compare the present situation with scenarios of more waste being recycled, incinerated or consigned to landfill. The investigations are made in accordance with ISO 14040-43 and based on the newly launched methodology of consequential LCA and following the recent guidelines of the European Centre on Waste and Material Flows. The LCA concerns the Danish consumption of paper in 1999, totalling 1.2 million tons. The results of the investigation indicate that the waste hierarchy is reliable; from an environmental point of view recycling of paper is better than incineration and landfilling. For incineration, the reason for the advantage of landfilling mainly comes from the substitution of fossil fuels, when incinerators provide heat and electricity. For recycling, the advantage is related to the saved wood resources, which can be used for generating energy from wood, i.e., from renewable fuel which does not contribute to global warming.

Conservation of Energy Resources↗

Utility of the dried blood on filter paper as a source of cytokine mRNA for the analysis of immunoreactions in Plasmodium yoelii infection.

We examined the utility of dried blood on filter paper for the source of cytokine messenger RNA (mRNA). Total RNA was isolated from the dried blood of mice infected with Plasmodium yoelii, and cDNA was amplified by reverse transcription-polymerase chain reaction (RT-PCR). As a reference, we extracted total RNA from peripheral blood collected at the same time as the preparation for dried blood. There was no difference in cytokine mRNA expression between the two sources; the dried blood on filter paper and the peripheral blood. Th1 cells, Th2 cells, and monocytes/macrophages derived cytokine mRNAs in the dried blood from infected mice were detected, and the increase of some of the cytokines mRNAs after infection was also observed. These results suggested that the dried blood on filter paper is satisfactory RNA source for immunological examination in field-based studies.

Animals↗

Determination of a large number of kinase activities using peptide substrates, P81 phosphocellulose paper arrays and phosphor imaging.

To perform phosphoproteomics and signal transduction studies, a number of protein kinase activities and levels must be simultaneously analyzed in different cell samples and correlated with phosphoprotein patterns to obtain conclusions with regard to the regulation of kinase networks. We describe here a miniaturized format of the classical phosphocellulose (P81) paper binding assay with which up to 594 kinase reactions can be simultaneously analyzed. Kinase peptide substrates possessing a minimum of three consecutive basic residues were subjected to phosphorylation in 96-well plates and aliquots of the phosphorylation reactions were spotted on arrays printed on P81 papers. Phosphorylation levels were quantified using a storage phosphor system imager. The versatility of the procedure was validated by analyzing casein kinase 2, protein kinase C, and p34cdc2/cyclin B in cell extracts and testing the effect of known inhibitors and activators on kinase activities. This improved, miniaturized version of the classical P81 paper method combines simplicity, high sensitivity, high reproducibility, high reliability, and optimal Z factors and takes into account possible sources of background signals. We discuss the possibility of automation and the advantages over other methods.

Amino Acid Sequence↗

The efficiency of oxidation ponds at the Kraft pulp and paper mill at Webuye in Kenya.

Two streams of wastewater from the Kraft Pulp and Paper Mills at Webuye are released from the pulping, bleaching and paper pressing departments. One stream is made up of clear wastewater and the second is made up of turbid wastewater. The wastewaters from the mills are treated using oxidation ponds, after which the treated wastewater is discharged into the River Nzoia. The wastewater was analysed for Cd, Cr, Cu, Ni, Pb. Zn, Ca, K, Mg and Na. The results are that the concentrations of Ca and Na significantly increased in the treated wastewater. The concentrations of Cd, Pb, Zn, K and Mg also increased in the treated wastewater, though not significantly. The concentrations of Cr, Cu and Ni decreased in the treated wastewater but not significantly. Mass loadings of the metals discharged into River Nzoia were calculated. It was found that the mean mass loading of two metals (Ca and Na) significantly increased in the treated wastewater. Five metals (Cd, Pb, Zn, K and Mg) increased in the treated wastewater although not significantly. Three metals (Cr, Cu and Ni) decreased in the treated wastewater but the decrease was not significant. The concentrations of Cd, Cu, Ni, Pb and Zn were all above the limits set by EC for drinking water. These findings pose serious questions of the effectiveness of oxidation ponds system to safeguard the receptor against pollutants from the pulp and paper industry at Webuye.

Environmental Monitoring↗

Mesophilic and thermophilic activated sludge post-treatment of paper mill process water.

Increasing system closure in paper mills and higher process water temperatures make the applicability of thermophilic treatment systems increasingly important. The use of activated sludge as a suitable thermophilic post-treatment system for anaerobically pre-treated paper process water from a paper mill using recycled wastepaper was studied. Two lab-scale plug flow activated sludge reactors were run in parallel for 6 months; a thermophilic reactor at 55 degrees C and a reference reactor at 30 degrees C. Both reactors were operated simultaneously at 20, 15 and 10 days SRT. The effects of temperature and SRT on sludge settleability and chemical oxygen demand (COD) removal efficiencies of different fractions were studied. Total COD removal percentages over the whole experimental period were 58+/-5% at 30 degrees C and 48 +/- 10% at 55 degrees C. The effect of the SRT on the total COD removal was negligible. Differences in total COD removal between both systems were due to a lesser removal of soluble and colloidal COD at 55 degrees C compared to the reference system. At 30 degrees C, colloidal COD removal percentages were 65+/-25%, 75+/-17% and 86+/-22% at 20, 15 and 10 days SRT, respectively. At 55 degrees C, these percentages were 48+/-34%, 40+/-28% and 70+/-25%, respectively. The effluent concentrations of colloidal COD in both systems were related to the influent concentration of colloidal material. The thermophilic sludge was not able to retain influent colloidal material as well as the mesophilic sludge causing a higher thermophilic effluent turbidity. Sludge settling properties were excellent in both reactor systems. These were neither temperature nor SRT dependent but were rather caused by extensive calcium precipitation in the aeration tanks creating a very dense sludge. For application in the board industry, a thermophilic in line treatment system seems feasible. The higher effluent turbidity is most likely offset by the energy gains of treatment under thermophilic conditions.

Bioreactors↗

The environmental fate of the primary degradation products of alkylphenol ethoxylate surfactants in recycled paper sludge.

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.

Agriculture↗