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Residual chlorine from widespread disinfection processes forms byproducts in water that are harmful to humans and ecosystems. Portable sensors are essential tools for the on-site monitoring of residual chlorine in environmental samples. Here, an inexpensive colorimetric sensor was developed by grafting via amidation the chromogen orthotolidine (OTO) to the surface of a TEMPO-oxidized cellulose filter paper (O-TOFP). A thorough characterization of the sensor strip demonstrated that it was highly stable and that it could be stored for a long period before usage. O-TOFP had a fast response time of 30 s, was highly selective for residual chlorine ions (ClO - ) with an accuracy of at least 95 %, and exhibited an excellent limit of detection of only 0.045 mg/L when combined with smartphone image acquisition. With its many positive features, the easy-to-use and robust O-TOFP sensor described here could become a useful tool for the determination of residual chlorine in different water samples., 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 B.V. All rights reserved.)

Chlorine bleaching technology (C process, CEH process, H process and theirs combination), which was identified as a primary formation source of PCDD/Fs, is still widely used by the vast majority of Chinese non-wood pulp and paper mills (non-wood PMs). The purpose of this study was to provide information and data support for further eliminating dioxin for non-wood PMs in China, and especially to evaluate the PCDD/Fs release reduction for those mills converting their pulp bleaching processes from CEH to ECF. The PCDD/Fs concentrations of the bleached pulp and bleaching wastewater with ECF bleaching were in the ranges of 0.13-0.8 ng TEQ kg -1 , and 0.15-1.9 pg TEQ L -1 , respectively, which were far lower than those with CEH process, indicating that the ECF process is an effective alternative bleaching technology to replace CEH in Chinese non-wood PMs to reduce dioxin release. The release factor via flue gas of the alkali recovery boiler in Chinese non-wood PMs was first reported to be 0.092 μg TEQ Ad t -1 in this study. On the assumption that pulp bleaching processes of all Chinese non-wood PMs were converted from CEH to ECF, the annual release of PCDD/Fs via the bleaching wastewater and bleached pulp would be reduced by 79.1%, with a total of 1.60 g TEQ., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

In order to validate previous field observations by the authors on whitefish, Coregonus lavaretus L. s.l., a 30-day laboratory experiment with concentrations (0, 1.3, 2.3, 3.5, and 7 vol%) of bleached kraft pulp and paper mill effluent (BKME) simulating those occurring in a polluted lake was conducted. Chlorine dioxide had almost entirely replaced chlorine gas in the bleaching of pulp. As a consequence, the concentrations of adsorbable organic halogens and chlorinated phenolics (CPs) in BKME were significantly lowered compared to earlier studies. This reduction was also seen in the concentrations of CPs in the bile and CPs and extractable organic halogens in the intestinal lipids: the concentrations were low and did not depend on the dilution of BKME. In contrast, the resin acid content of bile decreased with decreasing BKME concentration. The growth of fish was speeded up in all BKME concentrations. However, at the highest BKME concentration (7 vol%) the increase was lowest. The induction of hepatic ethoxyresorufin O-deethylase (EROD) activity revealed strong dose-response relationship with BKME. At 3.5 vol% BKME (corresponding to a distance of 3.3 km from the mill sewer in the field) the EROD activity increased 12-fold. There was a tendency for lower activity of uridinediphosphate glucuronosyltransferase in the liver, but the decrease (34%; P < 0.05) was statistically significant only at 7 vol% BKME. The activity of liver glutathione S-transferase remained unchanged. All dilutions of BKME significantly depressed the concentrations of plasma immunoglobulin M (IgM). Erythrocytic concentrations of nucleotide triphosphates decreased and of sodium increased as the BKME concentration increased. Also some other blood parameters (hematocrit, hemoglobin, plasma glucose, and aspartate aminotransferase) were changed in all BKME exposures, although without obvious dependence on effluent concentration. In conclusion, there was a good agreement between field studies and laboratory experiments using BKME concentrations occurring in the field, confirming close or similar causes for responsive toxicity endpoints.

The membrane characteristics controlling 125I and 36Cl transport across anion-exchange paper membranes are examined using three different paper membranes treated with different anion exchange groups: a trimethylhydroxypropylamino group, a diethylaminoethyl group, and a 50% quaternary diethylaminoethyl group. The membrane permeability for 125I is higher than that for 36Cl in all cases. Treatment with trimethylhydroxypropylamino group improves the 125I diffusion process, and the use of 50% quaternary diethylaminoethyl group improves the 125I solution/membrane distribution process.

Six elemental chlorine-free bleaching sequences were studied to see their effect on quality of pulp produced and quantity of pollutants generated during bleaching of wheat straw soda pulp. Impact of parameters like adsorbable organic halogens (AOX), chemical oxygen demand (COD), biochemical oxygen demand (BOD) and sodium adsorption ratio, pH and total dissolved solids generated during bleaching on environment as index of global pollution (I GP ) was also studied. The purpose of the study was to investigate six elemental chlorine-free bleaching sequences to compare the pulp quality, effluent properties and their impact on environment. An oxygen delignification stage before D 0 E OP D bleaching sequence reduced the AOX, COD, colour and BOD by 44%, 42%, 36% and 33%, respectively, whereas an ozonation stage before bleaching reduced the same by 70%, 66%, 73% and 60%, respectively, as compared to those of control. The generation of pollutants as AOX, COD, colour and BOD was reduced further by 88%, 80%, 90% and 77%, respectively, with the use of short bleaching sequences (DD, DP and PD) as compared to those of control. The environmental impact as I GP with D 0 E OP D bleaching sequence was 2.65 which got reduced to 1.44 with bleaching sequence OZPD. Bleaching sequence OZD 0 E OP D was found the most effective for improving brightness and whiteness of the pulp, whereas short bleaching sequence OZPD found the most effective for reducing generation of pollutants during bleaching among different bleaching sequences studied. Graphical abstract.

The article reviews the transition from bleaching kraft pulp with elemental chlorine to bleaching with chlorine dioxide with respect to formation of chlorinated dioxins and furans (PCDD/Fs). New data is also presented for bleaching with 100% chlorine dioxide and the effect of elemental chlorine impurities. The typical fingerprint of PCDD/Fs in pulp bleached with elemental chlorine was unique compared to all other sources such as incineration and metallurgic processes. 2,3,7,8-TCDD and 2,3,7,8-TCDF were the dominating congeners formed during the period pulp was bleached with elemental chlorine. Elimination of unchlorinated precursors lowered, but did not eliminate, the formation of 2,3,7,8-TCDD and 2,3,7,8-TCDF. The formation of 2,3,7,8-TCDD and 2,3,7,8-TCDF increases exponentially with the amount of elemental chlorine used. Replacing elemental chlorine with chlorine dioxide (with levels of elemental chlorine contamination of <0.3% in the chlorine dioxide) in pulp bleaching eliminates the formation of 2,3,7,8-TCDD and 2,3,7,8-TCDF. PCDD/Fs can also be found in background levels in ecosystems, food, soil and air as well as in unbleached pulp, bleached pulp, and paper and fiber products. Thus, the only way to determine if PCDD/Fs are present from bleaching is to make a full congener analysis and compare to known sources and processes as well as to laboratory blanks and unbleached reference samples., (Copyright © 2019 The Author. Published by Elsevier Ltd.. All rights reserved.)

The effectiveness of a biorefinery based on an HWE-Kraft-ECF bleaching process and the end use of pulp was systematically evaluated. Using a P-factor of 198, nearly 30% of xylan-based sugars were recovered. The resulting pulp and paper properties were found to be comparable with the control. A maximum xylan-based sugar recovery of nearly 50% was achieved at a P-factor of 738. Although the strength of this P-factor induced handsheet was lower than that of the control by about 20%, the corresponding pulp was sufficient for dissolving pulp application. However, once the P-factor rose above 1189, hemicellulose sugars were significantly degraded into furans; pulp and paper properties were also deteriorated due to cellulose degradation, lignin deposition and condensation. Thus, considering the different end use of pulps, the performance of an HWE-based biorefinery could be balanced by its HWE severity., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

In order to study immunomodulation, controlled laboratory experiments were carried out with roach (Rutilus rutilus) exposed to bleached kraft mill effluent (BKME) or spent bleach liquor (SBL) from two pulp and paper mills using elementary chlorine and chlorine dioxide for bleaching. The total number of immunoglobulin-secreting cells (ISC) and the number of specific antibody-secreting cells (ASC) were determined by ELISPOT assay. Exposure to BKME resulted in decreased numbers of ISC in the spleen. To study the capability of response against foreign antigens the fish were immunized with bovine gamma-globulin. Exposure to BKME or SBL reduced antigen-specific ASC response in fish. Moreover, the suppression of ASC response did not require exposure prior to immunization. Depuration of fish in clean water reveals that the immunosuppression caused by BKME is reversible. The ASC response in the BKME-pretreated fish returned to the same or even a higher level compared to untreated immunized fish and, in addition, the number of ISC increased greatly. The results of this study verify an earlier finding on poor antibody response due to exposure in a lake contaminated with BKME. Exposure to SBL alone suppresses antibody-mediated immunity, suggesting that compounds formed in bleaching are at least partly responsible for immunotoxic effects.

Roach (Rutilus rutilus), from a unpolluted lake, were caged in a lake receiving treated waste waters from a pulp and paper mill 16 km upstream, and simultaneously a group of fish were held in cages in the unpolluted reference lake. The level of serum immunoglobulin of the fish kept in cages in these lakes was quantified. Serum immunoglobulin levels decreased when the fish were transferred to the contaminated lake and remained significantly reduced for the 8-week period fish were monitored. In another experiment fish were immunized with bovine gamma-globulin (BGG) after 5 weeks caging in the lakes. The kinetics of specific antibody synthesis were determined by assaying the number of antibody secreting cells in the spleen using enzyme-linked immunospot assay and by measuring the concentration of specific antibody in the serum. The peak response of the effluent exposed fish against BGG was lower than that for fish kept in the unpolluted reference lake, and the antibody titers, due to immunization, increased more slowly in the exposed fish. These results demonstrate that subchronic exposure of fish in a lake receiving treated waste waters from a bleached kraft mill affects the antibody-mediated immunity resulting in, besides lower levels of Ig, weak responsiveness against antigen.

Chlorine bleaching is still practiced by most of nonwood pulp and paper mills, resulting in a considerable amount of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) formation and emission. In this study, the effects of primary chlorination conditions on the formation of PCDD/Fs from nonwood pulp bleaching with elemental chlorine were investigated. It was found that low-chlorinated PCDD/Fs were usually formed and then underwent further chlorination to form highly chlorinated PCDD/Fs with increasing chlorination time. Higher available chlorine dosages and lower system pH values greatly accelerated dioxin formation, and pH 3 was the threshold for the formation of tetra- to octa-CDD/Fs. Higher temperatures promoted the formation of lower-chlorinated PCDD/Fs, while caused significant reduction of tetra- to hepta-CDDs and penta- to octa-OCDFs. PCDFs were formed much faster than PCDDs. A first-order kinetic model showed a good fit to the data for tetra- to oct-CDFs formation under different chlorination conditions, indicating that chlorine substitution was the rate determining step for their formation. Finally, the optimum chlorination conditions for minimizing and eliminating the formation of 2,3,7,8-TCDD/TCDF in nonwood pulp bleaching with elemental chlorine were established.

The aim of the present work was to find a suitable Kraft cooking process for olive tree pruning (OTP), in order to produce pulp of kappa number about 17. The Kraft pulp produced under optimized conditions showed a viscosity of 31.5 mPa·s and good physical, mechanical, and optical properties, which are suitable for paper production. The physical-mechanical and optical properties were measured before and after bleaching. Although the OTP pulp was bleached to 90.9% ISO brightness (kappa<1), the process demanded a long sequence of stages, OZQPOZQPO. The bleached pulp showed a brightness reversion equal to 1.3%. Furthermore, this bleached pulp did not need a high intensity of beating due to high drainability degree in the unbeaten pulp. So that, OTP is suggested as an interesting raw material for cellulosic pulp production because its properties are comparable to those of other agricultural residues, currently used in the paper industry., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

In a previous study of older pulp and paper workers in Berlin, New Hampshire, decrements in spirometry results associated with accidental exposures to high levels of irritant gases depended on cumulative levels of pulp mill exposure and cigarette smoking. Many of those subjects were older and retired. A new study was initiated to assess whether gassing events were a problem among current workers. Three hundred white male pulp and paper workers from the mill in Berlin, New Hampshire, were surveyed in 1992. Testing included spirometry and questionnaires. The mean age was 40.4 yr, and the mean tenure with the company was 18.5 yr. A total of 105 of the 300 subjects (35%) reported ever having an episode of high exposure to chlorine gases (i.e., being gassed). The percentage gassed was 51% for pulp mill workers and only 13% for other employees. For subjects with no more than 26 pack-years of cigarette smoking, obstruction (i.e., abnormally low FEV1 and FEV1/FVC) was observed only among those with a history of gassing. Also, the combination of high cigarette smoking (i.e., > 26 pack-years) and gassing had a greater than additive effect on obstruction. These findings suggest that additional controls are needed to minimize the number of gassing events in this and other chemical pulp mills.

The studies were performed on perch (Perca fluviatilis) caught outside Husum and Iggesund kraft pulp mills in 1985 and 1987, respectively, and the results were compared to previous observations from 1984 to 1985 in the receiving waters of the Norrsundet kraft pulp mill. The studies revealed that the biochemical and physiological variables, i.e., EROD activity, gonad size, number of lymphocytes, carbohydrate metabolites, and plasma ion composition, can be used as sensitive and reliable indicators of toxic effects on natural populations of fish exposed to conventional chlorine-bleached kraft mill effluents. However; the effects were generally less pronounced and indicated less geographic extension than those seen in perch previously investigated in the receiving waters of the Norrsundet kraft pulp mill. Based on these studies on perch at Husum and Iggesund and the previous studies at Norrsundet it can be concluded that the chlorine-bleached kraft mill effluents cause serious disturbances to vital biochemical and physiological functions, which can affect the health status and presumably also the survival of the fish. Finally, the responses do not reflect the present situation in the receiving waters since all three mills have taken extensive measures for process alterations and discharge reductions after the time of the investigations.

Workers in pulpmills can be exposed to a multitude of gases hazardous to respiratory function, the most common of which is chlorine gas. First-aid reports of acute gas overexposure incidents ("gassings") over an 8 year period were used to generate exposure data on a group of pulpmill workers whose respiratory function had been studied cross-sectionally in 1981 and 1988. Three hundred forty-eight incidents representing 174 workers were identified, 78% of these being treated solely by the first-aid attendant with the administration of O2 and cough suppression medication. Among 316 workers tested during a 1988 respiratory health survey, 78 had at least one chlorine or chlorine dioxide "gassing" incident. There was a significant decrease in the FEV1/FVC ratio (p less than .05) as well as increased risk for workplace associated chest symptoms in this group with at least one "gassing" incident. In an age- and smoking-matched analysis, among workers tested both in 1981 and 1988, there was a greater decline in FEV2/FVC ratio and MMF (p less than .05) in the "gassed" group than in the nonexposed group over the 7 year period of observation. These results emphasize the need for worker protection against accidental chlorine gas exposures.

Introduction: There is no robust and simple way to quantify available chlorine from small volumes such as human root canals. Therefore, a new method was developed and assessed., Methods: Standardized size-40 paper points were soaked in a 15% (w/v) potassium iodide solution for 1 minute. Subsequently, the paper points were placed in an incubator and dried at 110°C for 4 hours. The paper points (n = 5 per measurement) were then dipped in different concentrations of NaOCl and photographed under standardized conditions in RAW format. The pictures were imported to image processing software and adjusted to the standardized background. The red, green, and blue levels of the paper points were assessed at a predefined area. Inverse regression was used to determine NaOCl concentration from red, green, and blue values, with both explanatory and outcome variables log-transformed to base 10., Results: The red value measurements were chosen for further analysis based on a comparison of the coefficient of determination (R(2)) and a residual analysis. The method was applied to concentrations of NaOCl between 0.0001% and 1% (R(2) = 0.92). In this range, NaOCI concentrations could be assessed with an error not larger than 3-fold the determined concentration., Conclusions: The present method proved to be robust to determine the order of magnitude of available chlorine that is present in a small volume. This should be useful for endodontic research., (Copyright © 2014. Published by Elsevier Inc.)

Long-term immobilization ratios of strontium (Sr2+) and cesium (Cs+) in paper sludge ash-based geopolymer (PS-GP) were investigated in one year. PS-GP paste specimens were prepared in the conditions of 20 °C and 100% R.H., using two kinds of paper sludge ash (PS-ash). Two kinds of alkaline solution were used in the PS-GP as activator. One was prepared by diluting aqueous Na-disilicate (water glass) with seawater. Another was a mixture of this solution and caustic soda of 10 M concentration. When seawater was mixed into the alkaline solution, unstable fixations of Sr2+ and Cs+ were greatly improved, resulting stable and high immobilization ratios at any age up to one year, no matter what kind of PS-ash and alkaline solution were used. Element maps obtained by EPMA exhibited nearly even distribution of Cs+. However Sr2+ was biased, making domains so firmly related to Ca2+ presence. The mechanism that seawater stabilizes immobilization of Sr2+ and Cs+ was discussed in this study, but still needs to further investigation. Chemical composition analyses of PS-GP were also conducted by SEM-EDS. Two categories of GP matrix were clearly observed, so called N-A-S-H and C-A-S-H gels, respectively. By plotting in ternary diagrams of SiO2-(CaO + Na2O)-Al2O3 and Al2O3-CaO-Na2O, compositional trends were discussed in view of ‘plagioclase gels’ newly found in this study. As a result, it is suggested that the N-A-S-H and C-A-S-H gels should be strictly called Na-rich N-C-A-S-H and Ca-rich N-C-A-S-H gels, respectively.

Scheme 1 The illustration of the synthesis of dual-emission type N, Cl-doped carbon dots by a simple hydrothermal route and the implications. [Display omitted] • Dual-emission N, Cl-CDs with strong orange fluorescence were simply synthesized. • The N, Cl-CDs exhibited precise sensing toward VB 2 , VB 9 , VB 12 in aqueous solution. • Visually semiquantitative detection of three VBs were performed on test strip. • The detection of VBs were successfully applied in real samples. Although a few of fluorescent probes based on carbon dots (CDs) for vitamin B (VB) determination have been emerged, none of them can realize the detection of different kinds of VB. In this paper, nitrogen, chlorine co-doped dual-emission CDs (N, Cl-CDs) with emissions at 404 nm and 595 nm have been easily synthesized. VB 2 , VB 9 and VB 12 can all induce obvious fluorescence turn-off response toward the N, Cl-CDs. Based on that, three types of VBs are quantitatively and sensitively evaluated in aqueous solution with wide concentration ranges of 14.9–135.0 μM, 34.7–89.8 μM and 29.8–79.8 μM, respectively. Importantly, visual semiquantitative detection of VBs on a test strip are also proposed. Moreover, the current N, Cl-CDs have been successfully applied to the detection of VBs in real samples. The N, Cl-CDs are sensitively multifunctional sensors for three kinds of VBs in aqueous solution and the visual semiquantitative detection by test paper assay is simple, portable and inexpensive. [ABSTRACT FROM AUTHOR]

In recent decades, metal-containing nanocomposites have attracted considerable attention from researchers. In this work, for the first time, a detailed analysis of the preparation of reactive indicator papers (RIPs) based on silver-containing nanocomposites derived from silver fumarate was carried out. Thermolysis products are silver-containing nanocomposites containing silver nanoparticles uniformly distributed in a stabilizing carbon matrix. The study of the optical properties of silver-containing nanocomposites made it possible to outline the prospects for their application in chemical analysis. RIPs were made by impregnating a cellulose carrier with synthesized silver fumarate-derived nanocomposites, which change their color when interacting with chlorine vapor. This made it possible to propose a method for the determination of chloride ions with preliminary oxidation to molecular chlorine, which is then separated from the solution by gas extraction. The subsequent detection of the active zone of RIPs using colorimetry makes it possible to identify mathematical dependences of color coordinates on the concentration of chloride ions. The red (R) color coordinate in the RGB (red-green-blue) system was chosen as the most sensitive and promising analytical signal. Calibration plots of exponential and linear form and their equations are presented. The limit of detection is 0.036 mg/L, the limits of quantification are 0.15–2.4 mg/L, and the time of a single determination is 25 min. The prospects of the developed technique have been successfully shown in the example of the analysis of the natural waters of the Don River, pharmaceuticals, and food products. [ABSTRACT FROM AUTHOR]

Background, Aims, and Scope: Currently, elemental chlorine-free (ECF) and totally chlorine-free (TCF) bleaching systems are widely used for pulp production. Low and medium molecular weight lignin break-down products are known to have harmful effects on the environment. According to some recent results, also high molecular weight (HMW) material consisting mainly of lignin and carbohydrates may cause toxic effects to the environment. For these reasons, toxicity and structure studies of HMW materials are of great importance. This investigation is a part of a larger project to obtain more structure information of HMW materials and toxicity of ECF and TCF bleaching effluents. Size-exclusion chromatography (SEC) has been commonly used for the characterization of organic macromolecules such as lignin, but to our knowledge, no reports have appeared dealing with the comparison of SEC of ECF and TCF bleaching liquors. The aim of the present study was to get more information about the molecular weight distribution (MWD) of HMW fractions of waste liquors from ECF and TCF bleaching sequences by SEC., Methods: The MWDs of organic materials dissolved during different stages of ECF bleaching (O-D-EOP-D-ED) and TCF bleaching (O-Z-Q-P-Z-Q-P-P) of softwood (Pinus sylvestris) kraft pulp were determined and compared by SEC. All effluent samples from the above bleaching stages were ultrafiltrated using a membrane with a cutoff value of 1,000 Da. SEC was performed on high and also low molecular weight fractions and non-fractionated effluents. In the SEC experiments, a Superdex 75 column was used with 0.1 M NaOH solution as the eluent. Standards used for calibrating the SEC system were albumin, carboanhydrase, cytochrome C, tannic acid, dehydrodiacetovanillone, and vanillin., Results and Discussion: The chromatograms of liquors from TCF bleaching stages vary more than those from ECF bleaching. Peroxide and chelating stages contained mostly high molecular weight (HMW) matter whereas chlorine dioxide and ozone stages had more low molecular weight compounds. The lignin content in HMW matter was higher than in stages that consisted of low molecular matter. Bleaching effluents contained the highest amounts of HMW material, mainly lignin, in the beginning of the sequences; the amounts decreased towards the end of the bleaching sequence., Conclusion: Determinations of MWD by the SEC method showed that effluents from the TCF sequence contained more HMW material than those from the ECF stage. This might be due to peroxide stages (P) that dissolve HMW lignin effectively. However, the molecular weights of ozone stages (Z) were very low compared to other stages. Chlorine dioxide stages also dissolved mostly low molecular weight lignin. Ultrafiltration of bleaching liquors showed that high molecular weight fraction also included some low molecular weight compounds and vice versa. High polydispersity and high lignin content correlated with the amount of HMW material in ECF and TCF bleaching stages., Recommendation and Outlook: Our liquor samples were studied by using a UV detector commonly used for lignin preparations; in upcoming investigations, it will be interesting to determine carbohydrates such as hemicelluloses. The results are applicable in papermaking in order to improve commonly used bleaching procedures, to test new potential bleaching systems, and to study chemical behavior of HMW materials in various bleaching liquors. The present results also form a good basis for toxicity measurements of ECF and TCF bleaching effluents and for more comprehensive spectroscopic and chromatographic experiments with samples taken from various bleaching stages. From the behavior of liquors studied, it appears that our other structure investigations by spectroscopic and chromatographic (NMR, Py-GC/MS, etc.) methods mostly correlate well with the present results.