Evaluation of UV/TiO(2) and UV/ZnO photocatalytic systems coupled to a biological process for the treatment of bleaching pulp mill effluent

This paper presents an exploratory study of pulp mill bleaching effluent treatment by a biological-photocatalytic coupled system. A fungus, Trametes pubescens, immobilized on polyurethane foam was used to inoculate the biological pre-treatment system. The pretreated effluent was then exposed to a photocatalytic treatment in which two catalysts (TiO₂ and ZnO) and two supports (aluminum foil and Luffa cylindrica) were tested. Catalyst characterization was carried out by means of X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Information about crystalline structure, chemical composition, morphology, homogeneity and distribution on the support surface area was obtained. The overall biological-photocatalytic coupled system achieved degradation of 96% of initial total organic carbon (TOC), 97% of 2-chlorophenol (2-CP), 90% of 2,4-dichlorophenol (2,4-CP) and 99% of 2,4,6-trichlorophenol (2,4,6-TCP). This approach of synergistic coupling of T. pubescens and a semiconductor photocatalyst appears to be a viable alternative for the treatment of these non-biodegradable effluents.     

The use of Microtox to assess toxicity removal of industrial effluents from the industrial district of Camaçari (BA, Brazil)

The treatment efficiency, as toxicity removal, of complex effluents from the Industrial District of Cama?ari (BA, Brazil), after biological treatment with activated sludge was evaluated using Microtox. Samples of the equalised effluent (EE) were collected prior to treatment together with samples of the treated effluent (TE), which remained 24 h in the treatment plant. Rehydrated colonies of Vibrio fischeri were exposed to sequential dilutions of EE and TE to assess luminosity interference. Values for EC50 were calculated, together with the respective toxicity units. In all, twenty assays of each effluent type were carried out and the mean toxicity removal was 92.71%, while the chemical oxygen demand (COD) presented mean reduction of 83.04%. There was a variability of an order of magnitude between the Microtox results for the two types of effluents. The mean EC50 values were 2.12 for EE and 47.78% for TE. In spite of its weakness in some conditions, the Microtox system demonstrated to work adequately in assessing effluent toxicity removal in this treatment plant and therefore can be used for further toxicity removal programs.     

Extractability of water-soluble soil organic matter as monitored by spectroscopic and chromatographic analyses

Purpose

Cold and hot water processes have been intensively used to recover soil organic matter, but the effect of extraction conditions on the composition of the extracts were not well investigated. Our objective was to optimize the extraction conditions (time and temperature) to increase the extracted carbon efficiency while minimizing the possible alteration of water extractable organic matter of soil (WEOM).

Method

WEOM were extracted at 20°C, 60°C, or 80°C for 24?h, 10?C60?min, and 20?min, respectively. The different processes were compared in terms of pH of suspensions, yield of organic carbon, spectroscopic properties (ultraviolet?Cvisible absorption and fluorescence), and by chromatographic analyses.

Results

For extraction at 60°C, the time 30?min was optimal in terms of yield of organic carbon extracted and concentration of absorbing and fluorescent species. The comparison of WEOM 20°C, 24?h; 60°C, 30?min; and 80°C, 20?min highlighted significant differences. The content of total organic carbon, the value of specific ultraviolet absorbance (SUVA₂₅₄), the absorbance ratio at 254 and 365?nm (E ₂/E ₃), and the humification index varied in the order: WEOM (20°C, 24?h)?Conclusions For the soil chosen, extraction at 60°C for 30?min is the best procedure for enrichment in organic chemicals and minimal alteration of the organic matter.     

Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV–Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.     

Treatment of bleach pulp mill effluent by MF-MBR

The types of treatment most commonly used by pulp mills are biological treatments in combination with sedimentation or coagulation/flocculation as pretreatment. The main issues faced by these types of treatment are low efficiency in the removal of organic matter and the loss of aggregate value for the recovered fiber. Therefore, this study aims to evaluate the use of microfiltration (MF) combined with a membrane bioreactor (MBR) for the treatment of bleach pulp mill effluents. The results showed that the use of the MF-MBR system was an excellent alternative for the treatment of bleach pulp mill effluents with an average COD removal of 95%. The microfiltration allowed the recovery of fibers, which can be returned to the production process without losing economic value, and produced a better quality effluent for further treatment in the MBR. The MBR presented high efficiency removal of organic matter.     

Comparative toxicity of effluents processed by different treatments in V79 fibroblasts and the algae Selenastrum capricornutum

The efficacy of ozonation and of photocatalysis processing in the treatment of pulp mill ECF (elementary chlorine free) bleaching and textile effluents was evaluated by determining total organic carbon reduction (TOC) and the toxicity. The chronic toxicity of the effluents was evaluated by the ability to inhibit the growth of algae Selenastrum capricornutum. Cultured hamster V79 fibroblasts were used to assess the cytotoxicity of effluents submitted to different detoxification processes. Two endpoints were measured in V79 cells: 3-(4,5-dimethylthiazole-2-yl)-2,5-biphenyl tetrazolium bromide (MTT) reduction and neutral red uptake (NRU). Both treatment processes were able to reduce the TOC, although ozonization was less effective for pulp mill ECF bleaching. The pulp mill ECF bleaching and textile effluents reduced the growth of S. capricornutum by 39% and 27%, respectively. However, at the highest concentration tested, the textile effluents treated by photochemical process for 60 min showed increased cytotoxicity in V79 cells compared to the untreated effluent when assessed by the NRU and MTT reduction assays (increases of 30% and 40%, respectively). Pulp mill ECF bleaching effluent treated by ozonization had a similar cytotoxicity to that of untreated effluent in the NRU assay. In contrast, the MTT reduction assay indicated that effluents treated with ozone were around 20% more cytotoxic than untreated effluents. These results show that cultured fibroblasts may be useful for studying cellular responses to pollutants and may be included in tests to monitor the efficiency of effluent detoxification processes.     

Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV–Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.     

Effects of tertiary treatment by fungi on organic compounds in a kraft pulp mill effluent

Background, aim and scope  

Pulp and paper mills generate a plethora of pollutants depending upon the type of pulping process. Efforts to mitigate the environmental impact of such effluents have been made by developing more effective biological treatment systems in terms of biochemical oxygen demand, chemical oxygen demand, colour and lignin content. This study is the first that reports an evaluation of the effects of a tertiary treatment by fungi (Pleurotus sajor caju, Trametes versicolor and Phanerochaete chrysosporium and Rhizopus oryzae) on individual organic compounds of a Eucalyptus globulus bleached kraft pulp and paper mill final effluent after secondary treatment (final effluent).     

An investigation of anthraquinone dye biodegradation by immobilized Aspergillus flavus in fluidized bed bioreactor

Purpose

Biodegradation and biodecolorization of Drimarene blue K₂RL (anthraquinone) dye by a fungal isolate Aspergillus flavus SA2 was studied in lab-scale immobilized fluidized bed bioreactor (FBR) system.

Method

Fungus was immobilized on 0.2-mm sand particles. The reactor operation was carried out at room temperature and pH?5.0 in continuous flow mode with increasing concentrations (50, 100, 150, 200, 300, 500?mg?l^?1) of dye in simulated textile effluent on the 1st, 2nd, 5th, 8th, 11th, and 14th days. The reactors were run on fill, react, settle, and draw mode, with hydraulic retention time (HRT) of 24?C72?h. Total run time for reactor operation was 17?days.

Results

The average overall biological oxygen demand (BOD), chemical oxygen demand (COD), and color removal in the FBR system were up to 85.57%, 84.70%, and 71.3%, respectively, with 50-mg?l^?1 initial dye concentration and HRT of 24?h. Reductions in BOD and COD levels along with color removal proved that the mechanism of biodecolorization and biodegradation occurred simultaneously. HPLC and LC?CMS analysis identified phthalic acid, benzoic acid, 1, 4-dihydroxyanthraquinone, 2,3-dihydro-9,10-dihydroxy-1,4-anthracenedione, and catechol as degradation products of Drimarene blue K₂RL dye. Phytotoxicity analysis of bioreactor treatments provided evidence for the production of less toxic metabolites in comparison to the parent dye.

Conclusion

The present fluidized bed bioreactor setup with indigenously isolated fungal strain in its immobilized form is efficiently able to convert the parent toxic dye into less toxic by-products.     

Decolorization and detoxification of two textile industry effluents by the laccase/1-hydroxybenzotriazole system

The aim of this work was to determine the optimal conditions for the decolorization and the detoxification of two effluents from a textile industry—effluent A (the reactive dye bath Bezactive) and effluent B (the direct dye bath Tubantin)—using a laccase mediator system. Response surface methodology (RSM) was applied to optimize textile effluents decolorization. A Box–Behnken design using RSM with the four variables pH, effluent concentration, 1-hydroxybenzotriazole (HBT) concentration, and enzyme (laccase) concentration was used to determine correlations between the effects of these variables on the decolorization of the two effluents. The optimum conditions for pH and concentrations of HBT, effluent and laccase were 5, 1 mM, 50 % and 0.6 U/ml, respectively, for maximum decolorization of effluent A (68 %). For effluent B, optima were 4, 1 mM, 75 %, and 0.6 U/ml, respectively, for maximum decolorization of approximately 88 %. Both effluents were treated at 30 °C for 20 h. A quadratic model was obtained for each decolorization through this design. The experimental and predicted values were in good agreement and both models were highly significant. In addition, the toxicity of the two effluents was determined before and after laccase treatment using Saccharomyces cerevisiae, Bacillus cereus, and germination of tomato seeds.     

Antimicrobial activity of metal oxide nanoparticles supported onto natural clinoptilolite

The antimicrobial activity of Cu₂O, ZnO and NiO nanoparticles supported onto natural clinoptilolite was investigated in the secondary effluent under dark conditions. After 24 h of contact the Cu₂O and ZnO nanoparticles reduced the numbers of viable bacterial cells of Escherichia coli and Staphylococcus aureus in pure culture for four to six orders of magnitude and showed consistent 100% of antibacterial activity against native E. coli after 1 h of contact during 48 exposures. The antibacterial activity of NiO nanoparticles was less efficient. The Cu₂O and NiO nanoparticles showed 100% of antiprotozoan activity against Paramecium caudatum and Euplotes affinis after 1 h of contact, while ZnO nanoparticles were less efficient. The morphology and crystallinity of the nanoparticles were not affected by microorganisms. The metal oxide nanoparticles could find a novel application in the disinfection of secondary effluent and removal of pathogenic microorganisms in the tertiary stage of wastewater treatment.     

Solar CPC pilot plant photocatalytic degradation of bisphenol A in waters and wastewaters using suspended and supported-TiO2. Influence of photogenerated species

Photocatalytic degradation of bisphenol A (BPA) in waters and wastewaters in the presence of titanium dioxide (TiO₂) was performed under different conditions. Suspensions of the TiO₂ were used to compare the degradation efficiency of BPA (20 mg L^?1) in batch and compound parabolic collector (CPC) reactors. A TiO₂ catalyst supported on glass spheres was prepared (sol–gel method) and used in a CPC solar pilot plant for the photodegradation of BPA (100 μg L^?1). The influence of OH·, O₂ ^·?, and h ⁺ on the BPA degradation were evaluated. The radicals OH· and O₂ ^·? were proved to be the main species involved on BPA photodegradation. Total organic carbon (TOC) and carboxylic acids were determined to evaluate the BPA mineralization during the photodegradation process. Some toxicological effects of BPA and its photoproducts on Eisenia andrei earthworms were evaluated. The results show that the optimal concentration of suspended TiO₂ to degrade BPA in batch or CPC reactors was 0.1 g L^?1. According to biological tests, the BPA LC₅₀ in 24 h for E. andrei was of 1.7?×?10^?2 mg cm^?2. The photocatalytic degradation of BPA mediated by TiO₂ supported on glass spheres suffered strong influence of the water matrix. On real municipal wastewater treatment plant (MWWTP) secondary effluent, 30 % of BPA remains in solution; nevertheless, the method has the enormous advantage since it eliminates the need of catalyst removal step, reducing the cost of treatment.     

Performance and efficiency of removal of pharmaceutical compounds from hospital wastewater by lab-scale biological treatment system

The fate of pharmaceuticals after discharged from hospital into wastewater was clarified experimentally by using a new lab-scale conventional activated sludge (CAS) treatment reactor. The 43 target compounds belong to nine therapeutic classes (antivirals, antibacterials, anticancer drugs, psychotropics, antihypertensives, analgesic–antipyretics, contrast media, herbal medicines, and phytoestrogens) were selected with inclusion of 16 newly estimated compounds. The efficiency of the present reactor was estimated by comparing the reaction rate constant of the solid-water partition coefficients (log K_d) between liquid and solid samples and half-life during 48-h experiment obtained by using hospital effluents with those obtained by using STP wastewater. The results that no significant difference in removal efficiency was observed between both water samples (P?>?0.05) indicate high reliability of the present lab-scale reactor. The actual rates of removal when hospital effluent was applied varied widely (mean, 59?±?40%) independent of type of the pharmaceuticals. More than 90% of 17 compounds were removed after 8 h of treatment. However, the values for psychotropics (mean, 19?±?26%) and contrast media (mean, 24?±?17%) were generally low, indicating high stability. The log K_d values ranged from 1.3 to 4.8. Notably, clarithromycin, acridine, and glycitein could be removed in both liquid and solid phases. The dominant removal mechanisms were found to be different for individual pharmaceutical. These results suggest the effectiveness of introduction of the lab-scale biological treatment system for development of a new solution for discharge of pharmaceuticals from hospital.

     

Dioxin formation in pulp and paper mills of India

Samples of effluents, sludge, pulp, final products (paper) and soil were collected from the identified pulp and paper mills in India. The samples were analysed for 2,3,7,8-tetrachloro-dibenzo-p-dioxin (2,3,7,8-TCDD) and other dioxin congeners and precursors. Pulp and paper mills using chlorine for the bleaching process showed the presence of 2,3,7,8-TCDD in effluent samples. In the effluent and pulp samples from mills where chlorine dioxide was used as a bleaching agent, the 2,3,7,8-TCDD congener ranged from below the detection limit 0.05 to 0.12 ngL⁻¹/ngg⁻¹. The relative standard deviation of reproducibility and the percent recovery of 2,3,7,8-TCDD were 2.07 and 82.4% in pulp and 2.8 and 92% in effluent, respectively. The 1,3,6,8-TCDD was the only other major dioxin congener found in the treated and untreated effluent and sludge samples. However, dichlorobenzene, trichlorophenyl, and hexachlorobiphenyl were detected in all samples. The formation of dioxins can be minimised by replacing chlorine with chlorine dioxide in bleaching processes in pulp and paper mills.     

Photocatalytic degradation of contaminants of concern with composite NF-TiO2 films under visible and solar light

This study reports the synthesis and characterization of composite nitrogen and fluorine co-doped titanium dioxide (NF-TiO₂) for the removal of contaminants of concern in wastewater under visible and solar light. Monodisperse anatase TiO₂ nanoparticles of different sizes and Evonik P25 were assembled to immobilized NF-TiO₂ by direct incorporation into the sol–gel or by the layer-by-layer technique. The composite films were characterized with X-ray diffraction, high-resolution transmission electron microscopy, environmental scanning electron microscopy, and porosimetry analysis. The photocatalytic degradation of atrazine, carbamazepine, and caffeine was evaluated in a synthetic water solution and in an effluent from a hybrid biological concentrator reactor (BCR). Minor aggregation and improved distribution of monodisperse titania particles was obtained with NF-TiO₂-monodisperse (10 and 50 nm) from the layer-by-layer technique than with NF-TiO₂?+?monodisperse TiO₂ (300 nm) directly incorporated into the sol. The photocatalysts synthesized with the layer-by-layer method achieved significantly higher degradation rates in contrast with NF-TiO₂-monodisperse titania (300 nm) and slightly faster values when compared with NF-TiO₂-P25. Using NF-TiO₂ layer-by-layer with monodisperse TiO₂ (50 nm) under solar light irradiation, the respective degradation rates in synthetic water and BCR effluent were 14.6 and 9.5?×?10^?3?min^?1 for caffeine, 12.5 and 9.0?×?10^?3?min^?1 for carbamazepine, and 10.9 and 5.8?×?10^?3?min^?1 for atrazine. These results suggest that the layer-by-layer technique is a promising method for the synthesis of composite TiO₂-based films compared to the direct addition of nanoparticles into the sol.     

Effects of solar radiation on the fluorescence properties and molecular weight of fulvic acids from pulp mill effluents

The pulp and paper industry generates large volume of wastewater that adversely affects water resources. Lignin derived macromolecular compounds, similar to natural humic substances, are the main waste products in the pulp mill effluents. The UV-Vis and fluorescence spectroscopies were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. Solar irradiation of the solutions of these fulvic acids caused solution acidification and decay both in the UV-Vis absorbance and in the fluorescence. This decay was not the same for the whole spectra but pointed to the selective photodegradation of lignin typical structures. Furthermore, by sequential ultrafiltration it was found that during irradiation, the high-molecular weight fractions were destroyed and low-molecular-weight constituents, potentially more able to penetrate the cell membranes of living organisms were formed. Photodegradation of macromolecular organic matter from a kraft pulp mill effluent may be a key process occurring in natural waters that modifies the physicochemical properties of such effluents.     

Experimental design of Fenton and photo-Fenton reactions for the treatment of cellulose bleaching effluents

Multivariate experimental design was applied to the treatment of a cellulose conventional bleaching effluent in order to evaluate the use of the Fenton reagent under solar light irradiation. The effluent was characterised by the general parameters total organic carbon (TOC), chemical oxygen demand and color, and it was analysed for chlorinated low molecular weight compounds using GC–MS. The main parameters that govern the complex reactive system: Fe(II) and H₂O₂ initial concentration, and temperature were simultaneously studied. Factorial experimental design allowed to assign the weight of each variable in the TOC removal after 15 min of reaction. Temperature had an important effect in the organic matter degradation, especially when the ratio of Fenton reagents was not properly chosen. Fenton reagent under solar irradiation proved to be highly effective for these types of wastewaters. A 90% TOC reduction was achieved in only 15 min of treatment. In addition, the GC–MS analysis showed the elimination of the chlorinated organic compounds initially detected in the studied bleaching effluents.     

Diagnosis of dissolved organic matter removal by GAC treatment in biologically treated papermill effluents using advanced organic characterisation techniques

Granular activated carbon (GAC) exhaustion rates on pulp and paper effluent from South East Australia were found to be a factor of three higher (3.62 cf. 1.47 kg m⁻³) on Kraft mills compared to mills using Thermomechanical pulping supplemented by Recycled Fibre (TMP/RCF). Biological waste treatment at both mills resulted in a final effluent COD of 240 mg L⁻¹. The dissolved organic carbon (DOC) was only 1.2 times higher in the Kraft effluent (70 vs. 58 mg L⁻¹), however, GAC treatment of Kraft and TMP/RCF effluent was largely different on the DOC persisted after biological treatment. The molecular mass (636 vs. 534 g mol⁻¹) and aromaticity (5.35 vs. 4.67 L mg⁻¹ m⁻¹) of humic substances (HS) were slightly higher in the Kraft effluent. The HS aromaticity was decreased by a factor of 1.0 L mg⁻¹ m⁻¹ in both Kraft and TMP/RCF effluent. The molecular mass of the Kraft effluent increased by 50 g mol⁻¹ while the molecular mass of the TMP/RCF effluent was essentially unchanged after GAC treatment; the DOC removal efficiency of the GAC on Kraft effluent was biased towards the low molecular weight humic compounds. The rapid adsorption of this fraction, coupled with the slightly higher aromaticity of the humic components resulted in early breakthrough on the Kraft effluent. Fluorescence excitation-emission matrix analysis of the each GAC treated effluent indicated that the refractory components were higher molecular weight humics on the Kraft effluent and protein-like compounds on the TMP/RCF effluent. Although the GAC exhaustion rates are too high for an effective DOC removal option for biologically treated pulp and paper mill effluents, the study indicates that advanced organic characterisation techniques can be used to diagnose GAC performance on complex effluents with comparable bulk DOC and COD loads.     

Bioremediation of chromium by novel strains Enterobacter aerogenes T2 and Acinetobacter sp. PD 12 S2

Purpose

This study had an objective to identify the most potent chromium-resistant bacteria isolated from tannery effluent and apply them for bioremediation of chromium in tannery effluents.

Methods

Two such strains (previously characterized and identified by us)??Enterobacter aerogenes (NCBI GenBank USA Accession no. GU265554) and Acinetobacter sp. PD 12 (NCBI GenBank USA Accession no. GU084179)??showed powerful chromium resistivity and bioremediation capabilities among many stains isolated from tannery waste. Parameters such as pH, concentration of hexavalent chromium or Cr (VI), and inoculum volume were varied to observe optimum bioconversion and bioaccumulation of Cr (VI) when the said strains were grown in M9 minimal salt media. E. aerogenes was used to remediate chromium from tannery effluents in a laboratory level experiment.

Results

Observation by Scanning Electron Microscope and chromium peak in Energy Dispersive X-ray Spectroscopic microanalysis revealed that E. aerogenes helped remediate a moderate amount of Cr (VI) (8?C16?mg?L^?1) over a wide range of pH values at 35?C37°C (within 26.05?h). High inoculum percentage of Acinetobacter sp. PD 12 also enabled bioremediation of 8?C16?mg?L^?1 of Cr (VI) over a wide range of temperature (25?C37°C), mainly at pH?7 (within 63.28?h). The experiment with real tannery effluent gave very encouraging results.

Conclusion

The strain E. aerogenes can be used in bioremediation of Cr (VI) since it could work in actual environmental conditions with extraordinarily high capacity.     

Aerobic inhibition assessment for anaerobic treatment effluent of antibiotic production wastewater

Biological treatment of antibiotic production effluents is an economical approach; however, there are still difficulties to overcome because of the recalcitrant characteristics of these compounds to biodegradation. This study aims to reveal that anaerobic treatment technology can be an option as pretreatment before the activated sludge system treatment to treat antibiotic production effluents. The ISO 8192 method was chosen to test the inhibitory effect of raw and treated antibiotic production effluents in this work. Inhibition tests, which were applied according to ISO 8192, highlighted that the anaerobic treatment effluent is less inhibitory than antibiotic production effluent for activated sludge system. Early EC₅₀ concentrations (30-min values) of raw and treated wastewaters were lower than 180-min values. Also, triple effects (sulfamethoxazole–erythromycin–tetracycline) of antibiotics are more toxic than dual effects (sulfamethoxazole–tetracycline). In light of the experimental results obtained and their evaluation, it can be concluded that anaerobic digestion can be applied as a biological pretreatment method for pharmaceutical industry wastewater including antibiotic mixtures prior to aerobic treatment.