Improvement of biodegradability of PVA-containing wastewater by ionizing radiation pretreatment

Background

Polyvinyl alcohol (PVA) has been widely used as sizing agents in textile and manufacturing industry, and it is a refractory compound with low biodegradability.

Objective

The objective of this paper was to treat the PVA-containing wastewater using gamma irradiation as a pretreatment strategy to improve its biodegradability and to determine the roles of different kinds of radical species played during pretreatment.

Methods

Gamma radiation was carried out in a ⁶⁰Cobalt source station, PVA concentration was analyzed by using a visible spectrophotometer and specific oxygen uptake rate (SOUR, milligram of O₂ per gram of mixed liquor volatile suspended solids (MLVSS) per hour) was measured by a microrespirometer.

Results

The results showed that the biodegradability of PVA-containing wastewater with low initial concentration (e.g., 327.8?mg/l) could be improved greatly with increasing irradiation dose. However, PVA gel formation was observed at higher initial PVA concentration (e.g., 3,341.6?mg/l) and higher irradiation dose, which inhibited PVA degradation by aerobic microorganisms. However, the formed gel could be separated by microfiltration, which led to more than 90% total organic carbon (TOC) removal.

Conclusion

Ionizing radiation could be used as a pretreatment technology for PVA-containing wastewater, and its combination with biological process is feasible.     

Biodegradation of polystyrene-graft-starch copolymers in three different types of soil

Materials based on polystyrene and starch copolymers are used in food packaging, water pollution treatment, and textile industry, and their biodegradability is a desired characteristic. In order to examine the degradation patterns of modified, biodegradable derivates of polystyrene, which may keep its excellent technical features but be more environmentally friendly at the same time, polystyrene-graft-starch biomaterials obtained by emulsion polymerization in the presence of new type of initiator/activator pair (potassium persulfate/different amines) were subjected to 6-month biodegradation by burial method in three different types of commercially available soils: soil rich in humus and soil for cactus and orchid growing. Biodegradation was monitored by mass decrease, and the highest degradation rate was achieved in soil for cactus growing (81.30 %). Statistical analysis proved that microorganisms in different soil samples have different ability of biodegradation, and there is a significant negative correlation between the share of polystyrene in copolymer and degree of biodegradation. Grafting of polystyrene on starch on one hand prevents complete degradation of starch that is present (with maximal percentage of degraded starch ranging from 55 to 93 %), while on the other hand there is an upper limit of share of polystyrene in the copolymer (ranging from 37 to 77 %) that is preventing biodegradation of degradable part of copolymers.     

Investigation on pretreatment of centrifugal mother liquid produced in the production of polyvinyl chloride by air-Fenton technique

Centrifugal mother liquid (CML) is one of the main sources of wastewater produced during the production of polyvinyl chloride in chlor-alkali industry. CML is a typical poorly biodegradable organic wastewater, containing many kinds of refractory pollutants. Specifically, it contains dissolved refractory polymers, especially polyvinyl alcohol (PVA), which can pass though the biotreatment processes and clog the membranes used for further treatment. In this study, to ensure the CML applicable to biotreatment and membrane treatment, a novel efficient and mild technique, air-Fenton treatment, was employed as a pretreatment technique to improve biodegradability of the CML and to break down the polymers in the CML. Firstly, the technique was optimized for the CML treatment by optimizing the main parameters, including the dosage of ferrous sulfate, initial pH of the wastewater, [H₂O₂]/[Fe²⁺], aeration rate, reaction time, and temperature, based on removal efficiency of COD and PVA from the CML. Then, the optimized technique was tested and evaluated. The results indicated that under the optimized conditions, the air-Fenton treatment could remove 66, 98, and 55 % of the COD, PVA, and TOC, respectively, from the CML. After the treatment, biodegradability of the wastewater increased significantly (BOD/COD increased from 0.31 to 0.68), and almost all of the PVA polymers were removed or broken down. Meanwhile, concentration of the remaining iron ions, which were added during the treatment, was also quite low (only 2.9 mg/L). Furthermore, most of the suspended materials and ammonia nitrogen, and some of the phosphorus in the wastewater were removed simultaneously.     

Removal of two cationic dyes from a textile effluent by filtration-adsorption on wood sawdust

BACKGROUND: Wastewater from textile industry contains various contaminants such as dyes, surfactants and heavy metals. Textile dyes have synthetic origin and complex aromatic molecular structures that make them difficult to biodegrade when discharged in the ecosystem. The objective of this study was to examine the decolourisation of textile effluents containing cationic dyes by filtration-adsorption on wood sawdust from two different origins; fir as an example of a conifer tree, and beech as an example of a deciduous one, and to explain the adsorption mechanism. METHODS: The process of dye removal was applied to a synthetic effluent in batch mode. Adsorption experiments were performed by suspending sawdust in the effluent and analyzing the supernatant by spectrophotometry. The effectiveness of the treatment process was evaluated by measuring coloration. RESULTS AND DISCUSSION: Experimental results showed a significant potential for wood sawdust, especially coniferous sawdust, to remove cationic dyes from textile effluents. Adsorption kinetics was influenced by the initial dye concentration, nature and amount of sorbent as well as sorbent particle size. The adsorption followed a pseudo first-order kinetics. For both basic dyes, the Langmuir adsorption equation showed a better fit than the Freundlich equation. CONCLUSION: Filtration-adsorption using an inexpensive and readily available biosorbent provided an attractive alternative treatment for dye removal, and it does not generate any secondary pollution. Recommendations and Perspectives. Laboratory studies provide promising perspectives for the utilization of wood sawdust as renewable adsorbent for reducing pollution while enhancing the reuse of textile effluents. However, the treatment process needs to be applied to the other textile dye classes in order to be used on an industrial scale.     

Effects of livestock wastewater variety and disinfectants on the performance of constructed wetlands in organic matters and nitrogen removal

Background, aim and scope  

Treatment performance of constructed wetlands (CWs) is largely dependent on the characteristics of the wastewater. Although livestock wastewater is readily biodegradable in general, its variety in biodegradability can still be significant in practice. In addition, it is a common practice to periodically use disinfectants in livestock activities for health concerns. Obviously, the residual of the disinfectants in livestock wastewater may have serious inhibitory effect on the microbial activities during wastewater treatment. Thus, the main objective of this study was to examine the variety of livestock wastewater in biodegradability and its effect on the performance of a pilot scale tidal flow CWs (TFCWs) in organic matter and nitrogen removal. Furthermore, investigation of the potential inhibition of the chosen disinfectants on organic matter biodegradation and nitrification was another aim of this study.     

Effect of textile auxiliaries on the biodegradation of dyehouse effluent in activated sludge

The textile industry is confronted with serious environmental problems associated with its immense wastewater discharge, substantial pollution load, extremely high salinity, and alkaline, heavily coloured effluent. Particular sources of recalcitrance and toxicity in dyehouse effluent are two frequently used textile auxiliaries; i.e. dye carriers and biocidal finishing agents. The present experimental work reports the observation of scientific and practical significance related with the effect of two commercially important textile dye carriers and two biocidal finishing agents on biological activated sludge treatment at a textile preparation, dyeing and finishing plant in Istanbul. Respirometric measurements of the dyehouse effluent spiked with the selected textile chemicals were carried out for the assessment of the "readily biodegradable COD fraction" of the wastewater. The respirometric data obtained to visualize the effect of the selected textile auxiliaries on biomass activity was evaluated by an adopted activated sludge model. Results have indicated that the tested biocides did not exert any significant inhibitory effect on the treatment performance of the activated sludge reactor at the concentrations usually encountered in the final, total dyehouse effluent. The situation with the dye carriers was inherently different; one dye carrier appeared to be highly toxic and caused serious inhibition of the microbial respirometric activity, whereas the other dye carrier, also known as the more ecological alternative, i.e. the "Eco-Carrier", appeared to be biodegradable. Finally, the respirometric profile obtained for the Eco-Carrier was described by a simplified respirometric model.     

Biodegradability of antineoplastic compounds in screening tests: influence of glucosidation and of stereochemistry

Some pharmaceuticals such as antineoplastics are carcinogenic, mutagenic, teratogenic and fetotoxic. Antineoplastics and their metabolites are excreted by patients into waste water. In laboratory testing the frequently used isomeric anti-tumour agents cyclophosphamide (CP) and ifosfamide (IF) were shown to be not biodegradable. They are not eliminated in municipal sewage treatment plants and therefore detected in their effluents. Structural related compounds are beta-D-glucosylisophosphoramidmustard (beta-D-Glc-IPM; INN = glufosfamide) and beta-L-glucosylisophosphoramidmustard (beta-L-Glc-IPM). beta-L-Glc-IPM has no antineoplastic effects whereas beta-D-Glc-IPM is active against tumours. In contrast to IF and CP and almost all other investigated antineoplastics beta-D-Glc-IPM is inherently biodegradable. Improved biodegradability of beta-D-Glc-IPM compared to IF shows that reducing the impact of pharmaceuticals on the aquatic environment is feasible by changing the chemical structure of a given compound exerting a similar mode of action and therapeutic activity. Stereochemistry may be crucial for pharmaceutical activity of the compounds as well as for its biodegradability in the environment.     

Ozonation of hydrolyzed azo dye reactive yellow 84 (CI).

The combination of chemical and biological water treatment processes is a promising technique to reduce recalcitrant wastewater loads. The key to the efficiency of such a system is a better understanding of the mechanisms involved during the degradation processes. Ozonation has been applied to many fields in water and wastewater treatment. Especially for textile mill effluents ozonation can achieve high color removal, enhance biodegradability, destroy phenols and reduce the chemical oxygen demand (COD). However, little is known about the reaction intermediates and products formed during ozonation. This work deals with the degradation of hydrolyzed Reactive Yellow 84 (Color Index), a widely used azo dye in textile finishing processes with two monochlorotriazine anchor groups. Ozonation of the hydrolyzed dye in ultra pure water was performed in a laboratory scale cylindric batch reactor. Decolorization, determined by measuring the light absorbance at the maximum wavelength in the visible range (400 nm), was almost complete after 60 and 90 min with an ozone concentration of 18.5 and 9.1 mg/l, respectively. The TOC/TOC0 ratio after ozonation was about 30%, the COD was diminished to 50% of the initial value. The BOD5/COD ratio increased from 0.01 to about 0.8. Oxidation and cleavage of the azo group yield nitrate. Cleavage of the sulfonic acid groups of aromatic rings caused increases in the amount of sulfate. Formic acid and oxalic acid were identified as main oxidation products by high performance ion chromatography (HPIC). The concentrations of these major products were monitored at defined time intervals during ozonation.     

Anaerobic degradation and toxicity of commercial cationic surfactants in anaerobic screening tests

Anaerobic biodegradability and toxicity on anaerobic bacteria of di(hydrogenated tallow) dimethyl ammonium chloride (DHTDMAC) and two esterquats have been investigated. A batch test system containing municipal digester solids as a source of anaerobic bacteria, based on the method proposed by the ECETOC, has been applied. To evaluate the potential toxicity of such surfactants on anaerobic sludge, a co-substrate, an easily biodegradable compound in anaerobic conditions, has been added to the samples to test and the effects on biogas production have been determined. For the esterquats studied high biodegradation levels were obtained and no toxic effects on anaerobic bacteria were observed even at the highest concentrations tested, 100 and 200 mg C/l, respectively. On the contrary, DHTDMAC was not degradated at the same test conditions. However, no inhibitory effects on the biogas production were detected for this surfactant at concentrations <100 mg C/l.     

Combination of biodegradable organic matter quantification and XAD-fractionation as effective working parameter for the study of biodegradability in environmental and anthropic samples

The present work proposes to couple quantification of biodegradable organic matter (BOM) with XAD-fractionation. Biodegradable dissolved organic carbon (BDOC) and assimilable organic carbon (AOC) analysis were applied to fractions extracted by XAD resin. An examination of mechanisms during consumption of BOM has been carried out, using comparison of biodegradability between the bulk BOM of samples (landfill leachate and surface water) and the sum of BOM contents obtained for the extracted fractions. Results point out that a cometabolism mechanism seems to be involved during the degradation of the surface water fractions. On the other hand, fractions extracted from the leachate seem to be degraded as primary substratum. The more reactive fractions of the leachate (HPO*) and the water (HPI) have been identified as well the less reactive (HPI* and HPO, respectively). The BDOC contents determined for the bulk leachate and surface water are 10+/-2% and 28+/-2%, respectively. The values of AOC are 107+/-18 microg C acetate L(-1) and 163+/-21 microg C acetate L(-1), respectively.     

Size removal on polyester fabrics by plasma source ion implantation device

Plasma treatment was evaluated as an alternative clean desizing technology in this work. As indicated by weight loss, O2 plasma treatment efficiently removed sizing agents such as polyvintyl alcohol (PVA), polyacrylic acid esters and their mixture (MIX) on polyethylene terephthalate (PET) fabrics. SEM pictures of the plasma treated samples directly proved the disappearance of the sizing agents. XPS analysis showed apparent changes in chemical composition and functional groups of the PET surface after O2 plasma treatment. Carbon content decreased due to the removal of sizing agents while oxygen content increased. O2 plasma treatment also increased hydrophilic functional groups of sizing agents, which is confirmed by C1s and O1s deconvolution analyses. After O2 plasma treatment, the PET fabric was subjected to conventional desizing process at different temperatures. Except for the PET fabric sized with PVA, plasma-treated fabrics showed more efficient desizing results when compared with untreated fabrics. Furthermore, the desizing effluent from the treated fabric gave lower TOC, COD and BOD values.     

Ozonation of an azo dye C.I. Remazol Black 5 and toxicological assessment of its oxidation products

The effect of ozonation (20.5 mgl(-1)) on the degradation processes of an azo dye, Remazol Black 5 (RB5; CI) was studied. Conventional parameters such as chemical oxygen demand (COD), total organic carbon (TOC), pH, conductivity, colour removal, biodegradability (BOD(5/28)), and toxic potential of the dye and its degradation products were monitored during the process. The results obtained indicated that ozonation is a highly effective way to remove the colour of a corresponding dye solution. However, a considerable organic load still remained as indicated by high COD and TOC residues. The COD, TOC reductions were about 40% and 25% for 6 h ozonation of 2 gl(-1) RB5 aqueous solution. During the ozonation process the rapid decrease of pH and the sharp increase of conductivity indicated the formation of acidic by-products and small fragments and ions which were identified by high performance ion chromatography. The BOD28 data revealed that first by-products after partial ozonation (10-150 min) of RB5 were more biodegradable than the parent compound and ozonation can enhance the biodegradability of azo dyes. During the first 150 min of total 360 min of oxidation, the formation of first by-products with high toxic potential took place as it could be confirmed by two acute toxicity-screening tests, the bioluminescence test (Vibrio fischerii) and the neutral red cytotoxicity assay (rat hepatoma cells). The significant enhancement of microbial biodegradability after long-term ozonation could also be seen as a decrease of toxic intermediates in correlation with the ozonation time as indicated in BOD28 biological degradation test results.     

Decolorization of mixtures of different reactive textile dyes by the white-rot basidiomycete Phanerochaete sordida and inhibitory effect of polyvinyl alcohol

We tried to decolorize mixtures of four reactive textile dyes, including azo and anthraquinone dyes, by a white-rot basidiomycete Phanerochaete sordida. P. sordida decolorized dye mixtures (200 mg l-1 each) by 90% within 48 h in nitrogen-limited glucose-ammonium media. Decolorization of dye mixtures needed Mn2+ and Tween 80 in the media. Manganese peroxidase (MnP) played a major role in dye decolorization by P. sordida. Decolorization of dye mixtures by P. sordida was partially inhibited by polyvinyl alcohol (PVA) that wastewaters from textile industries often contain. This was caused by an inhibitory effect of PVA on the decolorization of Reactive Red 120 (RR120) with MnP reaction system. Second addition of Tween 80 to the reaction mixtures in the presence of PVA improved the decolorization of RR120. These results suggest that PVA could interfere with lipid peroxidation or subsequent attack to the dye.     

微污染钦用水生物处理中痕量有机物生物降解研究述评

生物膜工艺可以有效去除微污染饮用水源中痕量有机污染物，第二级利用是稳态生物膜降解痕量有机物的主要机理。自然有机物可以作为初级基质支持稳态生物膜的生长，而痕量的合成有机物能作为第二级基质被生物膜降解，缓慢衰减的非稳态生物膜在一段时期内仍能保持对痕量有机物的高效降解。     

Aerobic biodegradability of the calcium channel antagonist verapamil and identification of a microbial dead-end transformation product studied by LC-MS/MS

In recent years pharmaceuticals and personal care products have been detected in increasing concentrations in hospital effluents, sewage treatment plants (STP) as well as in different environmental compartments such as surface water, groundwater and soil. Little is known about the elimination of these substances during sewage treatment or about the formation of potential metabolites in the environment caused by bacterial biotransformation. To assess the biodegradability of the popular cardiovascular drug verapamil and the possible formation of potential microbial degradation products, two tests from the OECD series were used in the present study: the widely used Closed Bottle test (OECD 301 D) and the modified Zahn-Wellens test (OECD 302 B). In the Closed Bottle test, a screening test that simulates the conditions of an environmental surface water compartment, no biological degradation was observed for verapamil at concentrations of 2.33mgl(-1). In the Zahn-Wellens test, a test for inherent biodegradability which allows evaluation of aerobic degradation at high bacterial density, only a partial biological degradation was found. Analysis of test samples by high performance liquid chromatography coupled to multiple stage mass spectrometry (HPLC-MSn) revealed 2-(3,4-dimethoxyphenyl)-2-isopropyl-5-(methylamino)pentane nitrile, already known as D617 (Knoll nomenclature), a metabolite of mammalian metabolism, which is the major degradation product and dead-end transformation product of aerobic degradation of verapamil.     

Enzyme-based solutions for textile processing and dye contaminant biodegradation—a review

The textile industry, as recognized conformist and stake industry in the world’s economy, is facing serious environmental challenges. In numerous industries, in practice, various chemical-based processes from initial sizing to final washing are fascinating harsh environment concerns. Some of these chemicals are corrosive to equipment and cause serious damage itself. Therefore, in the twenty-first century, chemical and allied industries quest a paradigm transition from traditional chemical-based concepts to a greener, sustainable, and environmentally friendlier catalytic alternative, both at the laboratory and industrial scales. Bio-based catalysis offers numerous benefits in the context of biotechnological industry and environmental applications. In recent years, bio-based processing has received particular interest among the scientist for inter- and multi-disciplinary investigations in the areas of natural and engineering sciences for the application in biotechnology sector at large and textile industries in particular. Different enzymatic processes such as chemical substitution have been developed or in the process of development for various textile wet processes. In this context, the present review article summarizes current developments and highlights those areas where environment-friendly enzymatic textile processing might play an increasingly important role in the textile industry. In the first part of the review, a special focus has been given to a comparative discussion of the chemical-based “classical/conventional” treatments and the modern enzyme-based treatment processes. Some relevant information is also reported to identify the major research gaps to be worked out in future.     

Biodegradability of biofilm extracellular polymeric substances

This study discovered that biofilm extracellular polymeric substances (EPS) are biodegradable by their own producers and by other microorganisms when they are starved. The study was performed in a comparative fashion to examine the biodegradability of biofilm EPS by the microorganisms from the original biofilm (its own producers) and from activated sludge (other microorganisms). Four distinctive phases were observed during EPS biodegradation. In the first phase, instantaneous concentration increases of carbohydrate and protein in the test solutions were observed when EPS was added; in the second phase, easily biodegradable EPS from the added EPS was quickly utilized; in the third phase, microorganisms began to produce soluble EPS, using the minimally biodegradable EPS left from the previously added EPS; in the fourth phase, cells consumed the newly produced EPS and microbial activity gradually stopped. This study suggests that EPS can be used as a substrate, and that the EPS carbohydrate can be utilized faster than the EPS protein. The EPS utilization rates (including carbohydrate and protein) in the activated sludge suspension were greater than those in the biofilm suspension. It may take microorganisms longer to get acclimated to a new nutrient environment if they are in a starved state.     

Derivation of synthetic fuel from waste plastic: investigation of engine operating characteristics on DI diesel engine

The utilization of plastic in day to day life is ever-increasing and has generated a large amount of plastic garbage that needs proper disposal to save the environment from harmful pollution. The plastic waste management becomes a pressing concern in the present scenario in developing countries like India. This research article evaluates the potential of synthetic fuel (SF) derived from waste plastics collected from the local shops. In this current investigation, the SF blends are tested in a direct injection diesel engine to analyze the performance and emission characteristics of the engine. Three different blends were made namely SF20, SF40, and SF60 on a volumetric basis and the tests were carried out. From the experimental results, it was found that brake thermal efficiency (BTE) of the fuel blends was reduced as compared with neat diesel operation regardless of loads whereas SF20 showed a similar trend as that of diesel operation. The analysis of the emission characteristics revealed that the SF20 blends reduced dangerous smoke and carbon monoxide emission as compared with other test fuels. From the overall results, SF20 showed superior performance and emission aspects as compared with other SF blends whereas the engine operated smoothly up to 60% of SF blending at all loading conditions.

     

Biodegradation of cyclodextrins in soil

Cyclodextrins, especially random methylated betaCD (RAMEB) and hydroxypropyl betaCD (HPbetaCD), are becoming common enhancing additives in the bioremediation of soils formerly contaminated by hydrocarbons and/or other poorly bioavailable organic pollutants. Therefore, their degradation in the soil, particularly the most persistent RAMEB, has been of great concern. Like oil contaminants, these additives should be biodegradable via an environmentally safe technology. Hence, in this paper, the biodegradability of eight different cyclodextrins (CDs) in four different soils was examined under various treatment conditions in laboratory and pilot scale field experiments. This paper is the first report on the potential biological fate of CDs studied under a large variety of environmental conditions and in different soil ecosystems. Data on the potential relationship between CD biodegradation and the biological removal of hydrocarbons in the CD-amended contaminated soils are also given. All CDs were found to be more or less biodegradable; even the most persistent RAMEB was depleted from soils under favourable conditions. In the field experiments, the depletion of RAMEB to about 40% of its initial level was observed for a period of 2 years in hydrocarbon-contaminated soils of high organic matter and cell concentration.     

Direct VUV photodegradation of gaseous α-pinene in a spiral quartz reactor: intermediates, mechanism, and toxicity/biodegradability assessment

Photodegradation of gaseous α-pinene by a vacuum ultraviolet (VUV) in a spiral reactor was investigated under various gaseous reaction media and residence time, and their respective effects on types and biodegradability of the intermediates were studied. Analysis of carbon amounts showed that about 33% and 43% of total carbon were converted to soluble organic carbon in the air medium with a relative humidity (RH) of 35-40% at empty bed residence times (EBRTs) of 18 and 45 s. Based on the identified intermediates by GC/MS and IC, a photodegradation pathway was proposed by the combined roles of photolysis, OH. photooxidation and O? photooxidation. Biodegradability to active sludge, toxicity to Chlorella vulgaris and 96-well microplates showed that α-pinene could be largely converted to more biodegradable and less toxic compounds through photodegradation in the air reaction medium with a RH of 35-40% at an EBRT of 18s, in which the initial concentration was 600 mg m?3. Therefore, VUV photodegradation could be applied as an effective pre-treatment method for detoxification and biodegradability improvement under the optimized photodegradation conditions. Such results supported the potential use of VUV photodegradation to improve the removal capacity of conventional biological treatments for hydrophobic and poorly biodegradable compounds.