Combined Analytical Study on Chemical Transformations and Detoxification of Model Phenolic Pollutants during Various Advanced Oxidation Treatment Processes.

Advanced oxidation processes (AOPs) have been introduced to deal with different types of water pollution. They cause effective chemical destruction of pollutants, yet leading to a mixture of transformation by-products, rather than complete mineralization. Therefore, the aim of our study was to understand complex degradation processes induced by different AOPs from chemical and ecotoxicological point of view. Phenol, 2,4-dichlorophenol, and pentachlorophenol were used as model pollutants since they are still common industrial chemicals and thus encountered in the aquatic environment. A comprehensive study of efficiency of several AOPs was undertaken by using instrumental analyses along with ecotoxicological assessment. Four approaches were compared: ozonation, photocatalytic oxidation with immobilized nitrogen-doped TiO2 thin films, the sequence of both, as well as electrooxidation on boron-doped diamond (BDD) and mixed metal oxide (MMO) anodes. The monitored parameters were: removal of target phenols, dechlorination, transformation products, and ecotoxicological impact. Therefore, HPLC-DAD, GC-MS, UHPLC-MS/MS, ion chromatography, and 48 h inhibition tests on Daphnia magna were applied. In addition, pH and total organic carbon (TOC) were measured. Results show that ozonation provides by far the most suitable pattern of degradation accompanied by rapid detoxification. In contrast, photocatalysis was found to be slow and mild, marked by the accumulation of aromatic products. Preozonation reinforces the photocatalytic process. Regarding the electrooxidations, BDD is more effective than MMO, while the degradation pattern and transformation products formed depend on supporting electrolyte.

An Assessment of Mass Flows, Removal and Environmental Emissions of Bisphenols in a Sequencing Batch Reactor Wastewater Treatment Plant.

This study analyzed 16 bisphenols (BPs) in wastewater and sludge samples collected from different stages at a municipal wastewater treatment plant based on sequencing batch reactor technology. It also describes developing an analytical method for determining BPs in the solid phase of activated sludge based on solid-phase extraction and gas chromatography-mass spectrometry. Obtained concentrations are converted into mass flows, and the biodegradation of BPs and adsorption to primary and secondary sludge are determined. Ten of the sixteen BPs were present in the influent with concentrations up to 434 ng L-1 (BPS). Only five BPs with concentrations up to 79 ng L-1 (BPA) were determined in the plant effluent, accounting for 8 % of the total BPs determined in the influent. Eleven per cent of the total BPs were adsorbed on primary and secondary sludge. Overall, BPs biodegradation efficiency was 81%. The highest daily emissions via effluent release (1.48 g day-1) and sludge disposal (4.63 g day-1) were for BPA, while total emissions reached 2 g day-1 via effluent and 6 g day-1 via sludge disposal. The data show that the concentrations of BPs in sludge are not negligible, and their environmental emissions should be monitored and further studied.

Comparison of end-of-life vehicles management in 31 European countries: A LMDI analysis.

In 2018, a total of 6,083,000 end-of-life vehicles (EVLs) with a total weight of 6,732,000 tonnes (including waste parts) were generated in the European Union. These vehicles are a subject of particular attention because of their bulky mass, the hazardous components they contain, and the valuable materials present. This article analyses the quantities of ELVs and parts of ELVs that have been recycled, energy recovered, disposed, and reused to assess the impact of the changes in these management options on the total quantities managed. The analysis covered the statistical data on EVLs in 31 European countries for the period 2006-2018, using a new extended version of the logarithmic mean divisia index (LMDI) analysis model, which allows analysts to compare and analyse different waste management options simultaneously. The results show that the changes in the waste intensities and household final consumption expenditure were the greatest drivers of changes in the total quantities managed, while changes in the quantities recycled, energy recovered, disposed of, and reused had the least impact. All countries met or were close to meeting the targets during the period analysed. Changes in the total quantities of waste managed depended on the economic activity, which influenced the quantities of ELVs generated and their subsequent management.

Delamination of plastic-coated waste paper by enzymes of the white rot fungus Dichomitus squalens.

Many paper products are coated with plastic to improve their quality and stability. However, this limits recycling and recovery options and the plastic-coated waste paper is mostly disposed in landfills. Such practices are uneconomical and contrary to sustainable waste management. In this work enzymes of the white rot fungus Dichomitus squalens were investigated for possible delamination of plastic-coated waste paper. Enzymes were found capable to release the polyethylene foil from plastic-coated paper which resulted in 88.6-91.5% mass loss. The delamination rate, however, was depended on the ratio between plastic-coated paper and volume of enzyme filtrate. Results of a consequent experiment showed that enzymes are also efficient when plastic-coated paper is treated in a sequencing batch reactor resulting in 88.2-90.6% mass loss. The system was fully functional up to the 5th cycle; afterwards, the delamination rate reduced due to high thickness of the waste paper sludge. The enzyme activity, however, was still very high; with the laccase activity at the end of the experiment above 900 U/L and manganese peroxidase above 250 U/L. Our results demonstrated, that plastic-coated waste paper has the potential to be efficiently recovered instead of being disposed in landfills.

The Enhancement of H2O2/UV AOPs for the Removal of Selected Organic Pollutants from Drinking Water with Hydrodynamic Cavitation.

Drinking water contains organic matter that occasionally needs to be treated to assure its sufficient quality and safety for the consumers. H2O2 and UV advanced oxidation processes (H2O2/UV AOPs) were combined with hydrodynamic cavitation (HC) to assess the effects on the removal of selected organic pollutants. Water samples containing humic acid, methylene blue dye and micropollutants (metaldehyde, diatrizoic acid, iohexol) were treated first by H2O2 (dosages from 1 to 12 mg L-1) and UV (dosages from 300 to 2800 mJ cm-2) AOPs alone and later in combination with HC, generated by nozzles and orifice plates (4, 8, 18 orifices). Using HC, the removal of humic acid was enhanced by 5-15%, methylene blue by 5-20% and metaldehyde by approx. 10%. Under favouring conditions, i.e. high UV absorbance of the matrix (more than 0.050 cm-1 at a wavelength of 254 nm) and a high pollutant to oxidants ratio, HC was found to improve the hydrodynamic conditions in the photolytic reactor, to improve the subjection of the H2O2 to the UV fluence rate distribution and to enhance the removal of the tested organic pollutants, thus showing promising potential of further research in this field.

Decomposition analysis of the waste generation and management in 30 European countries.

An often suggested method for waste prevention is substitution of currently-used materials with materials which are less bulky, contain less hazardous components or are easier to recycle. For policy makers it is important to have tools available that provide information on the impact of this substitution on the changes in total amounts of waste generated and managed. The purpose of this paper is to see how much changes in the mix of 15 waste streams generated in eight economic sectors from 30 European countries have influenced the amounts of waste generated and managed in the period 2004-2012. In order to determine these impacts, two variations of the logarithmic mean Divisia index (LMDI) analysis model were developed and applied. The results show that the changes in the mix of waste streams in most cases did not have a considerable influence on the changes in the amounts of generated waste. In the analyses of waste sent for landfill, incineration without energy recovery, incineration with energy recovery and recovery other than energy recovery, the results also show that the changes in the mix of waste streams in most cases did not have the expected/desired influence on the changes in the amounts of managed waste. This paper provides an example on the possibilities of applying the LMDI analysis as a tool for quantifying the potential of effects which implemented or planned measures could have on the changes in waste management systems.

Application of multiple toxicity tests in monitoring of landfill leachate treatment efficiency.

Leachate from a closed landfill used for co-disposal of municipal and tannery waste was submitted to coagulation treatment, air stripping, adsorption on granular activated carbon, and Fenton oxidation with the aim to reduce toxicity of the leachate. Optimal operational conditions for each process were identified. The performance of the treatment was monitored by determination of organic matter (COD, DOC, BOD5), inorganic components (N-NH4(+), Cl(-), alkalinity, metals), organic compounds (BTEX, PAHs, PCBs, OCPs) while changes in toxicity were followed by multiple toxicity tests. Among the applied treatment techniques, adsorption on granular activated carbon was the most efficient method for removal of organic matter and metals while air stripping was the most efficient for removal of N-NH4(+) and reduction of toxicity. Lower reduction of organic matter content and toxicity was obtained during coagulation treatment. Fenton oxidation was effective for removal of COD; however, it negatively affected toxicity reduction. The combination of adsorption on granular activated carbon and air stripping led to an appreciable reduction of organic and inorganic pollutants and to leachate detoxification. Application of bioassays was helpful for assessing suitability of treatment methods and demonstrated that they are, together with physicochemical parameters, an indispensable part for monitoring of treatment efficiency.

Evaluation of biotreatability of ionic liquids in aerobic and anaerobic conditions.

The aim of our study was to set up an approach for reliable biotreatability assessment of ionic liquids (ILs). As a case study, two different ILs were selected: pyridinium-based 1-butyl-3-methylpyridinium dicyanamide ([bmpyr][dca]) and imidazolium-based 1-butyl-3-methylimidazole tetrafluoroborate ([bmim][BF4]). Toxicity in aerobic conditions was determined by measurement of inhibition of oxygen consumption by activated sludge, while their biodegradability was calculated from measurements of oxygen consumption and dissolved organic carbon elimination. For their biotreatability in anaerobic conditions, the method with measurement of biogas production has been employed comparing flocculent and granular sludge. Both ILs were less toxic and more biodegradable in anaerobic conditions. IL [bmpyr][dca] was not toxic to granular sludge up to 742 mg L(-1) and it even has been degraded at this concentration in the presence of easily degradable glucose. Flocculent sludge was completely inhibited at the lower concentration of 318 mg L(-1), but it degraded by 44% at 106 mg L(-1) in the presence of glucose, indicating the appearance of cometabolism. IL [bmim][BF4] was less toxic but also resistant to biodegradation in anaerobic conditions. It degraded via cometabolism 21% at 1,452 mg L(-1). It has been concluded that any assessment of biotreatability of ILs should include parallel determination in aerobic and anaerobic conditions.

Biotreatability Improvement of Antibiotic-Contaminated Waters: High Efficiency of Direct Ozonation in Comparison to Hydroxyl Radical Oxidation.

Efficiencies of direct ozonation and hydroxyl radical oxidation by Fenton process were compared, aiming to improve biotreatability of antibiotics contaminated water (tiamulin, amoxicillin and levofloxacin).  Biodegradability, COD (chemical oxygen demand) and TOC (total organic carbon) were measured before and after applying oxidative process. It was confirmed that significantly smaller molar dose of ozone (1.1 mgO3 / mgatb) against the hydrogen peroxide (17 mgH2O2 / mgatb), deliver comparable improvements of biodegradability; Tiamulin biodegraded up to 60 %, levofloxacin close to 100 %. Ozonation removed more TOC (10%, 29% and 8% for tiamulin, levofloxacin and amoxicillin, respectively) than Fenton process. This is confirming mineralization of antibiotics, not only biodegradable intermediates formation. In terms of costs, ozonation is more feasible in oxidizing complex antibiotics in water, as it targets functional groups which carry antimicrobial properties. This brings not only improved biodegradability needed for a conventional biological treatment plant, but also reduces long-term impacts of the antibiotics in the environment.

Assessment of landfill leachate toxicity reduction after biological treatment.

In the present article, the efficiency of biological treatment of landfill leachates was evaluated by implementation of physicochemical characterisation and a complex toxicity assessment. An array of toxicity tests using bacterium Vibrio fischeri, alga Desmodesmus subspicatus, crustacean Daphnia magna, and embryo of fish Danio rerio, as well as unconventional methods using biochemical biomarkers (protein content, enzymes cholinesterase, and glutathione-S-transferase), were employed. Toxicity of leachates varied depending on the season of collection in relation to their different physicochemical characteristics. Uncommon effects of leachates on organisms, such as hormetic-like increases of algal growth and reproduction of daphnids, were identified. New approaches using the activities of enzymes were found unsuitable for routine hazard assessment of leachates. Although physicochemical parameters and toxicity decreased significantly after biological treatment, the effluents did not meet the demands of the current Slovenian legislation; thus, the existing biological treatment was found inappropriate. The development of advanced treatment techniques for landfill leachates is thus encouraged.

Artemia salina acute immobilization test: a possible tool for aquatic ecotoxicity assessment.

Despite the fact that the marine crustacean Artemia salina is extensively used in ecotoxicology, there is still a lack of information about its sensitivity to commonly used chemicals. In the presented study, acute toxicity of 18 commonly used chemicals - including organic solvents, industrial chemicals, metals and inorganic compounds - to A. salina was evaluated. A. salina showed a range of sensitivities to tested chemicals. Regarding all of the investigated organics, phenolic compounds expressed the highest toxicity to A. salina. Nitrite and mercury were the most toxic inorganic substances applied in the study. On the other hand, dimethyl sulfoxide, nitrate and ammonium were the least toxic. The possibility to use A. salina for interspecies correlation was assessed by comparison of sensitivities of different organisms (bacteria, fish, crustacean) to organic compounds. Correlation between various species was observed, especially between A. salina and fish. Due to the strong relation between toxicity and the logarithm of the octanol/water partition coefficient logP(OW,) lipophilicity was found to be the main factor influencing toxicity of the chosen organic compounds. No significant correlation between toxicity to A. salina and physico-chemical parameters of metals was observed.

Improvement of biotreatability of environmentally persistent antibiotic Tiamulin by O3 and O3/H2O2 oxidation processes.

The aim of the work was to assess the efficiency of ozonation and ozonation in combination with H2O2 in jet loop reactor to increase biotreatability of persistent veterinary antibiotic Tiamulin. The efficiency of oxidative processes was monitored by combined approach based on determination of efficiency of wastewater treatment and impact to waste sludge stabilization. Degradation of Tiamulin in model wastewater (100 mg L-1) during oxidation was followed by COD and DOC measurements while changes in biodegradability were determined by respirometric measurements. Biogas production potential was also determined to identify problems related to anaerobic digestion of waste sludge resulted in treatment of Tiamulin-contaminated wastewater. At ozone dose of 69 gozone gCOD-1 and 220 gozone gDOC-1removal for COD and DOC was 26% and 17%, respectively. Better biotreatability was confirmed by respirometric testing. H2O2 addition did not improve removal efficiency (11-13%). The second stage of nitrification was suppressed by the addition of Tiamulin and ozonation again recovered N-NO3- formation. O3/H2O2 treated sample reduced the nitrification, especially formation of N-NO2- in the first phase of the process. Simultaneously, quadratic model was developed to describe the relationship between oxygen uptake rate and changes in ammonium nitrogen concentration due to the oxidative treatment. The positive impact of ozone was also confirmed by ozonation of Tiamulin-contaminated (400 mg L-1) waste sludge where biogas production potential was increased for 6-times. Combination of approaches confirmed, that O3 effectively increase the treatability of Tiamulin in wastewater and sludge while addition of the hydrogen peroxide generally did not improve the performance of the processes.

Ozonation of Amoxicillin and Ciprofloxacin in Model Hospital Wastewater to Increase Biotreatability.

Amoxicillin (AMX) and Ciprofloxacin (CIP) are antibiotics commonly used in human medicine with high environmental toxicity and poor biodegradability. They have been found in various hospital effluents and groundwater, and their environmental impact is still not fully understood. In this work, we investigated the possibility of treating model wastewaters containing the antibiotics AMX and CIP using ozonation, with the addition of H2O2 under various conditions, including different pH values, H2O2, and ozone dosages. The quantification of and treatment efficacy for antibiotic removal were determined via solid phase extraction followed by chromatographic separation by liquid chromatography coupled with tandem triple quadrupole mass spectrometry (LC/MS/MS). This analytical system is quite efficient for the detection of all major antibiotic classes, even if they are present at very low concentrations. The efficiency of ozonation was determined by measuring the TOC (Total Organic Carbon) changes after ozonation of the model wastewater and by measuring the concentration of the two antibiotics. In a sequential activated sludge process of ozone-treated model wastewater, almost complete TOC removal and an overwhelming decrease in antibiotic concentrations (up to 99%) were observed. Ozonation resulted in complete removal of AMX and CIP in less than 30 and 120 min, respectively. The results of this work indicate that ozonation could be a suitable pretreatment method to reduce the toxicity of contaminants (AMX and CIP) and improve the biodegradability of hospital wastewater.

Feasibility of Fenton's Oxidation for Removal of Estrogens from Aqueous Solutions.

Presented research has been focused on the effectiveness of degradation of natural (17-estradiol - E2) and synthetic (17α-ethinylestradiol - EE2) hormones with Fenton's oxidation. Numerous studies have demonstrated, that the impact of hormones on organisms was shown already at environmental concentrations close to 1 pg L-1, so their effective removal from wastewaters is important. Fenton's oxidation is very efficient in terms of oxidation of organics, while its main withdrawal is the formation of waste sludge, leading to adsorption of organics, which sometimes makes it impossible to reliably value the extent of actual degradation. The ratio among degradation and adsorption of estrogens on sludge during oxidative treatment was determined as a part of our study. It depends upon the molar ratio of reagents Fe2+ and H2O2 (1:0.5, 1:10; 1:20; 1:33), reaction time and initial concentrations of the investigated estrogens E2 (0.279/27.9 mg L-1) and EE2 (0.296/29.6 mg L-1). The most efficient removal of E2 was achieved at 1:33 molar ratio of reagents (100%, 26-50% adsorption) while EE2 removed efficiently at 1:10 and 1:33 ratios (99-100%, 20-76% adsorption). It was confirmed, that adsorption plays an important role in Fenton's oxidative treatment of estrogens. It is prevailing process at higher pHs, while at lower ones (pH = 3.0-5.0) oxidation is dominant, because it is not limited by mass transport.

An exploratory ecotoxicity study of primary microplastics versus aged in natural waters and wastewaters.

Current understanding of how environmental aging of microplastics contributes to their ecotoxicity is low. We investigated whether incubation of microplastics in waters with different organic load and toxic potential alters the toxicity of microplastics to crustacean Daphnia magna, fish embryos Danio rerio and plant Lemna minor. Polyethylene primary microplastics; specifically microbeads from facial scrub; were subjected to 3-weeks incubation in low affected spring water, river water, effluent from the municipal wastewater treatment plant (WWTP) and municipal landfill leachate. Primary microplastics had no acute effect on D. magna mobility and D. rerio embryos development. While high organic load wastewaters; WWTP effluent and landfill leachate; showed evident toxicity for D. magna and D. rerio embryos, microplastics aged in these wastewaters had no effect. This suggests that adsorption of pollutants from wastewaters to microplastic particles was not high enough to induce acute toxicity to D. magna and D. rerio. On the contrary, primary microplastics affected the root growth of L. minor. Interestingly, aging of microplastics in low organic-load waters mitigated the toxicity of microplastics for L. minor, while microplastics aged in high-organic load waters had the same adverse effect as primary microplastics. Partly, these effects can be explained by different extent of coating on microplastics in different water samples. This study suggests that aging of microplastics in wastewaters and natural waters did not significantly enhance the toxicity to selected test species, but further studies on plants may be of interest.

Impact of polyethylene microbeads on the floating freshwater plant duckweed Lemna minor.

Microplastics (MP), small plastic particles below 5 mm, have become one of the central concerns of environmental risk assessment. Microplastics are continuously being released into the aquatic environment either directly through consumer products or indirectly through fragmentation of larger plastic materials. The aim of our study was to investigate the effect of polyethylene microbeads from cosmetic products on duckweed (Lemna minor), a freshwater floating plant. The effects of microbeads from two exfoliating products on the specific leaf growth rate, the chlorophyll a and b content in the leaves, root number, root length and root cell viability were assessed. At the same time, water leachates from microbeads were also prepared to exclude the contribution of cosmetic ingredients on the measured impacts. Specific leaf growth rate and content of photosynthetic pigments in duckweed leaves were not affected by polyethylene microbeads, but these microbeads significantly affected the root growth by mechanical blocking. Sharp particles also reduced the viability of root cells, while the impact of microbeads with a smooth surface was neglected. It was concluded that microbeads from cosmetic products can also have negative impacts on floating plants in freshwater ecosystems.

Hydrodynamic cavitation in combination with the ozone, hydrogen peroxide and the UV-based advanced oxidation processes for the removal of natural organic matter from drinking water.

Natural organic matter in drinking water is causing concern especially due to the formation of disinfection by-products (DBPs) by chlorine, as these are proven to have adverse health effects on consumers. In this research, humic acid was used as a source of dissolved organic carbon (DOC) in drinking water (up to 3mgL-1). The efficiency of DOC removal was studied by applying O3, H2O2/O3, H2O2/UV and O3/UV advanced oxidation processes (AOPs) alone and combined with hybrid hydrodynamic cavitation (HC), generated by an orifice plate, as this technology recently shows promising potential for the treatment of water, containing recalcitrant organic substances. It was observed that the combined treatment by HC could significantly affect the performance of the applied AOPs, with as little as 3-9 passes through the cavitation generators. For O3 and H2O2 dosages up to 2 and 4mgL-1, respectively, and UV dosage up to 300mJcm-2, HC enhanced DOC removal by 5-15% in all combinations, except for O3/UV AOPs. Overall, the potential benefits of HC for DOC removal were emphasized for low ratio between applied oxidants to DOC and high UV absorbance of the sample. Investigated DBPs formation potentials require special attention for H2O2/UV AOPs and combinations with HC.

Comparison of diethylene glycol and phenol biodegradability by different test methods.

Biodegradation is generally recognised as an important removal mechanism for pollutants in natural ecosystems. It determines the concentration of substances in the environment. According to the legislation of the European Union, there are three levels for biodegradability testing protocols for chemicals which cover different test conditions. This paper describes one such multilevel approach to biodegradation testing. Four different tests were performed on diethylene glycol and phenol. Diethylene glycol did not fulfill the requirements for ready biodegradable substances, while it degraded well in wastewater treatment plant simulation test. Phenol in turn, resulted ready biodegradable, and its biodegradability depended less on experimental conditions than the biodegradability of diethylene glycol. This corroborates the importance of combining different test methods to obtain relevant biodegradability data.

Hazard identification for 3,5-dichlorophenol in the aquatic environment.

The risk assessment of substances in various environmental compartments is essential for their proper, safe and environmentally friendly production, handling, use and final deposition or destruction. Hazard identification is an important part of risk assessment. The aim of our research was to present a methodology for the hazard identification of substances dangerous to the aquatic environment according to the 93/21/EEC Directive relating to the classification, packaging and labelling of dangerous substances, from the adverse effect assessment of chemicals in European Union. A battery of toxicity tests and biodegradability studies with 3,5-dichlorophenol were performed. The substance was classified as toxic to aquatic organisms with possible long-term adverse effects. The presented methodology assures reliable data for the classification and labelling of substances according to their harmful effect on aquatic biota, suitable for the competent authorities at the national and EU level.