Biochar from olive tree twigs and spent malt rootlets as electrodes in Zn-air batteries.

Biochars, i.e. porous carbons obtained by pyrolysis of biomass, can act as electrocatalysts for oxygen evolution and oxygen reduction reaction. In the present work, two biochars have been prepared by using materials of completely different biomass origin: olive-tree twigs and spent malt rootlets (brewery wastes). Both biomass species were subjected to pyrolysis under limited oxygen supply and then they were activated by mixing with KOH and pyrolysis again. The obtained biochars were characterized by several techniques in order to determine their structural characteristics and the composition of their active components. Despite their different origin, the two biochars demonstrated similar structural and compositional characteristics thus highlighting the importance of the pyrolysis and activation procedure. Both biochars were used as electrocatalysts in the operation of rechargeable Zn-air batteries, where they also demonstrated similar electrocatalytic capacities with only a small advantage gained by olive-tree-twigs biochar. Compared to bare nanoparticulate carbon (carbon black), both biochars demonstrated a marked advantage towards oxygen evolution reaction.

Wastewater treatment by high density algal flocs for nutrient removal and biomass production.

The present work investigated the efficiency of algal flocs biomass for the treatment of primary and secondary effluent in static and mixing conditions under different hydraulic retention time (HRT). Primary effluent fed cultures created a high-density biomass of 2.8 and 3.8 g L-1 under static and mixing conditions, respectively. Secondary effluent was more effective in order to create even higher density biomass of 7.8 and 6 g L-1 under static and mixing conditions, respectively. The algal floc biomass developed was quite effective for organic matter and nutrient removal. Primary effluent fed cultures seemed to be more efficient for chemical oxygen demand (COD) and ammonia nitrogen removal, while secondary effluent fed cultures for nitrates removal. At an HRT of 8 days using primary effluent, the removal of COD, ammonia nitrogen and total phosphorus was 86.2, 100 and 97.4%, respectively. The cultures fed with secondary effluent, even at low HRT of 1.2 days, achieved removals of 88.4, 77.5, 100 and 98.6% for COD, nitrates, ammonia, and total phosphorus, respectively. Supplementary Information: The online version contains supplementary material available at 10.1007/s10811-023-02931-2.

Sustainable treatment of primary and secondary effluent by algal-bacterial flocculent biomass in raceway ponds.

Two 5.5-L raceway open ponds were used to evaluate the removal of organic material and nutrients from wastewater. Algal-bacterial flocs were placed in the ponds to treat primary and secondary effluent. The organic loading rate ranged from 29 to 95 and 9 to 38 g sCOD m-3 d-1 for the reactor fed with primary and secondary effluent, respectively. The hydraulic retention time (HRT) gradually decreased in both reactors from 5.5 to 2.2 d during a period of 21 days, and after that, both reactors operated at an HRT of 1.1 d. A high biomass concentration of around 2.2 g L-1 was sustained using primary and secondary effluent after 130 days. The biomass, developed with both substrates was very active and completely removed organic material and nutrients in less than 12 h. The algal-bacteria biomass had excellent settling properties and could settle in less than 10 min.

Study of the Functionalities of a Biochar Electrode Combined with a Photoelectrochemical Cell.

Biochar has been obtained by pyrolysis of spent malt rootlets under limited oxygen supply and further activated by mixing with KOH and pyrolyzed again at high temperature. The total specific surface area of such activated biochar was 1148 m2 g-1, while that of micropores was 690 m2 g-1. This biochar was used to make a functional electrode by deposition on carbon cloth and was combined with a photoelectrochemical cell. The biochar electrode functioned as a supercapacitor in combination with the electrolyte of the cell, reaching a specific capacity of 98 Fg-1, and it was capable of storing charges generated by the cell, proving current flow both under illumination and in the dark. The same electrode could be used as an air-cathode providing oxygen reduction functionality and thus demonstrating interesting electrocatalyst properties.

Long-Term Toxicity of ZnO Nanoparticles on Scenedesmus rubescens Cultivated in Semi-Batch Mode.

The scope of this study was to investigate the toxic effects of zinc oxide (ZnO) nanoparticles (NPs) on freshwater microalgae, in long-term semi-batch feeding mode at two different hydraulic retention times (HRTs) (20 and 40 days). A freshwater microalgae, Scenedesmus rubescens, was employed and exposed to a semi-continuous supply of ZnO NPs at a low concentration of 0.081 mg/L for a period of 28 d. Experiments were conducted under controlled environmental conditions. Τhe impact of ZnO NPs on S. rubescens, which was assessed in terms of nutrient removal, biomass growth, and algal lipid content. Semi-batch mode cultures showed that low ZnO NP concentrations at an HRT of 40 d did not have any negative effect on microalgae growth after the fourth day of culture. In contrast, algal growth was inhibited up to 17.5% at an HRT of 20 d in the presence of ZnO NPs. This might be attributed to the higher flow rate applied and ZnO NPs load. A positive correlation between nutrient removal and microalgae growth was observed. The algal lipid content was, in most cases, higher in the presence of ZnO NPs at both HRTs, indicating that even low ZnO NPs concentration cause stress resulting in higher lipid content.

Degradation of sulfamethoxazole with persulfate using spent coffee grounds biochar as activator.

In the present study, biochar from spent coffee grounds was synthesized via pyrolysis at 850 °C for 1 h, characterized and employed as catalyst for the degradation of sulfamethoxazole (SMX) by persulfate activation. A variety of techniques, such as physisorption of N2, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and potentiometric mass titration, were employed for biochar characterization. The biochar has a surface area of 492 m2/g, its point of zero charge is 6.9, while mineral deposits are limited. SMX degradation experiments were performed mainly in ultrapure water (UPW) at persulfate concentrations between 100 and 1000 mg/L, biochar concentrations between 50 and 200 mg/L, SMX concentrations between 500 and 2000 µg/L and initial solution pH between 3 and 10. Real matrices, besides UPW, were also tested, namely bottled water (BW) and treated wastewater (WW), while synthetic solutions were prepared spiking UPW with bicarbonate, chloride, humic acid or alcohols. Almost complete removal of SMX can be achieved using 200 mg/L biochar and 1000 mg/L sodium persulfate (SPS) within 75 min. The presence of biochar is important for the degradation process, while the activity of the biochar increases linearly with SPS concentration. Degradation follows a pseudo-order kinetic model and the rate increases with increasing biochar concentration and decreasing SMX concentration. Although SMX adsorption onto the biochar surface is favored at acidic conditions, degradation proceeds equally fast regardless of the initial solution pH. Reactions in either real matrix are slower, resulting in 55% SMX removal in 60 min for WW. Bicarbonate causes severe inhibition as only 45% of SMX can be removed within 75 min in UPW. The addition of alcohol slightly inhibits degradation suggesting that the reaction pathway is either under electron transfer control or due to the generation of surface oxygen radicals with higher oxidation potential than the homogeneously produced radicals.

Physicochemical and Toxicological Assay of Leachate from Malt Spent Rootlets Biochar.

The aim of this study was to characterize the leachate derived from biochar produced from malt spent rootlets (MSR) and to evaluate the required washing level in order to provide water free from inorganic substances. MSR biochar was placed in a column and subjected to six serial washes with distilled water, and the leachate was analysed for main anions and heavy metals. The 1st wash aliquot contained increased levels of mainly phosphates (980 mg/L) and chlorides (760 mg/L), and lower levels of nitrates, sulfates, fluoride and bromide, which were decreased over washes. Zero concentrations were observed after three washes for most anions. The increased levels of Zn, Be, Cs, Mn, V and Se determined in the 1st wash aliquot were eliminated in the successive washes. The toxic potency of each wash aliquot, determined by the use of the fairy shrimp Thamnocephalus platyurus showed that the 1st and 2nd MSR biochar leachates were toxic with 4.52 and 1.46 toxic units (TU), respectively, followed by a significant elimination of toxicity after further washes.

Removal of caffeine, nicotine and amoxicillin from (waste)waters by various adsorbents. A review.

The fast growth in the anthropogenic activities, that involve a wide use of pharmaceuticals, has led to the appearance of new toxic and hazardous chemical compounds, called "emerging pollutants", which could cause unpredictable consequences to the ecosystems. The current review is focused on emerging pollutants occurring in food or air and include caffeine and nicotine, as well as on pharmaceuticals, in particular amoxicillin, and the concerns caused by its wide usage for medical purposes. This review, for the first time, analyzes and discusses the potential risks and implications of caffeine, nicotine and amoxicillin as emerging environmental pollutants, a field that remains underrepresented to date. Both caffeine and nicotine belong to life style compounds, while pharmaceutical amoxicillin is one of the very popular ß-lactam antibiotics used to take care of human and animal infections. The review covers the toxic effect caused by caffeine, nicotine and amoxicillin on humans and animals and describes some of the main adsorbents utilized for their removal (e.g., grape stalk, tea waste, wheat grains, bentonite, activated carbon, acid and base modified grape slurry wastes, graphene oxides, modified graphene oxides, zeolites, etc.). The isotherm and kinetic models for the analysis of caffeine, nicotine and amoxicillin adsorption by different adsorbents are presented. The impact of pH, temperature, adsorbent dosage and thermodynamic studies were deeply analyzed. The review also discusses the mechanism of adsorption for the above-mentioned emerging pollutants, which includes π-π interaction, cation-π bonding, electron-donor and electron-acceptor forces, van der Waals forces, electrostatic interactions, etc. The present review has a potential value for chemists, ecologists, toxicologists, environmental engineers, and other professionals that are involved in environmental protection.

Long-term toxicity of ZnO nanoparticles to Scenedesmus rubescens cultivated in different media.

The aim of this work was to investigate the long-term toxic effect of zinc oxide (ZnO) nanoparticles (NPs) on freshwater microalgae, combined with the nutrient consumption in the culture. For this purpose, two common microalgae media (Blue-Green 11, BG-11, and Bold's Basal Medium, BBM) were used. Scenedesmus rubescens was used as freshwater microalgae model species and was exposed to ZnO NPs at different concentrations (0.081 to 810 mg/L) for a period up to 28 d. The experimental results revealed that microalgae growth was affected by the time of exposure and the NPs concentrations, but mainly the culture medium used. Differences in microalgae growth rates were observed and attributed to the selected culture medium. The toxic effect of ZnO NPs was higher on microalgae cultured in modified BG-11 compared to BBM, despite the fact that S. rubescens exhibited higher growth rate in modified BG-11 without the exposure of ZnO NPs.

Mediated effect of ultrasound treated Diclofenac on mussel hemocytes: First evidence for the involvement of respiratory burst enzymes in the induction of DCF-mediated unspecific mode of action.

The present study investigates the toxic behavior of diclofenac (DCF) before and after its ultrasound (US) treatment, as well as the involvement of intracellular target molecules, such as NADPH oxidase and NO synthase, in the DCF-induced adverse effects on hemocytes of mussel Mytilus galloprovincialis. In this context, appropriate volumes (350 and 500mL) of DCF solutions (at concentrations of 2, 2.5, 5 and 10mgL(-1)) were treated under different ultrasound operating conditions (frequency at 582 and 862kHz, electric power density at 133 and 167W) for assessing US method efficiency. In parallel, DCF and US DCF-mediated cytotoxic (in terms of cell viability measured with the use of neutral red uptake/NRU method), oxidative (in terms of superoxide anions/(.)O2(-), nitric oxides such as NO2(-) and lipid peroxidation products, such as malondialdehyde/MDA content) and genotoxic (DNA damage measured by the use of Comet assay method) effects were investigated in hemocytes exposed for 1h to 5, 10 and 100ngL(-1) and 1, 10 and 20µgL(-1) of DCF. The involvement of NADPH oxidase and NO synthase to the DCF-induced toxicity was further investigated by the use of 10µΜ L-NAME, a NO synthase inhibitor and 10µΜ DPI, a NADPH oxidase inhibitor. According to the results, 350mL of 2mgL(-1) DCF showed higher degradation (>50%) under 167W electric power density and frequency at 862kHz for 120min, compared to degradation in all other cases, followed by a significant elimination of its toxicity. Specifically, US DCF-treated hemocytes showed a significant attenuation of DCF-mediated cytotoxic, oxidative and genotoxic effects, which appeared to be caused by NADPH oxidase and NO synthase activation, since their inhibition was followed by a significant elimination of (.)O2(-) and NO2(-) generation and the concomitant oxidative damage within cells. The results of the present study showed for the first time that unspecific mode of action of DCF, associated with the induction of NADPH oxidase and NO synthase in mussel hemocytes, could be significantly diminished after partial US degradation of DCF, at least under optimized operating conditions currently tested.

Effect of cultivation media on the toxicity of ZnO nanoparticles to freshwater and marine microalgae.

The aim of this work was to investigate the effect of zinc oxide nanoparticles (ZnO NPs) on freshwater and marine microalgae cultivated in different media. Freshwater species Chlorococcum sp. and Scenedesmus rubescens were cultivated in modified Blue-Green medium (BG-11) and Bold's Basal Medium (BBM), and marine species Dunaliella tertiolecta, and Tetraselmis suesica, cultured in salt modified BG-11 and f/2 medium. The microalgae species were exposed for 96 h with a daily reading of algal growth rate, to different ZnO NPs concentrations (0.081-810 mg/L). Significant differences were observed on microalgae growth rates, with the marine being more sensitive than the freshwater species, as revealed by their half inhibitory concentration values (IC50). The IC50 values in freshwater species were affected by the culture medium. The lowest IC50 values (<2.57 mg/L) were observed in the marine species. S. rubescens showed the less toxic effect in cultures with modified BG-11, compared to BBM cultures, with IC50 values >810 mg/L and 14.27 mg/L after 96 h exposure time, respectively. ZnO nanoparticles appeared to have toxic effects in all species tested, depended on the species type, the exposure time, the NPs concentration, and mainly the culture medium.

Aqueous phenanthrene toxicity after high-frequency ultrasound degradation.

Given that polycyclic aromatic hydrocarbons (PAHs), such as phenanthrene (PH), possess a potent risk for aquatic biota, a great attempt to develop and apply advanced oxidation processes, such as ultrasound (US), is of great concern nowadays. However, because US PAH-derived toxic intermediates are difficult to detect, the present study investigates aqueous PH toxicity before and after high-frequency US degradation, in hemocytes of mussel Mytilus galloprovincialis. Specifically, cell viability (with the use of neutral red uptake/NRU method), and oxidative-stress indices in terms of superoxide anions, (O2(-)), nitric oxides (NO, in terms of nitrites), lipid peroxidation products (in terms of malondialdehyde/MDA content) and DNA damage (with the use of Comet assay method) were investigated in mussel hemocytes exposed to environmentally relevant concentrations of PH (0.01, 0.1, 1 and 10 µg L(-1)), before and after US treatment for 120 min (at a frequency of 582 kHz). According to the results, the NRU method showed a significant attenuation of PH-induced mortality in US PH-treated hemocytes in all cases. Moreover, the increased levels of O2(-) and NO generation, as well as MDA content measured in PH-treated hemocytes, were drastically decreased after US degradation in any case. Similarly, the disturbance of DNA integrity (in terms of % DNA in tail, OM and TM), was negligible in case of US PH-treated hemocytes. Although further in vitro and in vivo studies are needed, the present study showed for the first time that high frequency US could be applied as a highly efficient and "environmentally friendly" process for degrading low molecular weight PAH, such as PH.

Selection of microalgae for wastewater treatment and potential lipids production.

In the present study, ten microalgal strains found in fresh and saline waters were cultured, and used to conduct batch experiments in order to evaluate their potential contribution to nutrient removal and biofuel production. The growth rate of microalgae was inversely analogous to their initial concentration. Three freshwater strains were selected, based on their growth rate, and their behavior with synthetic wastewater was further investigated. The strains studied were the Scenedesmus rubescens (SAG 5.95), the Neochloris vigensis (SAG 80.80), and the Chlorococcum spec. (SAG 22.83), and higher growth rate was observed with S. rubescens. Total phosphorus removal at an initial phosphate concentration of 6-7 mg P/L in the synthetic wastewater, was 53%, 25% and 11% for N. vigensis, Chlorococcum spec., and S. rubescens, respectively. Finally, the lipid content was determined at 20th and 30th day of cultivation, and the highest amount was observed at the 20th day.

Phenanthrene removal from aqueous solutions using well-characterized, raw, chemically treated, and charred malt spent rootlets, a food industry by-product.

Malt spent rootlets (MSR) are biomaterials produced in big quantities by beer industry as by-products. A sustainable solution is required for their management. In the present study, MSR are examined as sorbents of a hydrophobic organic compound, phenanthrene, from aqueous solutions. Raw MSR sorb phenanthrene but their sorptive properties are not competitive with the respective properties of commercial sorbents (e.g., activated carbons). Organic petrography is used as a tool to characterize MSR after treatment in order to produce an effective sorbent for phenanthrene. Chemical and thermal (at low temperature under nitrogen atmosphere) treatments of MSR did not result in highly effective sorbents. Based on organic petrography characterization, the pores of the treated materials were filled with humic colloids. When pyrolysis at 800 °C was used to treat MSR, a sorbent with new and empty pores was produced. Phenanthrene sorption capacity was 2 orders of magnitude higher for the pyrolized MSR than for raw MSR.

Virus inactivation by high frequency ultrasound in combination with visible light.

In this study, the effects of high frequency ultrasound (US) and visible light (VL) on virus inactivation were investigated. The bacteriophages ΦX174 and MS2 were used as model viruses. The experiments were performed at room temperature at three different, relatively high US frequencies (i.e., 582, 862, and 1142 kHz) with and without the use of VL, and different initial virus concentrations. The two bacteriophages were diluted in phosphate-buffered saline solution to a titer of 10(3)-10(4)pfu/mL. The experimental virus inactivation data were satisfactorily represented by a simple first-order kinetic expression. Virus inactivation was faster at the lower frequencies (582 and 862 kHz). Furthermore, it was observed that MS2 was inactivated faster than ΦX174. The simultaneous use of US and VL was found to be more effective than US alone for MS2 inactivation, indicating the existence of a synergistic effect. However, the use of VL in conjunction with high frequency US hindered the inactivation of ΦX174.

Degradation of PAHs by high frequency ultrasound.

Polycyclic aromatic hydrocarbons (PAHs) are persistent organic compounds, which have been reported in the literature to efficiently degrade at low (e.g. 20 kHz) and moderate (e.g. 506 kHz) ultrasound frequencies. The present study focuses on degradation of naphthalene, phenanthrene, and pyrene by ultrasound at three different relatively high frequencies (i.e. 582, 862, and 1142 kHz). The experimental results indicate that for all three frequencies and power inputs ≥ 133 W phenanthrene degrades to concentrations lower than our experimental detection limit (<1 µg/L). Phenanthrene degrades significantly faster at 582 kHz than at 862 and 1142 kHz. For all three frequencies, the degradation rates per unit mass are similar for naphthalene and phenanthrene and lower for pyrene. Furthermore, naphthalene degradation requires less energy than phenanthrene, which requires less energy than pyrene under the same conditions. No hexane-extractable metabolites were identified in the solutions.

Removal of biocolloids suspended in reclaimed wastewater by injection into a fractured aquifer model.

Two pilot-scale fractured aquifer models (FAMs) consisting of horizontal limestone slabs were employed to investigate the removal of biocolloids suspended in reclaimed wastewater. To better understand the behavior of real fractured aquifers, these FAMs intentionally were not "clean". The fracture apertures were randomly spread with soil deposits, and both FAMs were preflooded with reclaimed wastewater to simulate the field conditions of the Nardo fractured aquifer in the Salento area, Italy, where fractures are not clean due to artificial groundwater recharge. One of the FAMs was injected with secondary effluent from a wastewater treatment plant collected prior to the chlorination step and the other with exactly the same effluent, which was further treated in a commercial membrane reactor. Consequently, the organic and pathogen concentrations were considerably higher in the secondary effluent than in the membrane reactor effluent. Injected wastewater was continuously recirculated. Pathogen removal was greater for the secondary wastewater than the cleaner membrane reactor effluent. A simple mathematical model was developed to describe fracture clogging. The results suggest that the hydraulic conductivity of FAMs can be significantly degraded due to retention of viable and inactivated biocolloids suspended in reclaimed wastewater.

Design and analysis of a solar reactor for anaerobic wastewater treatment.

The aim of this research was to design a solar heated reactor system to enhance the anaerobic treatment of wastewater or biological sludge at temperatures higher than the ambient air temperature. For the proposed reactor system, the solar energy absorbed by flat plate collectors was transferred to a heat storage tank, which continuously supplied an anaerobic-filter reactor with water at a maximum temperature of 35 degrees C. The packed reactor was a metallic cylindrical tank with a peripheral twin-wall enclosure. Inside this enclosure was circulated warm water from the heat storage tank. Furthermore, a mathematical model was developed for the prediction of the temperature distribution within the reactor under steady state conditions. Preliminary results based on model simulations performed with meteorological data from various geographical regions of the world suggested that the proposed solar reactor system could be a promising and environmentally friendly approach for anaerobic treatment of wastewater and biological sludge.

Restart of anaerobic filters treating low-strength wastewater.

The anaerobic filter (AF) technology offers an alternative method for the direct treatment of low-strength wastewater and the study was undertaken to access AF-biomass reactivation after prolonged nonfeeding periods, an important characteristic making the process suitable for handling variable or intermittent pollution loads. Four upflow AF (three 12.5-L and one 3.9-L, each with different packing), which had treated municipal-type wastewaters (natural, amended or synthetic) for 34 months at 25 or 16 degrees C and varying hydraulic loads and had remained inactive for 24 months, were used. All units were fed synthetic wastewater [mean chemical oxygen demand (COD) 323 mg/L, total suspended solids (TSS) 47 mg/L] and operated at 27 degrees C for 2.5 months (phase 1); and following a 6-month idle period, the smaller filter treated municipal wastewater (mean COD and TSS 820 and 448 mg/L) at 16 degrees C for an additional 2.5 months (phase 2). The larger units operated at a 2.0-d hydraulic retention time and the smaller at 1.0-0.33-d in phase 1 and 2.0 or 1.0-d in phase 2. Reactivation was quick and yielded efficient treatment. Restart was affected by the AF history and packing morphology, the types of wastewater previously handled, and the duration of the nonfeeding period.

Adverse effects on Alfeios River Basin and an integrated management framework based on sustainability.

The Alfeios River, the longest and highest flow-rate river in Peloponnisos, constitutes an important water resource and ecosystem in Greece. In the present study, human activities in the Alfeios River Basin are described, and their impacts on water quality and the ecosystem are analyzed; effects resulting from interventions on river geomorphology between Flokas Dam and the river delta are determined. These actions have caused significant adverse impacts on the infrastructure (the dam, railroad, and road bridges), the level of aquifer water table and area water uses, and the aquatic and riparian ecosystem. A general integrated management strategy is formulated and a master management plan is proposed for resolving management problems in river basins. The plan considers local conditions and national requirements and complies with the European Communities legislation; it would help prevent further basin deterioration, improve water quality, and protect water resources and ecosystems in the area in accordance to sustainable development. The Alfeios River Basin serves as a case study in the development of the plan.