Exploring the effect on the environment of encapsulated micro- and nano-plastics into asphalt mastics for road pavement.

A new environmental problem is represented by the huge transformation of plastic waste released into the environment into small fragments, the so called micro- and nano-plastics, due to atmospheric phenomena. The smaller the size of the plastic fragments, the more their spreading into environmental compartments. The aim of this study is to test encapsulation into asphalt mastics of waste plastic material (WPM) as sustainable strategy to obtain road flexible pavements and to evaluate the potential release in water of micro and nano plastics. A new mastic mixing method was developed to blend the WPM with the bitumen contained into a bitumen emulsion (BE60/40) by adopting low mixing temperatures. Three different WPM contents, equal to 5, 10 and 20% by the weight of the bitumen contained in the BE60/40, were adopted to produce the mastics; the mastics' rheological properties, obtained by frequency sweep and multiple stress creep and recovery tests, were compared to those of a traditional asphalt mastic containing limestone filler. The aging of asphalt mastics was analyzed by soaking them in water and gradually lowering and raising temperature between -10 and 60 °C at predefined intervals. The addition of WPM improved greatly the asphalt mastic performance; in particular, for a WPM content of 10%, the rheological response in terms of stiffness remained unchanged after the mastic underwent thermal excursions in water. Encapsulation of micro and nano plastics into mastics reduced of more than 99% their potential water release.

A novel green approach for silver recovery from chloride leaching solutions through photodeposition on zinc oxide.

Silver is extensively used in electronics, industrial catalysis, and biomedical sector owing to its enhanced physicochemical properties. E-waste recycling may contribute significantly to enhance silver recovery in the view of a circular economy and limit the depletion of mineral sources. In this scenario, hydrometallurgical routes represent the most widely used techniques for silver extraction/recovery and require strong acidic solutions, high temperatures, and multiple operating units. An alternative sustainable route for silver recovery from leaching solutions used for silver extraction in industrial applications is herein proposed for the first time. The novel green process of silver recovery is based on the UV/vis light-driven photocatalytic deposition of pure metallic silver over low-cost and non-toxic ZnO photocatalyst. In the second step, ZnO is dissolved by slight acidification and pure metallic silver is easily recovered. Low environmental impact, mild operating conditions, and economic viability are among the major perks of the new silver recovery process developed. In the view of a full-scale implementation, several operating conditions of the recovery process (i.e., photocatalyst load, starting silver concentration, type of hole scavenger and irradiation) were thoroughly investigated. A mathematical model capable of describing the system behaviour under different operating conditions was also developed and allowed to estimate unknown kinetic parameters for the Ag-photodeposition process.

Operational strategies enhancing sewage sludge minimization in a combined integrated fixed-film activated sludge - oxic settling anaerobic system.

A lab-scale integrated fixed-film activated sludge (IFAS) reactor was mplemented with the oxic-settling anaerobic (OSA) cycle for reducing sewage sludge production through the addition of an anoxic/anaerobic sludge holding tank (SHT) along the sludge recycle line. The IFAS-OSA system was operated under the different hydraulic retention time (HRT) in the SHT (HRTSHT) of 12 h and 6 h, at an oxidation-reduction potential (ORP) < -91 mV and solid retention time (SRT) between 39 and 126 d. Furthermore, the effect of temperature increase in the SHT (TSHT) from ambient (19.8-25.6 °C) to mesophilic (35 °C) conditions was investigated. The system performances were monitored in terms of sludge minimization and dewaterability efficiencies as well as carbon and nutrients reduction. The observed sludge yield (Yobs) for the IFAS system was 0.37(±0.06) mg VSS/mg COD. After OSA implementation Yobs decreased by 32% and 46-65% at HRTSHT of 12 h and 6 h, respectively, indicating that prolonged exposure to anoxic/anaerobic conditions was not beneficial for sludge reduction. The lowest Yobs of 0.09(±0.05) mg VSS/mg COD (76% lower than that in the IFAS system) was obtained at an HRTSHT of 6 h and when TSHT was set at 35 °C. OSA implementation did not affect COD and NH4+ oxidation of the IFAS system (90-96% and 99%, respectively) and improved total nitrogen (TN) reduction (31-53%) due to improved denitrification in the SHT. On the contrary, sludge dewaterability worsened following OSA implementation, which was linked to the increased levels of exopolymeric substances in the suspended biomass.

Sludge minimization in mainstream wastewater treatment: Mechanisms, strategies, technologies, and current development.

Excess sludge production in wastewater treatment plants has become an enormous environmental issue worldwide mainly due to the increased efforts towards wastewater purification. Researchers and plant operators are looking for technological solutions to reduce sludge production through the upgrading of existing technologies and configurations or by substituting them with alternative solutions. Several strategies have been identified to reduce sludge production, including the use of biological and physical-chemical methods (or a combination of them) and novel technologies, although many have not been sufficiently tested at full-scale. To select the most suitable system for sludge reduction, understanding the reduction mechanisms, advantages, disadvantages, and the economic and environmental impact of each technology is essential. This work offers a comprehensive and critical overview of mainstream sludge reduction technologies and underlying mechanisms from laboratory to full scale, and describes potential application, configuration, and integration with conventional systems. Research needs are highlighted, and a techno-economic-environmental comparison of the existing technologies is also proposed.

Sustainable asphalt mastics made up recycling waste as filler.

The continuous growth of waste is generating worldwide more and more increasing related environmental concerns. Anything that is not recycled or recuperated from waste represents a loss of raw materials and other production factors used in the manufacture, transport and consumer phases of the product. This research explored the potential of three waste namely Construction and Demolition (CD) waste, Fly Ash (FA), and Jet Grouting (JG) waste as fillers in comparison to the traditional limestone one for making hot asphalt mastics for road pavement, through a rheological analysis and environmental compatibility tests towards the release of potentially toxic elements. A total of eight asphalt mastics were prepared by using two filler-to-binder weight ratios (f/b) of 0.5 and 1 for blending each filler with a neat bitumen 50/70 penetration grade. The Frequency Sweep test and the Multiple Stress Creep and Recovery (MSCR) test were carried out to investigate the rheological properties of the asphalt mastics. Asphalt mastics containing FA and JG fillers were found to be more mechanically and environmentally efficient than traditional limestone mastic in particular by adopting an f/b equal to 1 where it was observed higher complex shear modulus values, G*, (on average 50% compared to the traditional asphalt mastic) and lower non-recoverable creep compliance values, Jnr, (on average 35% compared to the traditional asphalt mastic) at all test temperatures investigated. Based on the suggested ranking methodology, CD emerged as the filler performing in the same way of the traditional one. All the waste containing mastics, showed up noticeable environmental compatibility, being the potentially toxic elements completely immobilized into the mastics' structure e practically not releasable into acidic water, highlighting the waste recycling for road pavements as primary strategy to immobilize hazardous wastes.

Insights into bioflocculation of filamentous cyanobacteria, microalgae and their mixture for a low-cost biomass harvesting system.

Cyanobacteria and microalgae are considered as interesting feedstocks for either the production of high value bio-based compounds and biofuels or wastewater treatment. Nevertheless, the high costs of production, mainly due to the harvesting process, hamper a wide commercialization of industrial cyanobacteria and microalgae based products. Recent studies have found in autoflocculation and bioflocculation promising spontaneous processes for a low-cost and environmentally sustainable cyanobacteria and microalgae biomass harvesting process. In the present work, bioflocculation process has been studied for three different inocula: filamentous cyanobacteria, microalgae and their mixture. Their cultivation has been conducted in batch mode using two different cultivation media: synthetic aqueous solution and urban wastewater. The removal of nutrients and flocculation process performance were monitored during the entire cultivation time. Results have proved that bioflocculation and sedimentation processes occur efficiently for filamentous cyanobacteria cultivated in synthetic aqueous solution, whereas such processes are less efficient in urban wastewater due to the specific characteristics of this medium that prevent bioflocculation to occur. Besides different efficiencies associated to cultivation media, this work highlighted that bioflocculation of sole microalgae is not as effective as when they are cultivated together with filamentous cyanobacteria.

Supramolecular aggregation of colloidal natural organic matter masks priority pollutants released in water from peat soil.

Natural organic matter (NOM) from Sphagnum peat soil is extracted in water and subjected to several investigations to obtain structural and conformational information. Data show that the extracted NOM is self-organized in colloidal aggregates of variable sizes (from nano to micro scales, depending on the solvent composition, i.e., ultrapure water, solutions with denaturing agents, acetone, ethanol). Aggregates are formed by highly heterogeneous classes of organic compounds. According to the results of nuclear magnetic resonance and fluorescence measurements, the three-dimensional structure of aggregates, revealed by scanning electron microscope imaging, is supposed to be stabilized by the exposition of polar functional groups to the solvent, with consequent formation of hydrogen bonds, dipole-interactions and cation bridging. In contrast, the inner part of the aggregates displays hydrophobic features and is hypothesized to be further reinforced by the establishment of π-stacking interactions. The structure is assumed to be a supramolecular aggregation of small-medium oligomeric fragments (Max 750 Da) in which priority pollutants are entrapped by dispersive forces. The structures are shown to be nanosized spheroidal particles further aggregated to form higher dimension supra-structures. Carbohydrates play primary role, stabilizing the structure and giving marked hydrophilic properties to the aggregates.

Air side-stream ammonia stripping in a thin film evaporator coupled to high-solid anaerobic digestion of sewage sludge: Process performance and interactions.

Air side-stream ammonia stripping in a thin-film evaporator (TFE) is proposed for the first time to control total ammonia nitrogen (TAN) concentration in a centralized full-scale plant performing high-solid anaerobic digestion (HSAD) of sewage sludge (SS). In this process, anaerobically digesting sludge (ADS) is continuously recirculated from the digester to the TFE unit where ammonia is stripped by an air stream. The stripped ammonia reacts with sulfuric acid in an absorption unit to produce ammonium sulfate. Overall, HSAD coupled to air side-stream ammonia stripping results in a twofold production of fertilizers (i.e. ammonium sulfate and SS digestate) recycling nutrients from organic wastes in agreement with the principles of circular economy. This study evaluates the influence of different operational airflow rates, temperatures and CO2 concentrations on air side-stream ammonia stripping in the TFE without alkali addition and the impact of air-based ammonia stripping on HSAD performance at full-scale. The study also investigates the chemistry and the interaction between the ammonia and carbonate subsystems of ADS and clarifies the stoichiometric relationship between ammonia and CO2 stripping.

Effect of nickel on the comparative performance of inverse fluidized bed and continuously stirred tank reactors for biogenic sulphur-driven autotrophic denitrification.

The comparative performance of an inverse fluidized bed reactor (IFBR) having high density polyethylene beads as carrier materials for biofilm formation and a continuous stirred tank reactor (CSTR), both maintaining autotrophic denitrification using biogenic sulphur (ADBIOS) in the absence and presence of nickel (Ni2+), was studied. The reactors were compared in terms of NO3--N and NO2--N removal and SO42--S production throughout the study. A simulated wastewater with an inlet NO3--N concentration of 225 mg/L and a decreasing concentration of biogenic sulphur (bio-S) from 1.5 to 0.375 g/L was used. Both reactors were operated at a hydraulic retention time (HRT) of 48 h for 140 days and at an HRT of 42 h for the following 68 days. A more efficient ADBIOS was observed in the CSTR than IFBR throughout the study due to a better mixing of the feed wastewater in the bulk liquid and a higher availability of bio-S to the suspended cells. The NO3--N removal efficiency in the IFBR decreased by approximately 41% when the feed bio-S was reduced to 0.375 g/L, while it remained unaffected in the CSTR. Conversely, the presence of Ni2+ did not significantly affect NO3--N removal in both reactors even at a feed Ni2+ concentration of 120 mg/L. The highest NO3--N removal rates achieved were 86 and 108 mg NO3--N/(L·day) in the IFBR and CSTR, respectively, in the presence of 120 mg/L of feed Ni2+ at an HRT of 42 h. Batch studies conducted with acclimatized biomass showed that the continuous-flow operation mode in both reactors played a major role in helping the autotrophic denitrifiers to tolerate Ni2+ toxicity.

Bioflocculation and settling studies of native wastewater filamentous cyanobacteria using different cultivation systems for a low-cost and easy to control harvesting process.

Bioflocculation phenomena for filamentous cyanobacteria were studied and analysed in two different cultivation systems (i.e. based on air-bubbling and on shaking) and for different initial biomass concentrations. Floc formation and biomass settling were monitored during batch cultivation tests according to an innovative protocol. Results showed that the two cultivation systems enhanced two different flocculation behaviours: air bubbling led to the formation of small and dense flocs, while the shaking table resulted in larger (14 mm2 vs 4 mm2) but mechanically weaker flocs. Floc analysis evidenced that the different mixing systems also affected the speciation of biomass. A mathematical model was developed to simulate and predict the settling performance during the bioflocculation process of filamentous cyanobacteria. Natural settling was examined at different phases of biomass growth. Optimal conditions were obtained at the end of the exponential growth phase, when 70% of the total cultivated biomass could be recovered.

Effect of carbon-to-nitrogen ratio on simultaneous nitrification denitrification and phosphorus removal in a microaerobic moving bed biofilm reactor.

In this study, long-term simultaneous nitrification denitrification (SND) and phosphorous removal were investigated in a continuous-flow microaerobic MBBR (mMBBR) operated at a dissolved oxygen (DO) concentration of 1.0 (±0.2) mg L-1. The mMBBR performance was evaluated at different feed carbon-to-nitrogen (C/N) ratios (2.7, 4.2 and 5.6) and HRTs (2 days and 1 day). Stable long-term mMBBR operation and chemical oxygen demand (COD), total inorganic nitrogen (TIN) and phosphorous (P-PO43-) removal efficiencies up to 100%, 68% and 72%, respectively, were observed at a feed C/N ratio of 4.2. Lower TIN removal efficiency and unstable performance were observed at feed C/N ratios of 2.7 and 5.6, respectively. HRT decrease from 2 days to 1 day resulted in transient NH4+ accumulation and higher NO2-/NO3- ratio in the effluent. Batch activity tests showed that biofilm cultivation at a feed C/N ratio of 4.2 resulted in the highest denitrifying activity (189 mg N gVSS-1 d-1), whereas the highest nitrifying activity (316 mg N gVSS-1 d-1) was observed after cultivation at a feed C/N ratio of 2.7. Thermodynamic modeling with Visual MINTEQ and stoichiometric evaluations revealed that P removal was mainly biological and can be attributed to the P-accumulating capacity of denitrifying bacteria.

The effect of bacterial and archaeal populations on anaerobic process fed with mozzarella cheese whey and buttermilk.

Dairy wastes can be conveniently processed and valorized in a biorefinery value chain since they are abundant, zero-cost and all year round available. For a comprehensive knowledge of the microbial species involved in producing biofuels and valuable intermediates from dairy wastes, the changes in bacterial and archaeal population were evaluated when H2, CH4 and chemical intermediates were produced. Batch anaerobic tests were conducted with a mixture of mozzarella cheese whey and buttermilk as organic substrate, inoculated with 1% and 3% w/v industrial animal manure pellets. The archaeal methanogens concentration increased in the test inoculated at 3% (w/v) when H2 and CH4 production occurred, being 1 log higher than that achieved in the test inoculated at 1% (w/v). Many archaeal species, mostly involved in the production of CH4, were identified by sequencing denaturing gradient gel electrophoresis (DGGE) bands. Methanoculleus, Methanocorpusculum and Methanobrevibacter genera were dominant archaea involved in the anaerobic process for bioenergy production from mozzarella cheese whey and buttermilk mixture.

Start-up of an anaerobic fluidized bed reactor treating synthetic carbohydrate rich wastewater.

The present work studied the start-up process of a mesophilic (37 ± 2 °C) anaerobic fluidized bed reactor (AFBR) operated at a hydraulic retention time (HRT) of 20 days using synthetic carbohydrate rich wastewater. Anox Kaldness-K1 carriers were used as biofilm carrier material. The reactor performance and biofilm formation were evaluated during the process. The start-up process at lower liquid recirculation flow rate enhanced the biofilm formation and reactor performance. The organic substrate composition had a major impact on early colonization of methanogenic archaea onto the surface of the Kaldness carriers during the start-up process. Specific organic substrates favouring the growth of methanogenic archaea, such as acetate, are preferred in order to facilitate the subsequent biofilm formation and AFBR start-up. The supply of 'bio-available' nutrients and trace elements, in particular iron, had an important role on optimal methanogenic activity and speeding-up of the biofilm development on the Kaldness carriers. This paper provides possible strategies to optimize the various operational parameters that influence the initial biofilm formation and development in an AFBR and similar high rate anaerobic reactors, hence can be used to reduce the long time required for process start-up.

Role of extracellular polymeric substances (EPS) production in bioaggregation: application to wastewater treatment.

This paper reviews the formation, structure, and stability of bioaggregates with an emphasis on the composition and distribution of extracellular polymeric substances (EPS) and their role in bioaggregation. Bioaggregation is ubiquitous in natural environment and is of great importance in biological wastewater treatment processes. It greatly influences the flocculability, settleability, and dewaterability for flocs and sludge retention and shear resistance for biofilms. The physico-chemical and microbial structures of bioaggregates are dependent on operational conditions as well as microbial diversity and spatial distribution. The formation of bioaggregates is mediated by the physico-chemical interactions as well as the microbial interactions such as EPS production and quorum sensing. EPS are composed of a mixture of macromolecules including proteins, polysaccharides, humic-like substances, and nucleic acids, which entrap the microbial cells in a three-dimensional matrix. The composition and physico-chemical characteristics of EPS have significant influence on the maintenance of the bioaggregate structure and the process performance of the wastewater treatment. However, the mechanisms of bioaggregation are still unclear and the conclusions on the role of EPS were mostly drawn from the established correlations and hypotheses. This paper expects to provide up-to-date knowledge on bioaggregation and insights for further studies and applications.

Dark fermentation of complex waste biomass for biohydrogen production by pretreated thermophilic anaerobic digestate.

The Biohydrogen Potential (BHP) of six different types of waste biomass typical for the Campania Region (Italy) was investigated. Anaerobic sludge pre-treated with the specific methanogenic inhibitor sodium 2-bromoethanesulfonic acid (BESA) was used as seed inoculum. The BESA pre-treatment yielded the highest BHP in BHP tests carried out with pre-treated anaerobic sludge using potato and pumpkin waste as the substrates, in comparison with aeration or heat shock pre-treatment. The BHP tests carried out with different complex waste biomass showed average BHP values in a decreasing order from potato and pumpkin wastes (171.1 ± 7.3 ml H2/g VS) to buffalo manure (135.6 ± 4.1 ml H2/g VS), dried blood (slaughter house waste, 87.6 ± 4.1 ml H2/g VS), fennel waste (58.1 ± 29.8 ml H2/g VS), olive pomace (54.9 ± 5.4 ml H2/g VS) and olive mill wastewater (46.0 ± 15.6 ml H2/g VS). The digestate was analyzed for major soluble metabolites to elucidate the different biochemical pathways in the BHP tests. These showed the H2 was produced via mixed type fermentation pathways.

Thermal pretreatment of olive mill wastewater for efficient methane production: control of aromatic substances degradation by monitoring cyclohexane carboxylic acid.

Anaerobic digestion is investigated as a sustainable depurative strategy of olive oil mill wastewater (OOMW). The effect of thermal pretreatment on the anaerobic biodegradation of aromatic compounds present in (OMWW) was investigated. The anaerobic degradation of phenolic compounds, well known to be the main concern related to this kind of effluents, was monitored in batch anaerobic tests at a laboratory scale on samples pretreated at mild (80±1 °C), intermediate (90±1 °C) and high temperature (120±1 °C). The obtained results showed an increase of 34% in specific methane production (SMP) for OMWW treated at the lowest temperature and a decrease of 18% for treatment at the highest temperature. These results were related to the different decomposition pathways of the lignocellulosic compounds obtained in the tested conditions. The decomposition pathway was determined by measuring the concentrations of volatile organic acids, phenols, and chemical oxygen demand (COD) versus time. Cyclohexane carboxylic acid (CHCA) production was identified in all the tests with a maximum concentration of around 200 µmol L(-1) in accordance with the phenols degradation, suggesting that anaerobic digestion of aromatic compounds follows the benzoyl-CoA pathway. Accurate monitoring of this compound was proposed as the key element to control the process evolution. The total phenols (TP) and total COD removals were, with SMP, the highest (TP 62.7%-COD 63.2%) at 80 °C and lowest (TP 44.9%-COD 32.2%) at 120 °C. In all cases, thermal pretreatment was able to enhance the TP removal ability (up to 42% increase).

Modified Anaerobic Digestion Model No.1 for dry and semi-dry anaerobic digestion of solid organic waste.

The role of total solids (TS) content in anaerobic digestion of selected complex organic matter, e.g. rice straw and food waste, was investigated. A range of TS from wet (4.5%) to dry (23%) was evaluated. A modified version of the Anaerobic Digestion Model No.1 for a complex organic substrate is proposed to take into account the effect of the TS content on anaerobic digestion. A linear function that correlates the kinetic constants of three specific processes (i.e. disintegration, acetate and propionate up-take) was included in the model. Results of biomethanation and volatile fatty acids production tests were used to calibrate the proposed model. Model simulations showed a good agreement between numerical and observed data.

Enhanced anaerobic digestion of food waste by thermal and ozonation pretreatment methods.

Treatment of food waste by anaerobic digestion can lead to an energy production coupled to a reduction of the volume and greenhouse gas emissions from this waste type. According to EU Regulation EC1774/2002, food waste should be pasteurized/sterilized before or after anaerobic digestion. With respect to this regulation and also considering the slow kinetics of the anaerobic digestion process, thermal and chemical pretreatments of food waste prior to mesophilic anaerobic digestion were studied. A series of batch experiments to determine the biomethane potential of untreated as well as pretreated food waste was carried out. All tested conditions of both thermal and ozonation pretreatments resulted in an enhanced biomethane production. The kinetics of the anaerobic digestion process were, however, accelerated by thermal pretreatment at lower temperatures (<120 °C) only. The best result of 647.5 ± 10.6 mlCH4/gVS, which is approximately 52% higher as compared to the specific biomethane production of untreated food waste, was obtained with thermal pretreatment at 80 °C for 1.5 h. On the basis of net energy calculations, the enhanced biomethane production could cover the energy requirement of the thermal pretreatment. In contrast, the enhanced biomethane production with ozonation pretreatment is insufficient to supply the required energy for the ozonator.

Effect of moisture on disintegration kinetics during anaerobic digestion of complex organic substrates.

The role of the moisture content and particle size (PS) on the disintegration of complex organic matter during the wet anaerobic digestion (AD) process was investigated. A range of total solids (TS) from 5% to 11.3% and PS from 0.25 to 15 mm was evaluated using carrot waste as model complex organic matter. The experimental results showed that the methane production rate decreased with higher TS and PS. A modified version of the AD model no.1 for complex organic substrates was used to model the experimental data. The simulations showed a decrease of the disintegration rate constants with increasing TS and PS. The results of the biomethanation tests were used to calibrate and validate the applied model. In particular, the values of the disintegration constant for various TS and PS were determined. The simulations showed good agreement between the numerical and observed data.

Effect of total solids content on methane and volatile fatty acid production in anaerobic digestion of food waste.

This work investigates the role of the moisture content on anaerobic digestion of food waste, as representative of rapidly biodegradable substrates, analysing the role of volatile fatty acid production on process kinetics. A range of total solids from 4.5% to 19.2% is considered in order to compare methane yields and kinetics of reactors operated under wet to dry conditions. The experimental results show a reduction of the specific final methane yield of 4.3% and 40.8% in semi-dry and dry conditions compared with wet conditions. A decreasing trend of the specific initial methane production rate is observed when increasing the total solids concentration. Because of lack of water, volatile fatty acids accumulation occurs during the first step of the process at semi-dry and dry conditions, which is considered to be responsible for the reduction of process kinetic rates. The total volatile fatty acids concentration and speciation are proposed as indicators of process development at different total solids content.