Exploring the superior adsorption capacity of multi-layer graphene/alginate granules for the removal of methylene blue dye from water.

Graphene-based materials are gaining increasing attention towards their use in manufacturing and environmental applications. In this context, multi-layer graphene (MG) has been recently applied for the adsorption of contaminants from water resulting in promising results. However, the extreme lightness of this material often makes it difficult to handle due to its potential dispersion in the surrounding environment as well as to its transport and loss with the effluent. In this study, a novel granular material was synthesized by embedding MG into an alginate matrix, resulting in the so-called granular MG (GMG). This material was tested for the adsorption of methylene blue (MB) from water, which is a typical dye used in textile industries and must be removed from the effluent. GMG materials with different MG contents (5 and 20 %) were compared with MG and a commercial adsorbent to assess their adsorption capacity and the most performing material was selected for in-depth physical and chemical characterization. The structural, surface, kinetic, isotherm, and thermodynamic properties, the pH and temperature dependence, as well as the regeneration and reuse of GMG 5% were investigated through batch adsorption tests under different operating conditions. The study reveals that GMG 5% has a superior adsorption capacity compared to the tested materials and can be considered as a promising alternative to commercial carbon-based materials according to techno-economic considerations.

Validation of a liquid chromatography coupled with tandem mass spectrometry method for the determination of drugs in wastewater using a three-phase solvent system.

Pharmaceuticals constitute one of the most important emerging classes of environmental pollutants. A three-phase solvent system of water, water containing 0.1% of formic acid and acetonitrile was successfully used to separate, by liquid chromatography with mass spectrometry (LC-MS), polarity-matched pharmaceuticals, that is, carbamazepine, clarithromycin, and erythromycin, as well as amoxicillin and metformin. Despite of polarity similarities, these pharmaceuticals were completely resolved in the analytical run time of 15 min. The optimized three-phase solvent system based-method was validated for the simultaneous analysis of six matched-polarity pharmaceuticals in wastewater samples. Good linearity (coefficient of determination more than 0.993) and precision (relative standard deviation less than 15.66%) were achieved. Recovery of analytes from the wastewater was between 0.70 and 1.18. Limits of detections ranged from 0.0001 to 0.5114 µg/L. No significant matrix effect, evaluated by post extraction addition, was observed in the electrospray ionization (ESI) source. Then, this methodology has been successfully applied to environmental study of pharmaceutical residues occurring in influent and effluent wastewater samples, from the main wastewater treatment plant in Potenza (Basilicata, Southern Italy).

Environmental factors influencing landfill gas biofiltration: Lab scale study on methanotrophic bacteria growth.

The post-management of landfills represents an important challenge for landfill gas treatment. Traditional systems (energy recovery, flares, etc.) present technical problems in treating flow with low methane (CH4) concentrations. The objective of this study was to isolate methanotrophic bacteria from a field-scale biofilter in order to study the bacteria in laboratories and evaluate the environmental factors that mostly influence Microbial Aerobic Methane Oxidation (MAMO). The soil considered was sampled from the biofilter located in the landfill of Venosa (Basilicata Region, Italy) and it was mainly composed of wood chips and compost. The results showed that methanotrophic microorganisms are mainly characterized by a slow growth and a significant sensitivity to CH4 levels. Temperature and nitrogen (N) also have a very important role on their development. On the basis of the results, biofilters for biological CH4 oxidation can be considered a viable alternative to mitigate CH4 emissions from landfills.

Removal of Hydrocarbons from Contaminated Soils by Using a Thermally Expanded Graphite Sorbent.

Lab-scale experiments on three soil matrices featured by increasing granulometry (sea sand, silica sand and gravel) were carried out in order to evaluate the adsorption capability and the removal efficiency of a new graphene-based material. Soil samples, firstly contaminated with different quantities of used lubricant oil up to final concentrations of 12.5, 25.0, 50.0 g kg-1, were treated with an opportune amount of thermally expanded graphite (TEG) (i.e. 1/10, 1/20, 1/40 as TEG/pollutant ratio). Results show that the removal efficiency of TEG is directly correlated to the contamination level of the soil. The best removal efficiency (87.04%) was obtained during the treatment of gravel samples at the maximum contamination level by using the highest dosage of TEG. A good removal efficiency (80.83%) was also achieved using lower TEG/pollutant ratio. Moreover, TEG at ratio 1/10 showed worse removal efficiencies in treating sea (81.17%) and silica sand (63.52%) than gravel. In this study, also the thermal regeneration was investigated in order to evaluate a possible reuse of TEG with subsequent technical and economic advantages. TEG-technique proves to be technologically and economically competitive with other currently used technologies, revealing the best choice for the remediation of hydrocarbon-contaminated soils.

Methane oxidation in a biofilter (Part 2): A lab-scale experiment for model calibration.

In this study an experimental study on a biological methane oxidation column presented with the aim to calibrate a mathematical model developed in an earlier study. The column was designed to reproduce at lab-scale a real biofilter trying to consider the more probable landfill boundary conditions. Although the methane oxidation efficiency in the column was lower than the expected (around 35%), an appropriate model implementation showed an acceptable agreement between the outcomes data of the model simulation and the experimental data (with Theil's Inequality Coefficient value of 0.08). A calibrated model allows a better management of the biofilter performance in terms of methane oxidation.

Methane oxidation in a biofilter (Part 1): Development of a mathematical model for designing and optimization.

The aim of this work is the evaluation of the efficiency of such a biofilter, through the application of a mathematical model which describes the biological oxidation process. This mathematical model is able to predict the efficiency of the system under varying operating conditions. Literature data have been used in order to build the model. The factors that mostly affect the process and which actually regulate the entire process have been highlighted in this work. Specifically, it was found that temperature, flow and methane concentration are the most important parameters that influence the system. The results obtained from the mathematical model showed also that the biofilter system is simple to implement and manage and allows the achievement of high efficiency of methane oxidation. In the optimal conditions for temperature (between 20-30°C), residence time (between 0.7-0.8 h) and methane molar fraction (between 20-25%) the efficiency of methane oxidation could be around 50%.

Removal of organic micropollutants from water by adsorption on thermo-plasma expanded graphite encapsulated into calcium alginate.

Nowadays, public concern is focused on the degradation of water quality. For this reason, the development of innovative technologies for water treatment in view of (micro)pollutant removal is important. Indeed, organic (micro)pollutants, such as pharmaceuticals, herbicides, pesticides and plasticizers at concentration levels of µg L-1 or even ng L-1 are hardly removed during conventional wastewater treatment. In view of this, thermo-plasma expanded graphite, a light-weight innovative material in the form of a powder, was encapsulated into calcium alginate to obtain a granular form useful as filtration and adsorption material for removal of different pollutants. The produced material was used to remove atrazine, bisphenol-A, 17-α-ethinylestradiol and carbamazepine (at concentration levels of 125, 250 and 500 µg L-1) by top-down filtration. The effect of flow rate, bed depth and adsorbent composition was evaluated based on breakthrough curves. The experimental data was analysed with the Adams-Bohart model in view of scale-up. Under optimal conditions, removal and adsorption capacity of respectively about 21%, 21%, 38%,42%, 43 µg g-1, 44 µg g-1, 37 µg g-1 and 87 µg g-1 were obtained for atrazine, bisphenol, 17-α ethinylestradiol and carbamazepine when using 0.12 g of thermo-plasma expanded graphite to treat 200 mL at 500 µg L-1 (for each compound) of solution obtaining at contact time of 20 min. The granular form of TPEG obtained (GTPEG) by entrapping in calcium alginate results to have a good adsorbent property for the removal of carbamazepine, atrazine, bisphenol A and 17-α ethinylestradiol from water at concentration levels between 250 and 500 µg L-1. Promising results confirm the adsorbent properties of TPEG and push-up us to investigate on its application and improve of its performance by evaluating different entrapping materials. Supplementary Information: The online version contains supplementary material available at 10.1007/s40201-023-00876-9.

Effect of site-specific conditions and operating parameters on the removal efficiency of petroleum-originating pollutants by using ozonation.

Soil contamination is a worldwide problem, mainly caused by a wide range of organic compounds: e.g., alkanes, aromatics, and polynuclear aromatics. Using ozone to help remediate contaminated soils is gaining interest due to its capability in oxidizing recalcitrant contaminants in short application time., although studies using ozonation for soil remediation are so far limited to the laboratory scale. This review attempts to summarize and discuss the state of the art in the treatment of soils contaminated with recalcitrant organic contaminants by using ozone, emphasizing the influence of operating conditions, such as the content and age of soil organic matter, grain size, moisture content, pH, and ozone dose. Special attention is given to the combination of ozonation and biodegradation. The main advantages in using ozonation as a remediation technique are its high oxidation potential applicable to a wide range of organic pollutants and its oxygen release after chemical decomposition that allow aerobic biodegradation. The review results show that ozonated soils can be reused after ozonation treatment, therefore ozonation can be considered an excellent remediation technique, even if combined with biodegradation, allowing removal percentages of 90% and more.

Assessing the fluvial system resilience of the river Bacchiglione to point sources of pollution in Northeast Italy: a novel Water Resilience Index (WRI) approach.

Modelling and evaluating the resilience of environmental systems has recently raised significant interest among both practitioners and researchers. However, it has not yet been used to measure the absorption and recovery capacities of a river subject to varying levels of pollution due to natural and anthropic sources of contamination within the basin. Fast worldwide population growth and climate change are contributing to an increased degradation status in surface water bodies and to a decreased efficiency of their natural self-purification processes. Decision-makers are, therefore, more and more encouraged to implement alternative management strategies focussed on improving the system resilience to current and future perturbations. To this end, a novel Water Resilience Index (WRI), based on different quality parameters, was developed, and it is here proposed to estimate the ability of the river Bacchiglione, located in Northeast Italy, absorb continuous and unpredictable changes due to potential effects of point sources of pollution, that is, urban and industrial wastewater, and still maintain its vital functions. This new index is integrated in a mathematical model, which represents the river as an influence diagram where the nodes are the gauged stations and the arcs are the fluvial reaches among the stations, to identify the river reaches in need of resilience improvement. In addition, in order to simplify the analytical procedure and lower the costs and times of the monitoring activities, a principal component analysis is also used, as it is able to reduce the number of the water quality parameters to be collected from the sampling stations, distributed along the main river, and thus to calculate a minimum WRI. The good agreement between the results obtained by both the original and minimum WRI shows the effectiveness of the proposed methodology. This approach could be applied to all basins with the same issues, and not just in the Italian case study here analysed, as it might be a valid tool to plan interventions and mitigation actions, protecting the resource from pollution risks and achieving environmental quality and Sustainable Development Goals both in the water bodies and their surrounding territories. In addition, this strategy could be integrated in the existing models supporting local decision-makers and administrators, aiming at increasing the resilience of urban and rural areas to pollution phenomena and facilitating the development of effective policies to reduce the impacts of global change on water quality.

Removal of diclofenac from aqueous solutions by adsorption on thermo-plasma expanded graphite.

The adsorption of diclofenac on thermo-plasma expanded graphite (a commercial product) from water solutions was investigated. The adsorbent material was characterized by SEM, TEM, BET, Raman and X-ray diffraction analyses. Typical diffractogram and Raman spectrum of graphitic material, dimension of 24.02 nm as crystallite dimension and a surface area of 47 m2 g-1 were obtained. The effect of pH on the adsorption capacity was evaluated in the range 1-7 and the adsorption mechanism was described by kinetic and isothermal studies. Pseudo-second order and Dubinin-Radushkevich models agreed with theoretical values of adsorption capacity (i.e. 400 and 433 mg g-1, respectively) and resulted to be the best fit for kinetics and isothermal experimental data. The thermodynamics of the process was evaluated by plotting the adsorption capacity/concentration ratio at the equilibrium as a function of different values of the multiplicative inverse of temperature. Moreover, the adsorbent regeneration was also investigated, comparing two different remediation techniques. Solvent washing performed with NaOH 0.2 M and thermo-treatment carried out by heating in an oven at 105 °C for 2 h and then at 200 °C for 4 h. The thermo-treatment was the best technique to regenerate the adsorbent, ensuring same performance after 4 cycles of use and regeneration.

Method development and optimization for the determination of benzene, toluene, ethylbenzene and xylenes in water at trace levels by static headspace extraction coupled to gas chromatography-barrier ionization discharge detection.

Benzene, toluene, ethylbenzene, and xylenes, more commonly named BTEX, represent one of the most ubiquitous and hazardous groups of atmospheric pollutants. The goal of our research was the trace quantification of BTEX in water by using a new simple, low-cost, and accurate method, based on headspace (HS) extraction and gas chromatography (GC) coupled to barrier ionization discharge detector (BID). This water application dealt with simple matrices without protein, fat, or humic material that adsorb target analytes, thus the external standard calibration was suitable to quantify each compound. The validation steps included the study of linearity, detection and quantification limits, and accuracy. LODs and LOQs varied from 0.159 to 1.845 µg/L and from 0.202 to 2.452 µg/L, respectively. The recovery was between 0.74 ±â€¯0.13 and 1.15 ±â€¯0.09; relative standard deviations (% RDSs) were less than 12.81% (n = 5) and 14.84% (n = 10). Also, GC performance was evaluated in term of efficiency, peak tailing and resolution. Preliminary results from practical applications to analyses of real samples are presented. The results indicate that static HS coupled to GC-BID is a successful method for BTEX analysis in water samples at the µg/L levels, provided that hydrocarbons interference occur at similar concentration levels. GC-BID may become a routine reference method alongside the official analytical techniques for quality control purposes of contaminated waters. Moreover, the new method is amenable to automation by using commercial HS units.

Validation of an analytical method for simultaneous high-precision measurements of greenhouse gas emissions from wastewater treatment plants using a gas chromatography-barrier discharge detector system.

Wastewater treatment plants (WWTPs) emit CO2 and N2O, which may lead to climate change and global warming. Over the last few years, awareness of greenhouse gas (GHG) emissions from WWTPs has increased. Moreover, the development of valid, reliable, and high-throughput analytical methods for simultaneous gas analysis is an essential requirement for environmental applications. In the present study, an analytical method based on a gas chromatograph (GC) equipped with a barrier ionization discharge (BID) detector was developed for the first time. This new method simultaneously analyses CO2 and N2O and has a precision, measured in terms of relative standard of variation RSD%, equal to or less than 6.6% and 5.1%, respectively. The method's detection limits are 5.3ppmv for CO2 and 62.0ppbv for N2O. The method's selectivity, linearity, accuracy, repeatability, intermediate precision, limit of detection and limit of quantification were good at trace concentration levels. After validation, the method was applied to a real case of N2O and CO2 emissions from a WWTP, confirming its suitability as a standard procedure for simultaneous GHG analysis in environmental samples containing CO2 levels less than 12,000mg/L.

Monitoring the aeration efficiency and carbon footprint of a medium-sized WWTP: experimental results on oxidation tank and aerobic digester.

The efficiency of aeration systems should be monitored to guarantee suitable biological processes. Among the available tools for evaluating the aeration efficiency, the off-gas method is one of the most useful. Increasing interest towards reducing greenhouse gas (GHG) emissions from biological processes has resulted in researchers using this method to quantify N2O and CO2 concentrations in the off-gas. Experimental measurements of direct GHG emissions from aerobic digesters (AeDs) are not available in literature yet. In this study, the floating hood technique was used for the first time to monitor AeDs. The floating hood technique was used to evaluate oxygen transfer rates in an activated sludge (AS) tank of a medium-sized municipal wastewater treatment plant located in Italy. Very low values of oxygen transfer efficiency were found, confirming that small-to-medium-sized plants are often scarcely monitored and wrongly managed. Average CO2 and N2O emissions from the AS tank were 0.14 kgCO2/kgbCOD and 0.007 kgCO2,eq/kgbCOD, respectively. For an AeD, 3 × 10-10 kgCO2/kgbCOD direct CO2 emissions were measured, while CO2,eq emissions from N2O were 4 × 10-9 kgCO2,eq/kgbCOD. The results for the AS tank and the AeD were used to estimate the net carbon and energy footprint of the entire plant.

Preliminary evaluation of Pleurotus ostreatus for the removal of selected pharmaceuticals from hospital wastewater.

The fungus Pleurotus ostreatus was investigated to assess its ability to remove diclofenac, ketoprofen, and atenolol spiked at 10 mg/L each one in hospital wastewater. The degradation test was carried out in a fluidized bed bioreactor testing both the batch and the continuous mode (hydraulic retention time in the range 1.63-3 days). In batch mode, diclofenac disappeared in less than 24 h, ketoprofen was degraded up to almost 50% in 5 days while atenolol was not removed. In continuous mode, diclofenac and ketoprofen removals were about 100% and 70% respectively; atenolol degradation was negligible during the first 20 days but it increased up to 60% after a peak of laccase production and notable biomass growth. In order to identify the enzymatic system involved, further experiments were carried out in flasks. Purified laccase completely transformed atenolol and diclofenac in less than 5 h, but not ketoprofen. In vivo experiments suggested that cytochrome P450 could be involved in diclofenac and ketoprofen degradation, while partial correlation studies confirmed the role of laccase in atenolol and diclofenac degradation. Two intermediates of diclofenac and ketoprofen were detected by nuclear magnetic resonance. Moreover P. ostreatus was able to reduce chemical oxygen demand of the hospital wastewater which is an important advantage comparing to other fungi in order to develop a wastewater treatment process. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:1529-1537, 2017.

Biodegradation of 2-naphthalensulfonic acid polymers by white-rot fungi: Scale-up into non-sterile packed bed bioreactors.

This paper presents a first scale up under non-sterile conditions of the biodegradation process of 2-naphthalensulfonic acid polymers (NSAP) contained in a petrochemical wastewater by two white-rot fungi (Bjerkandera adusta and Pleurotus ostreatus). The biodegradation experiment was conducted first in flasks and then in packed-bed bioreactors filled with inert and biodegradable carriers (straw), the latter acting as both physical support and carbon source. Reactor inoculated with P. ostreatus attached on straw worked under non-sterile conditions for three months showing 30 ± 5% NSAP degradation. Respirometric tests showed that the fungal treatment was also able to significantly increase the biodegradable fraction of the wastewater COD, which rose from 9% to 40%. It was observed that the fungal degradation of the straw in the bed releases non-biodegradable by-products. Taking into account this contribution to nbCOD, the combined treatment of fungi and activated sludge could theoretically be able to reduce the original COD by up to 73%.

Biodegradation of carbamazepine and clarithromycin by Trichoderma harzianum and Pleurotus ostreatus investigated by liquid chromatography - high-resolution tandem mass spectrometry (FTICR MS-IRMPD).

In this study, the capability of pharmaceutical biodegradation of fungus Trichoderma harzianum was evaluated through the comparison with the well-known biodegradation capability of white-rot fungus Pleurotus ostreatus. The study was performed in aqueous phase under aerobic conditions, using two of the most frequently detected drugs in water bodies: carbamazepine and clarithromycin, with concentrations commonly found in treated wastewater (4µg/l and 0.03µg/l respectively). For the first time, we demonstrated that T. harzianum is able to remove carbamazepine and clarithromycin. The analyses were performed by reversed-phase liquid chromatography/mass spectrometry, using high-resolution Fourier-transform ion cyclotron resonance mass spectrometry upon electrospray ionization in positive ion mode. The high selectivity and mass accuracy provided by high-resolution mass spectrometry, allowed us to identify some unknown metabolites. On the basis of our study, the major metabolites detected in liquid culture treated by T. harzianum were: 14-hydroxy-descladinosyl- and descladinosyl-clarithromycin, which are pharmacologically inactive products not dangerous for the environment.

Greenhouse gases from wastewater treatment - A review of modelling tools.

Nitrous oxide, carbon dioxide and methane are greenhouse gases (GHG) emitted from wastewater treatment that contribute to its carbon footprint. As a result of the increasing awareness of GHG emissions from wastewater treatment plants (WWTPs), new modelling, design, and operational tools have been developed to address and reduce GHG emissions at the plant-wide scale and beyond. This paper reviews the state-of-the-art and the recently developed tools used to understand and manage GHG emissions from WWTPs, and discusses open problems and research gaps. The literature review reveals that knowledge on the processes related to N2O formation, especially due to autotrophic biomass, is still incomplete. The literature review shows also that a plant-wide modelling approach that includes GHG is the best option for the understanding how to reduce the carbon footprint of WWTPs. Indeed, several studies have confirmed that a wide vision of the WWPTs has to be considered in order to make them more sustainable as possible. Mechanistic dynamic models were demonstrated as the most comprehensive and reliable tools for GHG assessment. Very few plant-wide GHG modelling studies have been applied to real WWTPs due to the huge difficulties related to data availability and the model complexity. For further improvement in GHG plant-wide modelling and to favour its use at large real scale, knowledge of the mechanisms involved in GHG formation and release, and data acquisition must be enhanced.

Application of fuzzy logic and sensitivity analysis for soil contamination hazard classification.

The present article is aimed at illustrating a methodology for a rapid and effective assessment of pollution hazard connected with the presence of uncontrolled landfills. In particular, by means of a fuzzy approach, the criterion adopted allowed a comparison of the results obtained from a cross analysis of some intrinsic characteristics of the single landfills and the territory where they are located. Their identification shows the most relevant environmental problem. Therefore, we have classified each site within a hazard scale enabling us to understand which one requires to be checked more urgently, to do instrumental surveys and, if needed, to do restoration and reclamation. Moreover, the sensitivity analysis we carried out allowed us to identify which is the best membership function belonging and which is the best defuzzification method. That is, in particular, the trapezoidal function and the centroid method. The proposed fuzzy approach, supported by the sensitivity analysis, has revealed to be an important tool for supporting decisions, in order to optimise technical and economic resources.