Benchmarking environmental and economic indicators of sludge management alternatives aimed at enhanced energy efficiency and nutrient recovery.

Wastewater treatment plants (WWTPs) have been developed as multifunctional systems that aim to eliminate pollutants present in wastewater, manage the sludge produced and improve energy efficiency. Specifically, sludge management accounts for the largest share in operational costs. Considering the relevant role of sludge treatment within the overall management scheme, this study aims to evaluate different alternatives and strategies for sludge management and treatment from the perspective of life cycle analysis, with special emphasis on those options that reduce environmental impacts and economic costs. Two pre-treatments (chemical or thermal) and two post-treatments (composting unit followed by land application or incineration) were evaluated to improve the eco-balance of the anaerobic digestion (AD) process in terms of operational (biogas production and digested sludge), environmental and economic indicators. According to the results obtained, both sludge pre-treatment alternatives proved to be an adequate alternative to improve biogas production without negatively affecting environmental and economic impacts. Finally, if the final disposal of the digestate is analysed, its application to the soil as a biofertiliser is recommended, since it presents a better environmental profile than incineration.

Iron oxide-mediated photo-Fenton catalysis in the inactivation of enteric bacteria present in wastewater effluents at neutral pH.

The pressure on natural water resources associated with increasing water scarcity highlights the value of using reclaimed water through the development of efficient and environmentally friendly treatment technologies. In this work, the use of magnetic nanoparticles in photo-Fenton catalysis for water disinfection was considered to inactivate natural enteric bacteria present in municipal wastewater effluents under white light and neutral pH. The most recommended ranges were evaluated in key variables such as the loading and composition of nanoparticles (NPs), hydrogen peroxide (H2O2) concentration, the light source (UV and visible) and treatment time were evaluated in wastewater disinfection expressed in terms of total coliforms and Escherichia coli colony forming units (CFU). The magnetic separation of NPs allowed the disinfection process to be carried out in different cycles, facilitating the recovery of the nanocatalyst and avoiding its discharge with the treated effluent.

Regionalizing eco-toxicity characterization factors for copper soil emissions considering edaphic information for Northern Spain and Portuguese vineyards.

The management of vineyards depends on the use of plant protection agents. Regardless of the numerous environmental impacts that these pesticides generate during their production, their dosage as pest control agents in vineyards causes an important toxic effect that must be monitored. Copper-based inorganic pesticides are the most widely used agents to control fungal diseases in humid wine-growing regions. It is, however, significant that the environmental analysis of their use through the Life Cycle Assessment (LCA) methodology does not provide detailed information on the potential toxicity of this type of pesticides. Hence, most studies report average values for copper characterization factors (CFs), excluding local soil characteristics. The objective of the study was the spatial characterization of the ecotoxicity factors of copper soil emissions as a function of the chemical characteristics of vineyard soils located in Portugal and Galicia (NW Spain). A multiple linear regression model was applied to calculate the comparative toxic potential. Subsequently, CFs for copper were calculated based on spatial differentiation considering the variable properties of the soil within each wine appellation. The CFs obtained for the area evaluated ranged from 141 to 5937 PAF·m3·day/kgCu emitted, for fibric histosols (HSf) and dystic cambisols (CMd), respectively. Moreover, the average values obtained for Galician and Portuguese soils were 1145 and 2274 PAF·m3·day/kgCu emitted, respectively. The results obtained illustrate the high variability of CF values as a function of the chemical characteristics of each type of soil. For example, Cu soil mobility was linked to organic carbon content and pH. Finally, to validate the representativeness of the calculated CFs, these were applied to the results of 12 literature life cycle inventories of grape production in the area evaluated, revealing that impact scores associated with Cu emissions can considerably vary when spatially-differentiated CFs are implemented.

Insight into antibiotics removal: Exploring the photocatalytic performance of a Fe3O4/ZnO nanocomposite in a novel magnetic sequential batch reactor.

The purpose of this research was the preparation and photocatalytic evaluation of a novel nanocomposite (NC) based on Fe3O4/ZnO, to eliminate four persistent antibiotics in surface waters: sulfamethoxazole, trimethoprim, erythromycin and roxithromycin. Prior to the operation of the photocatalytic reactor, the influence of pH (3-9), catalyst concentration (50-800 mg L-1), oxidant dose (0-100 mg L-1) and concentration of different targets (10-100 µg L-1) on the catalytic efficiency was evaluated. The analysis of reaction kinetics showed that degradation processes of the four antibiotics followed a pseudo-first-order kinetic model. Antibiotics adsorption onto the nanocomposite surface depended on their electrostatic nature and played an important role when decreasing the initial concentration of antibiotics. In this context, kinetic rates were higher at lower initial levels of organic pollutants, which is a favourable effect from a practical application perspective. On the other hand, a synergistic effect of the available Fe in the nanocomposite was found, contributing to the oxidation of antibiotics by photo-Fenton as a secondary reaction. Then, a magnetic photocatalytic reactor was operated under optimal conditions. The enhanced photonic efficiency of Fe3O4/ZnO in the system, as well as the ease of the magnetic separation and catalyst reusability, indicate the viability of this reactor configuration.

Comparative environmental assessment of alternative waste management strategies in developing regions: A case study in Kazakhstan.

The management of municipal solid waste in the Republic of Kazakhstan is still in its infancy. This situation poses a potential threat to the environment and public health and, therefore, it is necessary to introduce improved management schemes in the country. In this study, the life cycle assessment methodology was followed to evaluate the potential environmental benefits of implementing alternative management schemes based on low-waste generation and renewable energy production. The current situation of the capital city Astana was considered as the base case. Environmental results showed that air emissions in terms of landfill gases are the major contributor to climate change impacts, while landfill disposal of the non-recovered fraction of recyclable materials was responsible for the highest impacts in the other categories (especially land use). However, the reuse of recycled materials largely offsets the related environmental burdens, along with energy generation. In comparative terms, it was demonstrated that the proposed waste management scenarios are more environmentally friendly than current practices (S0), mainly owing to the credits associated with the valorisation of renewable energy (S2) and recovered materials (S3). Consequently, the evaluation showed that greater efforts should be made to exploit the energy potential of organic fraction, together with higher recycling rates, to move towards lower environmental impacts associated with municipal solid waste management.

Environmental assessment of alternative treatment schemes for energy and nutrient recovery from livestock manure.

The application of livestock manure on agricultural land is being restricted due to its significant content of phosphorus (P) and nitrogen (N), leading to eutrophication. At the same time, the growing demand for N and P mineral fertilizers is increasing their production costs and causing the depletion of natural phosphate rock deposits. In the present work, seven technologically feasible treatment schemes for energy (biogas) and nutrient recovery (e.g., struvite precipitation) and/or removal (e.g., partial nitritation/anammox) were evaluated from an environmental perspective. In general, while approaches based solely on energy recovery and use of digestate as fertilizer are commonly limited by community regulations, strategies pursuing the generation of high-quality struvite are not environmentally sound alternatives. In contrast, schemes that include further solid/liquid separation of the digestate improved the environmental profile, and their combination with an additional N-removal stage would lead to the most environmental-friendly framework. However, the preferred scenario was identified to be highly dependent on the particular conditions of each site, integrating environmental, social and economic criteria.

Environmental and water sustainability of milk production in Northeast Spain.

This study focuses on the assessment of the environmental profile of a milk farm, representative of the dairy sector in Northeast Spain, from a cradle-to-gate perspective. The Life Cycle Assessment (LCA) principles established by ISO standards together with the carbon footprint guidelines proposed by International Dairy Federation (IDF) were followed. The environmental results showed two critical contributing factors: the production of the livestock feed (e.g., alfalfa) and the on-farm emissions from farming activities, with contributions higher than 50% in most impact categories. A comparison with other LCA studies was carried out, which confirmed the consistency of these results with the values reported in the literature for dairy systems from several countries. Additionally, the Water Footprint (WF) values were also estimated according to the Water Footprint Network (WFN) methodology to reveal that feed and fodder production also had a predominant influence on the global WF impacts, with contributions of 99%. Green WF was responsible for remarkable environmental burdens (around 88%) due to the impacts associated with the cultivation stage. Finally, the substitution of alfalfa by other alternative protein sources in animal diets were also proposed and analysed due to its relevance as one of the main contributors of livestock feed.

The prospective use of biochar as adsorption matrix - A review from a lifecycle perspective.

Biochar is obtained from the thermochemical conversion of biomass in an oxygen-limited environment. Beyond its use for soil amendment and carbon sequestration, other value-added applications, such as a green environmental sorbent for different types of pollutants, are also of increasing interest. This paper reviews the available literature on the use of various feedstocks for biochar production as an initial step to compile the required inventory data from material flow data analysis. The environmental evaluation of different schemes of biochar production in a life cycle perspective reports the environmental impacts of the different alternatives, with more sustainable profiles than the use of activated carbon as conventional adsorption material. Moreover, most systems were validated as negative carbon processes with favorable performance regarding climate change mitigation. In particular, materials based on lignocellulosic waste were responsible for the highest environmental benefits, mainly due to their largest energy potential in comparison with other feedstocks.

Review of lignocellulolytic enzyme activity analyses and scale-down to microplate-based assays.

With the increasing use of enzymes in environmental applications, there is a need for analytical methods adapted to large factorial experiments. Existing reference methods are chemical and labor intensive and unsuitable to analyze in parallel a large number of samples. Based on an extensive literature review and on experimental results, this work compares reference and microplate adapted methods to define the most adequate filter paper, carboxymethylcellulase, ß-glucosidase and xylanase activity tests. In the adapted methods, the total reaction volume was reduced from 2.2-24.5 mL to 0.21-0.24 mL. Statistical analysis of the activities measured on enzyme mixtures by applying the 96-well plate reduced methods showed that they were not significantly different to the activities obtained with reference tests.

Recyclable cross-linked laccase aggregates coupled to magnetic silica microbeads for elimination of pharmaceuticals from municipal wastewater.

In the present work, the use of magnetic mesoporous silica microbeads (MMSMB) as supports was proposed to produce magnetically-separable cross-linked enzyme aggregates (MCLEAs). The effects of cross linking time, addition of bovine serum albumin as protein feeder, pH, glutaraldehyde concentration, and laccase:MMSMB mass ratio on the immobilization yield and enzyme load were investigated. The best conditions allowed the rapid preparation of MCLEAs with high enzyme load, i.e., 1.53 U laccase/mg MCLEAs. The stability of MCLEAs was improved with regard to low pH, presence of chemical denaturants, and real wastewater matrix, compared to free laccase. In addition, the novel biocatalyst exhibited good operational stability, maintaining up to 70 % of its initial activity after 10 successive batch reactions. Finally, MCLEAs demonstrated its catalytic potential to transform acetaminophen and various non-phenolic pharmaceutical active compounds as mefenamic acid, fenofibrate, and indomethacin from biologically treated wastewater effluent, with similar or even higher efficiency than free laccase.

Assessing the use of nanoimmobilized laccases to remove micropollutants from wastewater.

Enzymes immobilization is a useful way to allow enzyme reuse and increase their stability. A high redox potential laccase from Trametes versicolor (TvL) and a low redox potential, but commercially available low-cost laccase from Myceliophthora thermophila (MtL), were successfully immobilized and co-immobilized onto fumed silica nanoparticles (fsNP). Enzyme loads of 1.78 ± 0.07, 0.69 ± 0.03, and 1.10 ± 0.01 U/mg fsNP were attained for the optimal doses of TvL, MtL, and co-immobilized laccases, respectively. In general, the laccase-fsNP conjugates showed a higher resistance against an acidic pH value (i.e., pH 3), and a higher storage stability than free enzymes. In addition, immobilized enzymes exhibited a superior long-term stability than free laccases when incubated in a secondary effluent from a municipal wastewater treatment plant (WWTP). For instance, the residual activity after 2 weeks for the co-immobilized laccases and the mixture of free laccases were 40.2 ± 2.5% and 16.8 ± 1.0%, respectively. The ability of the laccase-fsNP to remove a mixture of (14)C-bisphenol A (BPA) and (14)C-sodium diclofenac (DCF) from spiked secondary effluents was assessed in batch experiments. The catalytic efficiency was highly dependent on both the microbial source and state of the biocatalyst. The high redox potential TvL in free form attained a four-fold higher percentage of BPA transformation than the free MtL. Compared to free laccases, immobilized enzymes led to much slower rates of BPA transformation. For instance, after 24 h, the percentages of BPA transformation by 1000 U/L of a mixture of free laccases or co-immobilized enzymes were 67.8 ± 5.2 and 27.0 ± 3.9%, respectively. Nevertheless, the use of 8000 U/L of co-immobilized laccase led to a nearly complete removal of BPA, despite the unfavorable conditions for laccase catalysis (pH ~ 8.4). DCF transformation was not observed for any of the enzymatic systems, showing that this compound is highly recalcitrant toward laccase oxidation under realistic conditions.

Fostering the action of versatile peroxidase as a highly efficient biocatalyst for the removal of endocrine disrupting compounds.

Response surface methodology (RSM) was used to optimize the removal of five endocrine disrupting compounds (EDCs) by the enzyme versatile peroxidase (VP): bisphenol A (BPA), triclosan (TCS), estrone (E1), 17ß-estradiol (E2) and 17α-ethinylestradiol (EE2). The optimal variables of enzyme activity (90-100 U L(-1)), sodium malonate (29-43 mM) and MnSO4 (0.8-1 mM) led to very high removal rates of the five pollutants (2.5-5.0 mg L(-1) min(-1)). The structural elucidation of transformation products arising from the enzymatic catalysis of the EDCs was investigated by Gas Chromatography coupled to Mass Spectrometry (GC-MS) and Liquid Chromatography Electrospray Time-of-Flight Mass Spectrometry (LC-ESI-TOF-MS). The presence of dimers and trimers, indicative of oxidative coupling, was demonstrated.

Enzymatic technologies for remediation of hydrophobic organic pollutants in soil.

Worldwide there are numerous contaminated sites as a result of the widespread production and use of chemicals in industrial and military activities as well as poor schemes of waste disposal and accidental spillages. The implementation of strategies for decontamination and restoration of polluted sites has become a priority, being bioremediation with biological agents a promising alternative. Enzyme-based technologies offer several advantages over the use of microbial cells, provided that the biocatalyst meets specific requirements: efficiency to remove the target pollutant/s, non-dependency on expensive coenzymes or cofactors, enzyme stability, and an affordable production system. In this mini-review, the direct application of enzymes for in situ soil bioremediation is explored, and also novel ex situ enzymatic technologies are presented. This new perspective provides a valuable insight into the different enzymatic alternatives for decontamination of soils. Examples of recent applications are reported, including pilot-scale treatments and patented technologies, and the principles of operation and the main requirements associated are described. Furthermore, the main challenges regarding the applicability of enzymatic technologies for remediation of hydrophobic organic pollutants from soil are discussed.

Potentiality of a ceramic membrane reactor for the laccase-catalyzed removal of bisphenol A from secondary effluents.

In this study, the removal of bisphenol A (BPA) by laccase in a continuous enzymatic membrane reactor (EMR) was investigated. The effects of key parameters, namely, type of laccase, pH, and enzyme activity, were initially evaluated. Once optimal conditions were determined, the continuous removal of the pollutant in an EMR was assessed in synthetic and real biologically treated wastewaters. The reactor configuration consisted of a stirred tank reactor coupled to a ceramic membrane, which prevented the sorption of the pollutant and allowed the recovery and recycling of laccase. Nearly complete removal of BPA was attained under both operation regimes with removal yields above 94.5 %. In experiments with real wastewater, the removal of BPA remained high while the presence of colloids and certain ions and the formation of precipitates on the membrane potentially affected enzyme stability and made necessary the periodic addition of laccase. Polymerization and degradation were observed as probable mechanisms of BPA transformation by laccase.

Continuous removal of nonylphenol by versatile peroxidase in a two-stage membrane bioreactor.

The ligninolytic enzymes versatile peroxidase (VP) and manganese peroxidase (MnP) have been previously described as efficient oxidizers of the endocrine disrupting chemical (EDC) nonylphenol at high concentrations of the pollutant. Envisaging the application of an enzymatic technology as a tertiary treatment in wastewater treatment plants, it is important to design a continuous reactor that performs the efficient removal of nonylphenol under environmental conditions. In the present research, a two-stage membrane bioreactor based on the production and use of Mn(3+)-malonate (chemical oxidant) was applied. The bioreactor consisted of an enzymatic reactor (R1) for the production of Mn(3+)-malonate by VP, coupled to an oxidation reactor (R2), where the oxidation of nonylphenol by Mn(3+)-malonate took place. The production of Mn(3+)-malonate in R1 was maintained constant: 500-700 µM with minimal deactivation of the enzyme. The oxidation reactor attained nearly complete removal of nonylphenol, even at a hydraulic retention time (HRT) shorter than 20 min. The operation with real wastewater containing nonylphenol at environmental concentrations (454 nM) was also successful, with a nonylphenol removal of 99.5% at a rate of 0.73 µM h(-1). Moreover, when the HRT of R2 was sharply reduced to 6.8 and 3.6 min, the removal of nonylphenol was maintained beyond 99%, which proves the feasibility of the system to remove the target compound present in a real effluent, even at very short HRTs.

Life cycle assessment of nutrient removal technologies for the treatment of anaerobic digestion supernatant and its integration in a wastewater treatment plant.

The supernatant resulting from the anaerobic digestion of sludge generated by wastewater treatment plants (WWTP) is an attractive flow for technologies such as partial nitritation-anammox (CANON), nitrite shortcut (NSC) and struvite crystallization processes (SCP). The high concentration of N and P and its low flow rate facilitate the removal of nutrients under more favorable conditions than in the main water line. Despite their operational and economic benefits, the environmental burdens of these technologies also need to be assessed to prove their feasibility under a more holistic perspective. The potential environmental implications of these technologies were assessed using life cycle assessment, first at pilot plant scale, later integrating them in a modeled full WWTP. Pilot plant results reported a much lower environmental impact for N removal technologies than SCP. Full-scale modeling, however, highlighted that the differences between technologies were not relevant once they are integrated in a WWTP. The impacts associated with the WWTP are slightly reduced in all categories except for eutrophication, where a substantial reduction was achieved using NSC, SCP, and especially when CANON and SCP were combined. This study emphasizes the need for assessing wastewater treatment technologies as part of a WWTP rather than as individual processes and the utility of modeling tools for doing so.

Solvent screening methodology for in situ ABE extractive fermentation.

Solvent screening for in situ liquid extraction of products from acetone-butanol-ethanol (ABE) fermentation was carried out, taking into account biological parameters (biocompatibility, bioavailability, and product yield) and extraction performance (partition coefficient and selectivity) determined in real fermentation broth. On the basis of different solvent characteristics obtained from literature, 16 compounds from different chemical families were selected and experimentally evaluated for their extraction capabilities in a real ABE fermentation broth system. From these compounds, nine potential solvents were also tested for their biocompatibility towards Clostridium acetobutylicum. Moreover, bioavailability and differences in substrate consumption and total n-butanol production with respect to solvent-free fermentations were quantified for each biocompatible solvent. Product yield was enhanced in the presence of organic solvents having higher affinity for butanol and butyric acid. Applying this methodology, it was found that the Guerbet alcohol 2-butyl-1-octanol presented the best extracting characteristics (the highest partition coefficient (6.76) and the third highest selectivity (644)), the highest butanol yield (27.4 %), and maintained biocompatibility with C. acetobutylicum.

Activation of Kraft Lignin by an enzymatic treatment with a versatile peroxidase from Bjerkandera sp. R1.

Enzymatic lignin activation may be an environmentally friendly alternative to the use of chemicals in the production of wood fibers composites. Most studies on enzymatic activation of lignin for improving the adhesion of lignocellulosic products have been carried out using laccases. In this work, the use of a versatile peroxidase (VP) from the white-rot fungus Bjerkandera sp. (anamorph R1) for activating Kraft lignin was studied. The effect of enzyme dosage, incubation time, and H(2)O(2) addition profile on lignin activation was evaluated by quantifying the phenoxy radicals formed using electron paramagnetic resonance (EPR) spectroscopy. Two alternative enzymatic systems based on the use of VP (a two-stage and an enzymatic cascade system) were also assayed. At optimal conditions (dose of 15 U g(-1) and continuous addition of H(2)O(2) (5.24 µmol h(-1)) during 1 h) the content of phenoxy radicals was doubled as compared with an untreated control. Moreover, using the two-stage VP system, a lignin activation similar to that found at optimal conditions could be reached in a shorter time.

Continuous operation of a fluidized bed reactor for the removal of estrogens by immobilized laccase on Eupergit supports.

The feasibility of the operation of a fluidized bed reactor for the removal of estrogens by immobilized laccase was investigated in order to improve the degradation yields and enzyme stability previously obtained with packed bed reactors. High removal levels (between 76 and 90%) and significantly prolonged stability of the biocatalyst over 16 days were attained. In parallel, a decrease up to 90% in the estrogenic activity of the effluent was measured. Thus, the technology presented seems a promising tool to increase the applicability of laccases in bioremediation processes.

Degradation of estrogens by laccase from Myceliophthora thermophila in fed-batch and enzymatic membrane reactors.

Several studies reported that natural and synthetic estrogens are the major contributors to the estrogenic activity associated with the effluents of wastewater treatment plants. The ability of the enzyme laccase to degrade these compounds in batch experiments has been demonstrated in previous studies. Nevertheless, information is scarce regarding in vitro degradation of estrogens in continuous enzymatic bioreactors. The present work constitutes an important step forward for the implementation of an enzymatic reactor for the continuous removal of estrone (E1) and estradiol (E2) by free laccase from Myceliophthora thermophila. In a first step, the effect of the main process parameters (pH, enzyme level, gas composition (air or oxygen) and estrogen feeding rate) were evaluated in fed-batch bioreactors. E1 and E2 were oxidized by 94.1 and 95.5%, respectively, under the best conditions evaluated. Thereafter, an enzymatic membrane reactor (EMR) was developed to perform the continuous degradation of the estrogens. The configuration consisted of a stirred tank reactor coupled with an ultrafiltration membrane, which allowed the recovery of enzyme while both estrogens and degradation products could pass through it. The highest removal rates at steady state conditions were up to 95% for E1 and nearly complete degradation for E2. Furthermore, the residual estrogenic activity of the effluent was largely reduced up to 97%.