Efficient degradation of various emerging pollutants by wild type and evolved fungal DyP4 peroxidases

The accumulation of emerging pollutants in the environment remains a major concern as evidenced by the increasing number of reports citing their potential risk on environment and health. Hence, removal strategies of such pollutants remain an active area of investigation. One way through which emerging pollutants can be eliminated from the environment is by enzyme-mediated bioremediation. Enzyme-based degradation can be further enhanced via advanced protein engineering approaches. In the present study a sensitive and robust bioanalytical liquid chromatography-tandem mass spectrometry (LCMSMS)-based approach was used to investigate the ability of a fungal dye decolorizing peroxidase 4 (DyP4) and two of its evolved variants—that were previously shown to be H2O2 tolerant—to degrade a panel of 15 different emerging pollutants. Additionally, the role of a redox mediator was examined in these enzymatic degradation reactions. Our results show that three emerging pollutants (2-mercaptobenzothiazole (MBT), paracetamol, and furosemide) were efficiently degraded by DyP4. Addition of the redox mediator had a synergistic effect as it enabled complete degradation of three more emerging pollutants (methyl paraben, sulfamethoxazole and salicylic acid) and dramatically reduced the time needed for the complete degradation of MBT, paracetamol, and furosemide. Further investigation was carried out using pure MBT to study its degradation by DyP4. Five potential transformation products were generated during the enzymatic degradation of MBT, which were previously reported to be produced during different bioremediation approaches. The current study provides the first instance of the application of fungal DyP4 peroxidases in bioremediation of emerging pollutants.

Nanomechanical Atomic Force Microscopy to Probe Cellular Microplastics Uptake and Distribution

The concerns regarding microplastics and nanoplastics pollution stimulate studies on the uptake and biodistribution of these emerging pollutants in vitro. Atomic force microscopy in nanomechanical PeakForce Tapping mode was used here to visualise the uptake and distribution of polystyrene spherical microplastics in human skin fibroblast. Particles down to 500 nm were imaged in whole fixed cells, the nanomechanical characterization allowed for differentiation between internalized and surface attached plastics. This study opens new avenues in microplastics toxicity research.

Multifunctional Membranes—A Versatile Approach for Emerging Pollutants Removal

This paper presents a comprehensive literature review surveying the most important polymer materials used for electrospinning processes and applied as membranes for the removal of emerging pollutants. Two types of processes integrate these membrane types: separation processes, where electrospun polymers act as a support for thin film composites (TFC), and adsorption as single or coupled processes (photo-catalysis, advanced oxidation, electrochemical), where a functionalization step is essential for the electrospun polymer to improve its properties. Emerging pollutants (EPs) released in the environment can be efficiently removed from water systems using electrospun membranes. The relevant results regarding removal efficiency, adsorption capacity, and the size and porosity of the membranes and fibers used for different EPs are described in detail.

Nanoremediation: Nanomaterials and Nanotechnologies for Environmental Cleanup

Different global events such as industrial development and the population increment have triggered the presence and persistence of several organic and inorganic contaminants, representing a risk for the environment and human health. Consequently, the search and application of novel technologies for alleviating the challenge of environmental pollution are urgent. Nanotechnology is an emerging science that could be employed in different fields. In particular, Nanoremediation is a promising strategy defined as the engineered materials employed to clean up the environment, is an effective, rapid, and efficient technology to deal with persistent compounds such as pesticides, chlorinated solvents, halogenated chemicals, or heavy metals. Furthermore, nanoremediation is a sustainable alternative to eliminate emerging pollutants such as pharmaceutics or personal care products. Due to the variety of nanomaterials and their versatility, they could be employed in water, soil, or air media. This review provides an overview of the application of nanomaterials for media remediation. It analyzes the state of the art of different nanomaterials such as metal, carbon, polymer, and silica employed for water, soil, and air remediation.

Assessing the Fungal Simultaneous Removal Efficiency of Carbamazepine, Diclofenac and Ibuprofen in Aquatic Environment

Unused pharmaceutical compounds (PhCs) discharged into the aquatic environment have been regarded as emerging pollutants due to potential harmful effects on humans and the environment. Microbial bioremediation is considered as a viable option for their removal from wastewater. The aim of this study was to assess the simultaneous removal of carbamazepine (CBZ), diclofenac (DCF) and ibuprofen (IBP) by previously isolated fungi (Aspergillus niger, Mucor circinelloides, Trichoderma longibrachiatum, Trametes polyzona, and Rhizopus microsporus). The tolerance to PhCs was conducted by tracking the fungal mycelium mat diameters in solid media and its dry biomass in liquid media, at the drug concentration range of 0.1 to 15 mg/L. The fungal enzymatic activities were determined for lignin peroxidase (LiP), manganese peroxidase (MnP) and laccase (Lac), respectively. The PhC removal efficiency of the fungi was assessed in aerated batch flasks and the drug concentrations and intermediate compounds formation were determined by using SPE-UPLC/MS. A tolerance over 70% was recorded for all the fungi at drug concentration of 0.1 mg/L. Manganese peroxidase was produced by all the fungi with very low amount of LiP, while all the enzymes were produced by T. polyzona. The pH of 4.3, temperature 37 ± 1.5°C and incubation time of 6 days were the optimum parameters for the fungal enzymatic activities. The best removal of CBZ (87%) was achieved by R. microsporus after 10 days. Between 78 and 100% removal of DCF was observed by all the fungi after 24 h, while 98% of IBP was removed after 2 days by M. circinelloides. Only a few intermediate compounds were identified after 3 days and disappeared after 10 days of incubation. This study demonstrated that apart from the basidiomycetes, the ascomycetes and zygomycetes are also producers of ligninolytic enzymes and have the ability to biodegrade emerging pollutants such as PhCs.

Removal of Emerging Pollutants in Horizontal Subsurface Flow and Vertical Flow Pilot-Scale Constructed Wetlands

We assessed constructed wetland (CW) performance in the removal of six emerging pollutants (EPs) from university campus wastewater. The EPs considered were: diethyl phthalate (DEP), di-isobutyl phthalate (DIBP), di-n-octyl phthalate (DNOP), bis(2-ehtylxexyl) phthalate (DEHP), tris(1-chloro-2-propyl) phosphate (TCPP) and caffeine (CAF). Six pilot-scale CWs, i.e., three horizontal subsurface flow (HSF) and three vertical flow (VF), with different design configurations were used: two types of plants and one unplanted for both the HSF and the VF, two hydraulic retention times (HRT) for the HSF, and two wastewater feeding strategies for the VF units. The results showed that the median removals in the three HSF-CWs ranged between 84.3 and 99.9%, 79.0 and 95.7%, 91.4 and 99.7%, 72.2 and 81.0%, 99.1 and 99.6%, and 99.3 and 99.6% for DEP, DIBP, DNOP, DEHP, TCPP, and CAF, respectively. In the three VF-CWs, the median removal efficiencies range was 98.6–99.4%, 63.6–98.0%, 96.6–97.8%, 73.6–94.5%, 99.3–99.5% and 94.4–96.3% for DEP, DIBP, DNOP, DEHP, TCPP and CAF, respectively. The study indicates that biodegradation and adsorption onto substrate were the most prevalent removal routes of the target EPs in CWs.