Possible Synergies of Nanomaterial-Assisted Tissue Regeneration in Plasma Medicine: Mechanisms and Safety Concerns.

Cold atmospheric plasma and nanomedicine originally emerged as individual domains, but are increasingly applied in combination with each other. Most research is performed in the context of cancer treatment, with only little focus yet on the possible synergies. Many questions remain on the potential of this promising hybrid technology, particularly regarding regenerative medicine and tissue engineering. In this perspective article, we therefore start from the fundamental mechanisms in the individual technologies, in order to envision possible synergies for wound healing and tissue recovery, as well as research strategies to discover and optimize them. Among these strategies, we demonstrate how cold plasmas and nanomaterials can enhance each other's strengths and overcome each other's limitations. The parallels with cancer research, biotechnology and plasma surface modification further serve as inspiration for the envisioned synergies in tissue regeneration. The discovery and optimization of synergies may also be realized based on a profound understanding of the underlying redox- and field-related biological processes. Finally, we emphasize the toxicity concerns in plasma and nanomedicine, which may be partly remediated by their combination, but also partly amplified. A widespread use of standardized protocols and materials is therefore strongly recommended, to ensure both a fast and safe clinical implementation.

Applications of Plasma-Liquid Systems: A Review.

Plasma-liquid systems have attracted increasing attention in recent years, owing to their high potential in material processing and nanoscience, environmental remediation, sterilization, biomedicine, and food applications. Due to the multidisciplinary character of this scientific field and due to its broad range of established and promising applications, an updated overview is required, addressing the various applications of plasma-liquid systems till now. In the present review, after a brief historical introduction on this important research field, the authors aimed to bring together a wide range of applications of plasma-liquid systems, including nanomaterial processing, water analytical chemistry, water purification, plasma sterilization, plasma medicine, food preservation and agricultural processing, power transformers for high voltage switching, and polymer solution treatment. Although the general understanding of plasma-liquid interactions and their applications has grown significantly in recent decades, it is aimed here to give an updated overview on the possible applications of plasma-liquid systems. This review can be used as a guide for researchers from different fields to gain insight in the history and state-of-the-art of plasma-liquid interactions and to obtain an overview on the acquired knowledge in this field up to now.

Removal of alachlor in water by non-thermal plasma: Reactive species and pathways in batch and continuous process.

Pesticides are emerging contaminants frequently detected in the aquatic environment. In this work, a novel approach combining activated carbon adsorption, oxygen plasma treatment and ozonation was studied for the removal of the persistent chlorinated pesticide alachlor. A comparison was made between the removal efficiency and energy consumption for two different reactor operation modes: batch-recirculation and single-pass mode. The kinetics study revealed that the insufficient removal of alachlor by adsorption was significantly improved in terms of degradation efficiency and energy consumption when combined with the plasma treatment. The best efficiency (ca. 80% removal with an energy cost of 19.4 kWh m-³) was found for the single-pass operational mode of the reactor. In the batch-recirculating process, a complete elimination of alachlor by plasma treatment was observed after 30 min of treatment. Analysis of the reactive species induced by plasma in aqueous solutions showed that the decomposition of alachlor mainly occurred through a radical oxidation mechanism, with a minor contribution of long-living oxidants (O3, H2O2). Investigation of the alachlor oxidation pathways revealed six different oxidation mechanisms, including the loss of aromaticity which was never before reported for plasma-assisted degradation of aromatic pesticides. It was revealed that the removal rate and energy cost could be further improved with more than 50% by additional O3 gas bubbling in the solution reservoir.

Removal of micropollutants from water in a continuous-flow electrical discharge reactor.

The emergence of micropollutants into our aquatic resources is regarded as an issue of increasing environmental concern. To protect the aquatic environment against further contamination with micropollutants, treatment with advanced oxidation processes (AOPs) is put forward as a promising technique. In this work, an innovative AOP based on electrical discharges in a continuous-flow pulsed dielectric barrier discharge (DBD) reactor with falling water film over activated carbon textile is examined for its potential application in water treatment. The effect of various operational parameters including feed gas type, gas flow rate, water flow rate and power on removal and energy efficiency has been studied. To this end, a synthetic micropollutant mixture containing five pesticides (atrazine, alachlor, diuron, dichlorvos and pentachlorophenol), two pharmaceuticals (carbamazepine and 1,7-α-ethinylestradiol), and 1 plasticizer (bisphenol A) is used. While working under optimal conditions, energy consumption was situated in the range 2.42-4.25 kW h/m³, which is about two times lower than the economically viable energy cost of AOPs (5 kW h/m³). Hence, the application of non-thermal plasma could be regarded as a promising alternative AOP for (industrial) wastewater remediation.

Study of an AC dielectric barrier single micro-discharge filament over a water film.

In the last decades, AC powered atmospheric dielectric barrier discharges (DBDs) in air with a liquid electrode have been proposed as a promising plasma technology with versatile applicability in medicine, agriculture and water treatment. The fundamental features of the micro-discharge filaments that make up this type of plasma have, however, not been studied yet in sufficient detail. In order to address this need, we investigated a single DBD micro-discharge filament over a water film in a sphere-to-sphere electrode configuration, by means of ICCD imaging and optical emission spectroscopy. When the water film temporarily acts as the cathode, the plasma duration is remarkably long and shows a clear similarity with a resistive barrier discharge, which we attribute to the resistive nature of the water film and the formation of a cathode fall. As another striking difference to DBD with solid electrodes, a constant glow-like plasma is observed at the water surface during the entire duration of the applied voltage cycle, indicating continuous plasma treatment of the liquid. We propose several elementary mechanisms that might underlie the observed unique behavior, based on the specific features of a water electrode.

Removal of alachlor, diuron and isoproturon in water in a falling film dielectric barrier discharge (DBD) reactor combined with adsorption on activated carbon textile: Reaction mechanisms and oxidation by-products.

A falling film dielectric barrier discharge (DBD) plasma reactor combined with adsorption on activated carbon textile material was optimized to minimize the formation of hazardous oxidation by-products from the treatment of persistent pesticides (alachlor, diuron and isoproturon) in water. The formation of by-products and the reaction mechanism was investigated by HPLC-TOF-MS. The maximum concentration of each by-product was at least two orders of magnitude below the initial pesticide concentration, during the first 10 min of treatment. After 30 min of treatment, the individual by-product concentrations had decreased to values of at least three orders of magnitude below the initial pesticide concentration. The proposed oxidation pathways revealed five main oxidation steps: dechlorination, dealkylation, hydroxylation, addition of a double-bonded oxygen and nitrification. The latter is one of the main oxidation mechanisms of diuron and isoproturon for air plasma treatment. To our knowledge, this is the first time that the formation of nitrificated intermediates is reported for the plasma treatment of non-phenolic compounds.

Removal of several pesticides in a falling water film DBD reactor with activated carbon textile: Energy efficiency.

Bio-recalcitrant micropollutants are often insufficiently removed by modern wastewater treatment plants to meet the future demands worldwide. Therefore, several advanced oxidation techniques, including cold plasma technology, are being investigated as effective complementary water treatment methods. In order to permit industrial implementation, energy demand of these techniques needs to be minimized. To this end, we have developed an electrical discharge reactor where water treatment by dielectric barrier discharge (DBD) is combined with adsorption on activated carbon textile and additional ozonation. The reactor consists of a DBD plasma chamber, including the adsorptive textile, and an ozonation chamber, where the DBD generated plasma gas is bubbled. In the present paper, this reactor is further characterized and optimized in terms of its energy efficiency for removal of the five pesticides α-HCH, pentachlorobenzene, alachlor, diuron and isoproturon, with initial concentrations ranging between 22 and 430 µg/L. Energy efficiency of the reactor is found to increase significantly when initial micropollutant concentration is decreased, when duty cycle is decreased and when oxygen is used as feed gas as compared to air and argon. Overall reactor performance is improved as well by making it work in single-pass operation, where water is flowing through the system only once. The results are explained with insights found in literature and practical implications are discussed. For the used operational conditions and settings, α-HCH is the most persistent pesticide in the reactor, with a minimal achieved electrical energy per order of 8 kWh/m3, while a most efficient removal of 3 kWh/m3 or lower was reached for the four other pesticides.

Removal of atrazine in water by combination of activated carbon and dielectric barrier discharge.

Efficiency of modern wastewater treatment plants to remove or decompose persistent contaminants in low concentration is often insufficient to meet the demands imposed by governmental laws. Novel, efficient and cheap methods are required to address this global issue. We developed a new type of plasma reactor, in which atrazine decomposition by atmospheric dielectric barrier discharge (DBD) in dry air is combined with micropollutant adsorption on activated carbon textile and with extra bubbling of generated ozone. Investigation of reaction kinetics and by-product analysis shows that increasing input power with a factor 3.5 leads to deeper atrazine oxidation without significantly changing energy yield of atrazine removal. By-products of first and later generations are detected with HPLC-MS analysis in water and adsorbed on the activated carbon textile. Our reactor is compared in energy efficiency with reactors described in literature, showing that combination of plasma discharge with pollutant adsorption and ozone recycling is attractive for future applications of water treatment.

Decomposition of atrazine traces in water by combination of non-thermal electrical discharge and adsorption on nanofiber membrane.

In recent decades, several types of persistent substances are detected in the aquatic environment at very low concentrations. Unfortunately, conventional water treatment processes are not able to remove these micropollutants. As such, advanced treatment methods are required to meet both current and anticipated maximally allowed concentrations. Plasma discharge in contact with water is a promising new technology, since it produces a wide spectrum of oxidizing species. In this study, a new type of reactor is tested, in which decomposition by atmospheric pulsed direct barrier discharge (pDBD) plasma is combined with micropollutant adsorption on a nanofiber polyamide membrane. Atrazine is chosen as model micropollutant with an initial concentration of 30 µg/L. While the H2O2 and O3 production in the reactor is not influenced by the presence of the membrane, there is a significant increase in atrazine decomposition when the membrane is added. With membrane, 85% atrazine removal can be obtained in comparison to only 61% removal without membrane, at the same experimental parameters. The by-products of atrazine decomposition identified by HPLC-MS are deethylatrazine and ammelide. Formation of these by-products is more pronounced when the membrane is added. These results indicate the synergetic effect of plasma discharge and pollutant adsorption, which is attractive for future applications of water treatment.