Direct Current Atmospheric Pressure Glow Research Articles

Coupled multi-dimensional modelling of warm plasmas: Application and validation for an atmospheric pressure glow discharge in CO2/CH4/O2

To support experimental research into gas conversion by warm plasmas, models should be developed to explain the experimental observations. These models need to describe all physical and chemical plasma properties in a coupled way. In this paper, we present a modelling approach to solve the complete set of assumed relevant equations, including gas flow, heat balance and species transport, coupled with a rather extensive chemistry set, consisting of 21 species, obtained by reduction of a more detailed chemistry set, consisting of 41 species. We apply this model to study the combined CO2 and CH4 conversion in the presence of O2, in a direct current atmospheric pressure glow discharge. Our model can predict the experimental trends, and can explain why higher O2 fractions result in higher CH4 conversion, namely due to the higher gas temperature, rather than just by additional chemical reactions. Indeed, our model predicts that when more O2 is added, the energy required to reach any set temperature (i.e., the enthalpy) drops, allowing the system to reach higher temperatures with similar amounts of energy. This is in turn related to the higher H2O fraction and lower H2 fraction formed in the plasma, as demonstrated by our model. Altogether, our new self-consistent model can capture the main physics and chemistry occurring in this warm plasma, which is an important step towards predictive modelling for plasma-based gas conversion.

Multiparameter optimization of non-thermal plasma-driven synthesis of carbohydrate-stabilized rhenium nanoparticles towards enhancement of their catalytical activity for reduction of nitroaromatic compounds

This study aims to optimize the synthesis of carbohydrate-stabilized rhenium nanoparticles (ReNPs) utilizing cold atmospheric pressure plasma (CAPP), specifically direct current atmospheric pressure glow discharge (dc-APGD), hypothesizing that controlling synthesis parameters will enhance catalytic efficiency in the reduction of nitroaromatic compounds (NACs). The dc-APGD system operated in flowing liquid cathode (FLC-dc-APGD) and flowing liquid anode (FLA-dc-APGD) modes. Design of experiments (DOE) and response surface methodology (RSM) were employed for the first time to optimize ReNPs synthesis by adjustment of the concentration of ReO4- in ReNPs precursor solution, its flow rate, as well as the discharge current. ReNPs were characterized using high-resolution transmission electron microscopy (HRTEM), dynamic light scattering (DLS), and X-Ray photoelectron spectroscopy (XPS). In turn, optical emission spectroscopy (OES) was employed for the identification of reactive species generated in the plasma phase that contributed to the synthesis of ReNPs. The resultant sizes, surface charges, and phase compositions were linked with synthesis parameters and then with catalytic activities revealed by the variety of ReNPs. HRTEM photomicrographs showed spherical and spherical-like morphologies of the obtained ReNPs synthesized using FLC-dc-APGD and FLA-dc-APGD modes with the actual sizes of 7.28 ± 2.90 nm and 3.24 ± 0.57 nm, respectively. The optimized conditions yielded ReNPs of exceptional catalytic activity, that reduced 94.9 % (FLC-dc-APGD) and 90.5 % (FLA-dc-APGD) of 4-nitrophenol (4-NP) with the apparent rate constants (k1) 0.269 and 0.107 min−1, respectively. Further, the conversions of 90 % were achieved over FLC-dc-APGD-based ReNPs for nitrobenzene (NB), 2,4,6-trinitrophenol (2,4,6-TNP), 2,4-dinitrophenol (2,4-DNP), and 4-nitroaniline (4-NA). In these cases, the k1 values were 0.235, 0.174, 0.070, 0.001 min−1, respectively. The results allowed to find a correlation between ReNP size distribution, oxidation state, and catalytic activity that suggested a potential for tailored Re nanocatalysts in environmental remediation.

Microplasma characteristics of direct-current atmospheric pressure glow discharge in dependence of gap distance and discharge current

Microplasma at atmospheric pressure has been widely used in many fields due to the lower power consumption, higher plasma density, as well as better uniformity and stability. In this work, the microplasma characteristics of direct current atmospheric pressure glow discharge, including discharge morphology and electrical properties have been investigated with various interelectrode gaps (10–600 μm) and discharge currents (1–6 mA), and simultaneously, a finite element simulation has been conducted to obtain the distribution of the electric field and particle density. The evolution of cathode layer, anode layer and Faraday dark space at this scale was captured with a higher spatial resolution (∼1 μm) for the first time, demonstrating that the cathode layer, especially the cathode sheath rather than the positive column, plays a dominant role in the transition of the microplasma. As the gap shrinks to a size less than cathode layer (∼40 μm), the cathode sheath with a high electric field is compressed, leading to a rapid decrease of the discharge voltage. The discharge voltage remains basically unchanged regardless of the discharge current, because the electric field in the cathode sheath is limited by the accumulated space charge. The experimental results are well verified and explained by the simulation results. This study provides an in-depth understanding of the glow discharge mechanism at microscale, and of the stability of glow discharge at atmospheric pressure, and benefits to future research on the atmospheric pressure large-area microplasma and its related application.

Analysis of different modeling approaches for simulation of glow discharge in helium at atmospheric pressure

One-dimensional numerical models of a direct current atmospheric pressure glow discharge in helium are developed and examined. The models use a fluid description of charged and neutral particles and a drift-diffusion approximation for particle fluxes. The effects of plasma-chemical models, the form of the electron energy distribution function (Maxwellian vs non-Maxwellian), the energy loss due to gas heating and the width of the gas gap on the discharge characteristics are analyzed. The performance of different modeling approaches is examined by superimposing computed current–voltage characteristic (CVC) curves with each other and with measured and computed CVCs available in the literature.

How does direct current atmospheric pressure glow discharge application influence on physicochemical, nutritional, microbiological, and cytotoxic properties of orange juice?

We proposed an innovative and economic method for rapid production of functionalized orange juice (OJ) with excellent nutritional properties, prolonged shelf life, and safe consumption. To reach this goal, we have employed direct current atmospheric pressure glow discharge, generated in contact with a flowing liquid cathode (FLC-dc-APGD) in a highly-throughput reaction-discharge system. It was found that controlled FLC-dc-APGD-treatment of OJ lead to increase the concentration of selected metals and phenolic compounds.The so-obtained OJ had the same qualitative composition of fragrance as the untreated one, however, its shelf life was prolonged up to 26 days. Furthermore, OJ exposed to FLC-dc-APGD-treatment did not exhibit any cytotoxic properties towards non-malignant human intestinal epithelial cell lines. On the other hand, the induction of cell cytotoxicity was observed in human colorectal adenocarcinoma cells line after FLC-dc-APGD-treated OJ application. We truly believe that produced by us functionalized OJ might be a tempting alternative to classic, non-treated by FLC-dc-APGD OJ.

Direct Ultratrace Detection of Lead in a Single Hair Using Portable Electromagnetic Heating Vaporization-Atmospheric Pressure Glow Discharge-Atomic Emission Spectrometry.

In this paper, the first demonstration of direct ultratrace determination of lead in a single human hair by direct current-atmospheric pressure glow discharge-atomic emission spectrometry (DC-APGD-AES) coupled with electromagnetic heating vaporization (EMV) was described. Only the ultramicro mass of a human hair sample (about 0.15 mg, often a single human hair) was required during the analysis, and fast detection was implemented without tedious pretreatment processes, such as grinding and digestion. A limit of detection (LOD) of 30.8 μg kg-1 (4.8 pg) for Pb was obtained under optimized conditions, which was even equivalent to that of conventional LA-ICP-MS/ETV-ICP-MS/GFAAS. EMV-APGD-AES, meanwhile, can facilitate miniaturization and portability with low power and small size. The accuracy and practicality of the method were verified by the analysis of certified reference materials (CRMs) GBW09101b (human hair) and human hair samples from three volunteers. A simple, efficient, and low-cost method for detecting Pb in human hair has been developed.

Multivariate Optimization of the FLC-dc-APGD-Based Reaction-Discharge System for Continuous Production of a Plasma-Activated Liquid of Defined Physicochemical and Anti-Phytopathogenic Properties

To the present day, no efficient plant protection method against economically important bacterial phytopathogens from the Pectobacteriaceae family has been implemented into agricultural practice. In this view, we have performed a multivariate optimization of the operating parameters of the reaction-discharge system, employing direct current atmospheric pressure glow discharge, generated in contact with a flowing liquid cathode (FLC-dc-APGD), for the production of a plasma-activated liquid (PAL) of defined physicochemical and anti-phytopathogenic properties. As a result, the effect of the operating parameters on the conductivity of PAL acquired under these conditions was assessed. The revealed optimal operating conditions, under which the PAL of the highest conductivity was obtained, were as follows: flow rate of the solution equaled 2.0 mL min−1, the discharge current was 30 mA, and the inorganic salt concentration (ammonium nitrate, NH4NO3) in the solution turned out to be 0.50% (m/w). The developed PAL exhibited bacteriostatic and bactericidal properties toward Dickeya solani IFB0099 and Pectobacterium atrosepticum IFB5103 strains, with minimal inhibitory and minimal bactericidal concentrations equaling 25%. After 24 h exposure to 25% PAL, 100% (1−2 × 106) of D. solani and P. atrosepticum cells lost viability. We attributed the antibacterial properties of PAL to the presence of deeply penetrating, reactive oxygen and nitrogen species (RONS), which were, in this case, OH, O, O3, H2O2, HO2, NH, N2, N2+, NO2−, NO3−, and NH4+. Putatively, the generated low-cost, eco-friendly, easy-to-store, and transport PAL, exhibiting the required antibacterial and physicochemical properties, may find numerous applications in the plant protection sector.

Non-thermal atmospheric pressure plasma as a powerful tool for the synthesis of rhenium-based nanostructures for the catalytic hydrogenation of 4-nitrophenol.

Here we have presented a new method for the synthesis of Re nanostructures with defined optical, structural, and catalytic properties. The Re-based nanoparticles (NPs) were obtained using a reaction-discharge system that is unique in its class, because of its working in the high-throughput mode. Within this application, direct current atmospheric pressure glow discharge (dc-APGD) was used as a non-thermal atmospheric pressure plasma (NTAP) source, which led to the reduction of Re(vii) ions and the formation of Re nanostructures through the plasma–liquid interactions. The Re-based NPs were synthesized in a flow-mode reaction-discharge system, where their precursor solution was a flowing liquid anode (FLA) or a flowing liquid cathode (FLC). The resultant NPs were analyzed using UV/Vis absorption spectrophotometry and transmission electron microscopy (TEM), which were supported by selected area X-ray diffraction (SAED) and the energy dispersive X-ray spectroscopy (EDX). Additionally, the mechanism for the reduction of Re(vii) ions was explained by the differences in the concentrations of the selected reactive nitrogen species (RNS) and reactive oxygen species (ROS) produced by dc-APGD. It was found that the application of dc-APGD, operating in a FLA configuration (FLA-dc-APGD), resulted in the formation of ReNPs with Re0, while the use of dc-APGD operating in a FLC configuration (FLC-dc-APGD) led to the formation of Re oxide NPs. In the latter case, a much greater oxidizing environment was likely provided, therefore the RNS and ROS contributed to the formation of Re oxide nanostructures. The ReNPs with Re0 were characterized by a size of 6.02 ± 3.01 nm, and the Re oxide NPs were characterized by a size of 4.97 ± 3.82 nm. Both types of nanostructures were then employed in the catalytic hydrogenation of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). Based on the results, both of the nanocatalysts effectively reduced 4-NP with an apparent rate constant (kapp) of 2.6 × 10−3 s−1. At the same time, the catalytic activity was linked with the average size distribution of the Re nanostructures, as opposed to their morphology.

Dual-Mode Solution Plasma Processing for the Production of Chitosan/Ag Composites with the Antibacterial Effect.

The development of novel biocompatible and biodegradable materials for medical applications has been drawing significant interest in the scientific community for years. Particularly, chitosan loaded with silver nanoparticles (Ag NPs) has a strong antimicrobial potential and could be applied, for example, as wound dressing material. In this work, chitosan/Ag NP composites were produced utilizing a single-step plasma-solution process, which is simple and environmentally friendly. An acetic solution of chitosan containing AgNO3 was treated by the direct current (DC) atmospheric pressure glow discharge, with the liquid serving as either cathode or anode. The plasma-solution system with liquid anode is more useful for the production of Ag NPs. Nevertheless, the NP size is comparable for both cases. The plasma treatment with both polarities led to chitosan degradation. The cleavage of glucosidic chains mostly occurred in the system with the liquid cathode, whereas the side oxidation reactions took place when the solution served as the anode. The oxidation processes were possibly induced by the hydrogen peroxide H2O2 efficiently formed in the last case. The composite materials produced with both polarities of liquid electrode demonstrated the bactericidal action against Gram-negative Escherichia coli, Gram-positive Staphylococcus aureus, and Gram-positive Bacillus subtilis.

Plant Extracts Activated by Cold Atmospheric Pressure Plasmas as Suitable Tools for Synthesis of Gold Nanostructures with Catalytic Uses.

Because cold atmospheric pressure plasma (CAPP)-based technologies are very useful tools in nanomaterials synthesis, in this work we have connected two unique in their classes approaches—a CAPP-based protocol and a green synthesis method in order to obtain stable-in-time gold nanoparticles (AuNPs). To do so, we have used an aqueous Gingko biloba leave extract and an aqueous Panax ginseng root extract (untreated or treated by CAPP) to produce AuNPs, suitable for catalytical uses. Firstly, we have adjusted the optical properties of resulted AuNPs, applying UV/Vis absorption spectrophotometry (UV/Vis). To reveal the morphology of Au nanostructures, transmission electron microscopy (TEM) in addition to energy dispersive X-ray scattering (EDX) and selected area X-ray diffraction (SAED) was utilized. Moreover, optical emission spectrometry (OES) in addition to a colorimetric method was used to identify and determine the concentration of selected RONS occurring at the liquid-CAPP interface. Additionally, attenuated total reflectance Fourier transform-infrared spectroscopy (ATR FT-IR) was applied to reveal the active compounds, which might be responsible for the AuNPs surface functionalization and stabilization. Within the performed research it was found that the smallest in size AuNPs were synthesized using the aqueous P. ginseng root extract, which was activated by direct current atmospheric pressure glow discharge (dc-APGD), generated in contact with a flowing liquid cathode (FLC). On the contrary, taking into account the aqueous G. biloba leave extract, the smallest in size AuNPs were synthesized when the untreated by CAPP aqueous G. biloba leave extract was involved in the Au nanostructures synthesis. For catalytical studies we have chosen AuNPs produced using the aqueous P. ginseng root extract activated by FLC-dc-APGD as well as AuNPs synthesized using the aqueous G. biloba leave extract also activated by FLC-dc-APGD. Those NPs were successfully used as homogenous catalysts for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP).

Hydrogel-based nanocomposite catalyst containing uncoated gold nanoparticles synthesized using cold atmospheric pressure plasma for the catalytic decomposition of 4-nitrophenol

We demonstrate the synthetic route for obtaining hydrogel-based nanocomposite (h-NC), suitable for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). The synthesized h-NC catalyst consisted of the uncoated Au nanostructures, produced via direct current atmospheric pressure glow discharge (dc-APGD) and immobilized into the water phase consisting of [2-(Acryloyloxy)ethyl]trimethylammonium chloride (AOETAC) further cross-linked using N,N-methylenebis(acrylamide) (MBA). Next, the so-produced h-NC was characterized to reveal the structural properties of the raw-AuNPs as well as to survey the chemical structure of h-NC. To reach this aim, several experimental techniques were used, including dynamic light scattering (DLS), transmission electron microscopy (TEM) supported by energy dispersive X-ray scattering (EDX) and selected area electron diffraction (SAED), as well as attenuated total reflectance Fourier-transform infrared spectroscopy (ATR FT-IR) for the material characterization. Finally, it was found that the h-NC facilitated the complete reduction of 4-NP to 4-AP.

Production of antimicrobial silver nanoparticles modified by alkanethiol self‐assembled monolayers by direct current atmospheric pressure glow discharge generated in contact with a flowing liquid anode

AbstractDirect current atmospheric pressure glow discharge (dc‐APGD) generated in contact with a flowing liquid anode (FLA) is used for continuous synthesis of size‐defined silver nanoparticles (AgNPs) modified by a (11‐mercaptoundecyl)‐N,N,N‐trimethylammonium chloride (TMA) alkanethiol self‐assembled monolayer. The impact of the operating parameters (concentration of Ag(I) ions, solution flow rate, discharge current) on the size of TMA‐AgNPs is examined. Design of experiments along with response surface methodology reveals that it is possible to obtain size‐defined TMA‐AgNPs, the smallest being 1.21 ± 0.80 nm. Furthermore, the reactive species involved in formation of TMA‐AgNPs are identified using optical emission spectrometry. TMA‐AgNPs are characterized by several other experimental techniques, which confirm production of approximately spherical, well‐dispersed TMA‐AgNPs. Additionally, attenuated total reflection Fourier transform infrared spectroscopy and UV/Vis absorption spectrophotometry confirmed that the surface of Ag nanostructures is covered by TMA. TMA‐AgNPs display antimicrobial activity toward multiple human pathogens (Escherichia coli, Staphylococcus aureus, and Candida albicans) with minimal bactericidal concentrations or minimal fungicidal concentrations of 3.90 ± 0.15, 7.79 ± 0.30, and 3.90 ± 0.15 mg/L, respectively.

Direct current atmospheric pressure glow discharge generated in contact with a flowing liquid cathode as a method for rapid eradication of phytopathogenic bacteria

The miniaturized atmospheric pressure glow discharge (APGD) sustained between a liquid flowing cathode and a He nozzle jet anode was combined with hydride generation (HG) to improve the performance of the determination of As, Sb and Se with optical emission spectrometry (OES). As(III), Sb(III) and Se(IV) species were converted into volatile hydrides in the reaction with NaBH4 and right after that they were delivered to the near-anode region of APGD through the nozzle. The transport efficiency of As, Sb and Se to the discharge was several times higher, while intensities of atomic emission lines of As, Sb and Se were improved 3 orders of magnitude (as compared to intensities acquired for the near-cathode region in a APGD system with a typical introduction of analytes through sputtering of the flowing liquid cathode). The effect of the concentration of NaBH4 and HCl in a sample solution, the discharge current, the flow rate of He carrier/jet-supporting and He shielding gases on the emission yield coming from As, Sb, Se, He and H atomic lines and OH and N2 band heads as well as the electron number density was thoroughly studied. Under compromised conditions, limits of detection (3σ criterion) of As, Sb and Se were respectively 4.2, 1.2 and 3.1 µg L−1. Usefulness of the method was confirmed by the analysis of Sniadecki and Marchlewski highly mineralized spring waters (Kudowa Zdroj, Poland) on the content of As, Sb and Se. Recoveries of elements added to these spring waters were within 90.3–103.7% proving good accuracy of the HG–APGD–OES method.

Antibacterial Activity of Fructose-Stabilized Silver Nanoparticles Produced by Direct Current Atmospheric Pressure Glow Discharge towards Quarantine Pests.

Development of efficient plant protection methods against bacterial phytopathogens subjected to compulsory control procedures under international legislation is of the highest concern having in mind expensiveness of enforced quarantine measures and threat of the infection spread in disease-free regions. In this study, fructose-stabilized silver nanoparticles (FRU-AgNPs) were produced using direct current atmospheric pressure glow discharge (dc-APGD) generated between the surface of a flowing liquid anode (FLA) solution and a pin-type tungsten cathode in a continuous flow reaction-discharge system. Resultant spherical and stable in time FRU-AgNPs exhibited average sizes of 14.9 ± 7.9 nm and 15.7 ± 2.0 nm, as assessed by transmission electron microscopy (TEM) and dynamic light scattering (DLS), respectively. Energy dispersive X-ray spectroscopy (EDX) analysis revealed that the obtained nanomaterial was composed of Ag while selected area electron diffraction (SAED) indicated that FRU-AgNPs had the face-centered cubic crystalline structure. The fabricated FRU-AgNPs show antibacterial properties against Erwinia amylovora, Clavibacter michiganensis, Ralstonia solanacearum, Xanthomonas campestris pv. campestris and Dickeya solani strains with minimal inhibitory concentrations (MICs) of 1.64 to 13.1 mg L−1 and minimal bactericidal concentrations (MBCs) from 3.29 to 26.3 mg L−1. Application of FRU-AgNPs might increase the repertoire of available control procedures against most devastating phytopathogens and as a result successfully limit their agricultural impact.

Atmospheric Pressure Plasma-Mediated Synthesis of Platinum Nanoparticles Stabilized by Poly(vinylpyrrolidone) with Application in Heat Management Systems for Internal Combustion Chambers.

Poly(vinylpyrrolidone)-stabilized Pt nanoparticles (PVP-PtNPs) were produced in a continuous-flow reaction-discharge system by application of direct current atmospheric pressure glow discharge (dc-APGD) operated between the surface of a flowing liquid anode (FLA) and a pin-type tungsten cathode. Synthesized PVP-PtNPs exhibited absorption across the entire UV/Vis region. The morphology and elemental composition of PVP-PtNPs were determined with transmission electron microscopy (TEM) and energy dispersive X-ray scattering (EDX), respectively. As assessed by TEM, PVP-PtNPs were approximately spherical in shape, with an average size of 2.9 ± 0.6 nm. EDX proved the presence of Pt, C, and O. Dynamic light scattering (DLS) and attenuated total reflectance Fourier transform-infrared spectroscopy (ATR FT-IR) confirmed PtNPs functionalization with PVP. As determined by DLS, the average size of PtNPs stabilized by PVP was 111.4 ± 22.6 nm. A fluid containing resultant PVP-PtNPs was used as a heat conductive layer for a spiral radiator managing heat generated by a simulated internal combustion chamber. As compared to water, the use of PVP-PtNPs enhanced efficiency of the system, increasing the rate of heat transfer by 80% and 30% during heating and cooling, respectively.

Polymerization-Driven Immobilization of dc-APGD Synthesized Gold Nanoparticles into a Quaternary Ammonium-Based Hydrogel Resulting in a Polymeric Nanocomposite with Heat-Transfer Applications.

A new method for the production of nanocomposites, composed of gold nanoparticles (AuNPs) and (vinylbenzyl)trimethylammonium chloride-co-N,N-methylene bisacrylamide (VBTAC-co-MBA) hydrogel, is described. Raw-AuNPs of defined optical and granulometric properties were synthesized using direct current atmospheric pressure glow discharge (dc-APGD) generated in contact with a solution of HAuCl4. Different approaches to the polymerization-driven synthesis of Au/VBTAC-co-MBA nanocomposites were tested. It was established that homogenous dispersion of AuNPs in this new nanomaterial with was achieved in the presence of NaOH in the reaction mixture. The new nanocomposite was found to have excellent heat-transfer properties.

Rapid eradication of bacterial phytopathogens by atmospheric pressure glow discharge generated in contact with a flowing liquid cathode.

Diseases caused by phytopathogenic bacteria are responsible for significant economic losses, and these bacteria spread through diverse pathways including waterways and industrial wastes. It is therefore of high interest to develop potent methods for their eradication. Here, antibacterial properties of direct current atmospheric pressure glow discharge (dc-APGD) generated in contact with flowing bacterial suspensions were examined against five species of phytopathogens. Complete eradication of Clavibacter michiganensis subsp. sepedonicus, Dickeya solani, and Xanthomonas campestris pv. campestris from suspensions of OD600 ≈ 0.1 was observed, while there was at least 3.43 logarithmic reduction in population densities of Pectobacterium atrosepticum and Pectobacterium carotovorum subsp. carotovorum. Analysis of plasma-chemical parameters of the dc-APGD system revealed its high rotational temperatures of 2,300 ± 100 K and 4,200 ± 200 K, as measured from N2 and OH molecular bands, respectively, electron temperature of 6,050 ± 400 K, vibrational temperature of 4000 ± 300 K, and high electron number density of 1.1 × 1015 cm-1 . In addition, plasma treatment led to formation of numerous reactive species and states in the treated liquid, including reactive nitrogen and oxygen species such as NOx , NH, H2 O2 , O2 , O, and OH. Further examination revealed that bactericidal activity of dc-APGD was primarily due to presence of these reactive species as well as to UVA, UVB, and UVC irradiation generated by the dc-APGD source. Plasma treatment also resulted in an increase in temperature (from 24.2 to 40.2 °C) and pH (from 6.0 to 10.8) of bacterial suspensions, although these changes had minor effects on cell viability. All results suggest that the newly developed dc-APGD-based system can be successfully implemented as a simple, rapid, efficient, and cost-effective disinfection method for liquids originating from different industrial and agricultural settings.

Application of Silver Nanostructures Synthesized by Cold Atmospheric Pressure Plasma for Inactivation of Bacterial Phytopathogens from the Genera Dickeya and Pectobacterium.

Pectinolytic bacteria are responsible for significant economic losses by causing diseases on numerous plants. New methods are required to control and limit their spread. One possibility is the application of silver nanoparticles (AgNPs) that exhibit well-established antibacterial properties. Here, we synthesized AgNPs, stabilized by pectins (PEC) or sodium dodecyl sulphate (SDS), using a direct current atmospheric pressure glow discharge (dc-APGD) generated in an open-to-air and continuous-flow reaction-discharge system. Characterization of the PEC-AgNPs and SDS-AgNPs with UV/Vis absorption spectroscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, and selected area electron diffraction revealed the production of spherical, well dispersed, and face cubic centered crystalline AgNPs, with average sizes of 9.33 ± 3.37 nm and 28.3 ± 11.7 nm, respectively. Attenuated total reflection-Fourier transformation infrared spectroscopy supported the functionalization of the nanostructures by PEC and SDS. Antibacterial activity of the AgNPs was tested against Dickeya spp. and Pectobacterium spp. strains. Both PEC-AgNPs and SDS-AgNPs displayed bactericidal activity against all of the tested isolates, with minimum inhibitory concentrations of 5.5 mg∙L−1 and 0.75–3 mg∙L−1, respectively. The collected results suggest that the dc-APGD reaction-discharge system can be applied for the production of defined AgNPs with strong antibacterial properties, which may be further applied in plant disease management.

Determination of nitrite in water samples using atmospheric pressure glow discharge microplasma emission and chemical vapor generation of NO species

In this work, a low-power (<25 W), portable direct current (dc) atmospheric pressure glow discharge microplasma (4 mm × 10 mm) molecular emission spectrometer (APGD-MES) is developed for the determination of nitrite by using chemical vapor generation. Nitrite is on-line reduced to volatile nitric oxide (NO) by 1.5% (m/v) ascorbic acid and 1.0 mol L−1 hydrochloric acid. Then, the generated NO was separated and transferred into the APGD microplasma by an argon stream (100 mL min−1) for its excitation, and NO emission was measured by a microspectrometer. The effects of operational parameters of the APGD microplasma source and vapor generation of nitrite were investigated and the analytical figures of merit for nitrite detection was evaluated. The limit of detection of the proposed method was calculated to be 0.26 μg mL−1 of nitrite by measuring NO emission at 237.0 nm. The calibration curve is linear for the nitrite concentration in the range of 2.0–100.0 μg mL−1 and good precision (2.3%, RSD) is readily achieved for 5.0 μg mL−1 nitrite. The accuracy of this procedure was demonstrated by nitrite detection in a certified reference material. Analyte recoveries test were also performed to verify the accuracy of the method for nitrite determination in a series of environmental water samples. It was found that the concentration of nitrite of these samples were all below the LOD, and the obtained recoveries were in the range of 95–117%. The proposed APGD–MES method provides an alternative useful technique for screening potential nitrite pollution of potable waters.

Sensitive Determination of Cd in Small-Volume Samples by Miniaturized Liquid Drop Anode Atmospheric Pressure Glow Discharge Optical Emission Spectrometry.

A novel liquid drop anode (LDA) direct current atmospheric pressure glow discharge (dc-APGD) system was applied for direct determination of Cd in liquid microsamples (50 μL) by optical emission spectrometry (OES). The microdischarge was generated in open-to-air atmosphere between a solid pin type tungsten cathode and a liquid drop placed on a graphite disk anode. The arrangement of the graphite disk placed on a PTFE chip platform as well as the solid pin type cathode was simple and robust. The limit of detection (LOD) of Cd for the developed LDA-APGD-OES method was 0.20-0.40 μg L-1, while precision (as the relative standard deviation for the repeated measurements) was within 2-5%. By using the liquid drop of 50 μL, the linearity range of 1-1000 μg L-1 was achieved. The effect of addition of the low-molecular weight (LMW) organic compounds, easily ionized elements (EIEs), i.e., Ca, K, Mg, and Na, as well as the foreign ions (Al, Cu, Fe, Mn, Zn) to the solution on the in situ atomization and excitation processes occurred during operation of the LDA-APGD system, and the response of Cd was studied. Validation of the proposed method was demonstrated by analysis of Lobster hepatopancreas (TORT-2), pig kidney (ERM-BB186), and groundwater (ERM-CA615) certified reference materials (CRMs) and recoveries of Cd from water samples spiked with 25 μg L-1 of Cd. Very good agreement between the found and certified values of Cd in the CRMs (the recoveries were within the range of 96.3-99.6%) indicated trueness of the method and its reliability for determination of traces of Cd. In the case of the spiked water samples, the recoveries obtained were in the range from 95.2 to 99.5%.