This paper comprises two main parts: a review of the literature on atmospheric-pressure discharges used for micro-organism inactivation, focused on the inactivation mechanisms, and a presentation of our research results showing, in particular, that UV photons can be the dominant species in the inactivation process.The possibility of achieving spore inactivation through UV radiation using an atmospheric-pressure discharge or its flowing afterglow is the object of a continuing controversy. In fact, the review of the literature that we present shows that a majority of researchers have come to the conclusion that, at atmospheric pressure, chemically reactive species such as free radicals, metastable atoms and molecules always control the inactivation process, while UV photons play only a minor role or no role at all. In contrast, only a few articles suggest or claim that UV photons coming from atmospheric-pressure discharges can, in some cases, inactivate micro-organisms, but the experimental data presented and the supporting arguments brought forward in that respect are relatively incomplete.Using a dielectric-barrier discharge operated at atmospheric pressure in an N2–N2O mixture, we present, for the first time, experiments where micro-organisms are subjected to plasma conditions such that, on the one hand, UV radiation is strong or, on the other hand, there is no UV radiation, the two different situations being obtained with the same experimental arrangement, including the same gas mixture, N2–N2O. To achieve maximum UV radiation, the concentration of the oxidant molecule (N2O) added to N2 needs to be tuned carefully, resulting then in the fastest inactivation rate. The concentration range of the oxidant molecule in the mixture for which the UV intensity is significant is extremely narrow, a fact that possibly explains why such a mode of plasma sterilization was not readily observed. The survival curves obtained under dominant UV radiation conditions are, as we show, akin to those recorded at reduced pressure. Relatively fast spore inactivation can also be obtained under no UV radiation as a result of radicals diffusing deeply inside the spores, leading to oxidative lethal damage.

The flowing afterglow of an N2–O2 discharge in the 0.6–10 Torr range is examined in the perspective of achieving sterilization of medical devices (MDs) under conditions ensuring maximum UV intensity with minimum damage to polymer-based MDs. The early afterglow is shown to be responsible for creating strong erosion damage, requiring that the sterilizer be operated in a dominant late-afterglow mode. These two types of afterglow can be characterized by optical emission spectroscopy: the early afterglow is distinguished by an intense emission from the 1st negative system (band head at 391.4 nm) while the late afterglow yields an overpopulation of the v′ = 11 ro–vibrational level of the N2(B) state, indicating a reduced contribution from the early afterglow N2 metastable species. We have studied the influence of operating conditions (pressure, O2 content in the N2–O2 mixture, distance of the discharge from the entrance to the afterglow (sterilizer) chamber) in order to achieve a dominant late afterglow that also ensures maximum and almost uniform UV intensity in the sterilization chamber. As far as operating conditions are concerned, moving the plasma source sufficiently far from the chamber entrance is shown to be a practical means for significantly reducing the density of the characteristic species of the early afterglow.Using the NO titration method, we obtain the (absolute) densities of N and O atoms in the afterglow at the NO injection inlet, a few cm before the chamber entrance: the N atom density goes through a maximum at approximately 0.3–0.5% O2 and then decreases, while the O atom density increases regularly with the O2 percentage. The spatial variation of the N atom (relative) density in the chamber is obtained by recording the emission intensity from the 1st positive system at 580 nm: in the 2–5 Torr range, this density is quite uniform everywhere in the chamber. The (relative) densities of N and O atoms in the discharge are determined by using the actinometry method: the density of N atoms decreases from its maximum value at 0% O2 as the percentage of O2 is increased while the density of O atoms increases, almost linearly, as a function of the percentage of O2, as in the afterglow. The intensity variation of the NOβ UV emission as a function of the percentage of O2 is characterized by a maximum around 0.6% O2 (2 Torr) followed by an approximately exponential decay. We observe that, in the 0–1% O2 range, the UV emission is limited by the availability of O atoms. Beyond this point, the decrease of the UV intensity follows the decrease in the N atom density, while on the average, the O atom density keeps on increasing with O2%. Erosion of polymer microspheres is found to be strongest at the chamber axis when no O2 is present, implying a dominant early afterglow. Adding even only 1% O2 causes a strong quenching of the N2 metastable species, leading to a dominant late afterglow and therefore considerably reducing the etching rate at the axis. In contrast, at 5 cm from the axis under the same operating conditi...

As a rule, medical devices (MDs) made entirely from metals and ceramics can withstand, for sterilization purposes, elevated temperatures such as those encountered in autoclaves (moist heat ⩾120 °C) or Poupinel (Pasteur) ovens (dry heat ⩾160 °C). This not the case with MDs containing polymers: 70 °C seems to be a limit beyond which their structural and functional integrity will be compromised. Nonetheless, all the so-called low-temperature sterilization techniques, relying essentially on some biocidal chemistry (e.g. ethylene oxide, H2O2, O3), are operated at temperatures close to 65 °C, essentially to enhance the chemical reactivity of the biocidal agent. Based on this fact, we have examined the influence of increasing the temperature of the polystyrene Petri dish containing B. atrophaeus bacterial spores when exposing them to UV radiation coming from an N2–O2 flowing plasma afterglow. We have observed that, for a given UV radiation intensity, the inactivation rate increases with the temperature of the Petri dish, provided heat and UV photons are applied simultaneously, a clear case of synergistic effect. More specifically, it means that (i) simply heating the spores at temperatures below 65 °C without irradiating them with UV photons does not induce mortality; (ii) there is no additional increase in the inactivation rate when the Petri has been pre-heated and then brought back to ambient temperature before the spores are UV irradiated; (iii) no additional inactivation results from post-heating spores previously inactivated with UV radiation. Undoubtedly, the synergistic effect shows up only when the physico-chemical agents (UV photons and temperature) are simultaneously in action.

This paper introduces a new type of high-frequency (HF) sustained discharge where the HF field applicator is a planar transmission line that allows us to fill with plasma a long chamber of rectangular cross-section (typically 1 m × 15 cm × 5 cm). Peculiar interesting features of this plasma source are a low gas temperature (typically below 40 °C in the 1 Torr range in argon), broadband impedance matching with no need for retuning, stability and reproducibility of the discharge (non-resonant behaviour). This type of plasma source could be useful for web processing; nonetheless, it is applied here to plasma sterilization, taking advantage of its low gas temperature to inactivate microorganisms on polymer-made medical devices to avoid damaging them. The predominant biocide species are the UV photons emitted by the discharge whereas most plasma sterilization techniques call for reactive species such as O atoms and OH molecules, which induce significant erosion damage on polymers. Polystyrene microspheres are actually observed to be erosion-free under the current plasma sterilization conditions (scanning electron micrographs have been examined). Moreover, inactivation is quite fast: 106 B. atrophaeus spores deposited on a Petri dish are inactivated in less than 1 min. Correlation of the UV radiation with the spore inactivation rate is examined by (i) considering the emitted light intensity integrated over the 112–180 nm vacuum UV (VUV) range with a photomultiplier; (ii) looking with an optical spectrometer at the emission spectrum over the 200–400 nm UV range; (iii) using absorption spectroscopy to determine the role of the VUV argon resonant lines (105 and 107 nm) on spore inactivation. It is found that the test-reference spores are mainly inactivated by VUV photons (112–180 nm) that are primarily emitted by impurities present in the argon plasma.