# Formation of reactive oxygen and nitrogen species including peroxynitrite in physiological buffer exposed to cold atmospheric plasma

Fanny Girard, Vasilica Badets, Sylvie Blanc, Neso Sojic, Franck Clement, Stéphane Arbault

► To cite this version:

Fanny Girard, Vasilica Badets, Sylvie Blanc, Neso Sojic, Franck Clement, et al.. Formation of reactive oxygen and nitrogen species including peroxynitrite in physiological buffer exposed to cold atmospheric plasma. International Conference on Plasmas with Liquids (ICPL 2017), Mar 2017, Prague, Czech Republic. hal-02271089

HAL Id: hal-02271089

https://univ-pau.hal.science/hal-02271089v1

Submitted on 4 Jan 2026

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<figure><img src="image_1.png" /></figure>

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# Formation of reactive oxygen and nitrogen species including peroxynitrite in physiological buffer exposed to cold atmospheric plasma

Fanny Girard-Sahun,ab Vasilica Badets,b Sylvie Blanc,a Neso Sojic,b

Franck Clémenta and Stéphane Arbaultb

fanny.girard@univ-pau.fr

franck.clement@univ-pau.fr

stephane.arbault@enscbp.fr

cost
EUROPEAN COOPERATION
IN SCIENCE AND TECHNOLOGY

March 5-9, 2017 - Prague, Czech Republic

<footnote>a UPPA, IPREM, CNRS UMR 5254, 2 avenue Président Angot, 64000 Pau, France.</footnote>

<footnote>b Univ. BORDEAUX, ISM, CNRS UMR 5255, NSYSA group, ENSCBP, 16 avenue Pey Berland, 33607 Pessac, France.</footnote>
<figure><img src="image_2.png" /></figure>

1) Plasma generation

<figure><img src="image_3.png" /></figure>

**Physical parameters**
Gas, Voltage, frequency, duty cycle...

2) Plasma
caracterization

<figure><img src="image_4.png" /></figure>

**Plasma analysis**
Physico-chemical components (UV, e.m. fields, gaseous RONS)

3) Plasma-liquid
interactions

<figure><img src="image_5.png" /></figure>

**Liquid analysis**
RONs, pH, σ, evaporation
<figure><img src="image_6.png" /><figcaption>Jobin Yvon 1000 M</figcaption></figure>

Optical fiber with
diaphragm
(variable position)

<figure><img src="image_7.png" /><figcaption>Spectrometer</figcaption></figure>
## Setup 1: Air environment

### ❖ Fixed physical parameters :

* 7.5 kV
* 10 kHz
* duty cycle : 1 %
* 2 slm
* Various working gases

<figure><img src="image_8.png" /></figure>

### ❖ Analysis by Optical Emissive Spectroscopy (OES)
<figure><img src="image_9.png" /></figure>

<figure><img src="image_10.png" /></figure>

► Rotational structures of OH and N₂(SPS) → Tgas ≈ 300 K *

<footnote>*From Gazeli et al., Journal of Applied Physics 117, 093302. 2015</footnote>
Excited chemical
species in the plasma

<figure><img src="image_11.png" /></figure>

What effects on liquid
chemistry ?

1) Plasma treatment

- Working gas He/1%N₂

- Various exposure times

<figure><img src="image_12.png" /></figure>

<figure><img src="image_13.png" /></figure>

PBS -- (10 mM) pH 7.4

2) Liquid analysis

<figure><img src="image_14.png" /></figure>

POST-TREATMENT
Analysis

<figure><img src="image_15.png" /></figure>
<figure><img src="image_16.png" /></figure>

He/1%N₂

Stable Oxygen and Nitrogen Species

<figure><img src="image_17.png" /><figcaption>Electrochemistry</figcaption></figure>

<figure><img src="image_18.png" /></figure>

<figure><img src="image_19.png" /></figure>
pH measurements

7.5 kV
10 kHz
$duty cycle = 1 \%$

<figure><img src="image_20.png" /><figcaption>He/1%N₂</figcaption></figure>

<figure><img src="image_21.png" /></figure>

➤ Acidification

➤ Hypothesis : HNO₂ and HNO₃
➤ H₂O₂, NO₂⁻ and NO₃⁻: stable species in solution

What strategies to detect
Reactive Oxygen and Nitrogen Species (RONS)
in liquids ?

Switch the pH of PBS
to alkaline values

Stabilize basic anionic
species
PBS pH 12, UV-visible absorption spectroscopy *

7.5 kV
10 kHz
$duty~cycle = 1 \%$

He/1%N₂

<figure><img src="image_22.png" /></figure>

<figure><img src="image_23.png" /></figure>

➤ Hypothesis : ONOO⁻ ($ε_{302nm}$=1670 M⁻¹·cm⁻¹)

<footnote>*Girard *et al.*, RSC Adv., 2016, 6, 78457–78467</footnote>
PBS pH 12, UV-visible absorption spectroscopy *

7.5 kV
10 kHz
duty cycle = 1 %

He/1%N₂

<figure><img src="image_24.png" /></figure>

Beer-Lambert law :

$$A_{\lambda} = \sum_{i} \varepsilon_{\lambda,i} | C_{i}$$

<figure><img src="image_25.png" /></figure>

* ✓ ONOO⁻: hypothesis validated

* ✓ [ONOO⁻] ≈ 50 µM (10 minutes of treatment)

* ✓ Stabilized at pH 12 but probably also exists at pH 7.4

<footnote>*Girard et al., RSC Adv., 2016, 6, 78457–78467</footnote>
# Influence of the surrounding atmosphere on chemical species ?

## Setup 2 : Shielding gas device

<figure><img src="image_26.png" /><figcaption>7.5 kV
10 kHz
duty cycle = 1 %</figcaption></figure>

<figure><img src="image_27.png" /></figure>

<figure><img src="image_28.png" /></figure>
Optical Emissive Spectroscopy

<figure><img src="image_29.png" /></figure>

✓ O emission higher for 100% O₂

✓ OH and NOγ emissions higher for 100% N₂

<figure><img src="image_30.png" /></figure>
ONOO⁻ quantification

7.5 kV
10 kHz
duty cycle = 1 %

<figure><img src="image_31.png" /></figure>

<figure><img src="image_32.png" /></figure>

✓ [ONOO⁻]max for 20% O₂/80% N₂ in the shielding gas ("air shielding")

What about the stable oxygen and nitrogen species ?
7.5 kV
10 kHz
duty cycle = 1 %

<figure><img src="image_33.png" /><figcaption>NO₂⁻, H₂O₂ and NO₃⁻ quantification</figcaption></figure>

<figure><img src="image_34.png" /></figure>

* ✓ [NO₂⁻]max for the "air shielding" (20% O₂/80% N₂)

* ✓ [H₂O₂]max and [NO₃⁻]max for 100% N₂ in the shielding gas
Nitrite-pH correlation

<figure><img src="image_35.png" /></figure>

➤ Acidification

➤ Hypothesis : HNO₂
* The concentrations of species depend on the shielding gas composition

* The final ratios of species in the liquid are different

What really happens during the plasma
treatment ?

<figure><img src="image_36.png" /></figure>

in situ electrochemistry
has to be performed
# Conclusions and hypotheses...

<figure><img src="image_37.png" /></figure>
INTERNATIONAL CONFERENCE ON PLASMAS WITH LIQUIDS (ICPL 2017)

Thank you for your
attention

➤ Particular thanks to Laurent Marlin, Natacha Dumont, Mathieu Peret and Kristaq Gazeli for their respective contribution

fanny.girard@univ-pau.fr

<figure><img src="image_38.png" /></figure>
Additional slide
7.5 kV
10 kHz
duty cycle = 1 %

Switch to alkaline values : PBS pH 12 *

UV-visible absorption spectroscopy

<figure><img src="image_39.png" /></figure>

➤ 1st Hypothesis : hypochlorite ClO⁻ (ε₂₉₂nm = 365 M⁻¹.cm⁻¹)

➤ 2nd Hypothesis : ONOO⁻ (ε₃₀₂nm = 1670 M⁻¹.cm⁻¹)

<footnote>*Girard et al., RSC Adv., 2016, 6, 78457–78467</footnote>