# Measurements of HCl in the volcanic plumes of Calbuco (2015) and Raikoke (2019)

Lieven Clarisse, Alexandre Deguine, Tim Hultberg, Nicolas Theys, Simon Carn, Karen Fontijn, Luna Decoster, Juliette Hadji-Lazaro, Daniel Hurtmans, Claude Camy-Peyret, et al.

► To cite this version:

Lieven Clarisse, Alexandre Deguine, Tim Hultberg, Nicolas Theys, Simon Carn, et al. Measurements of HCl in the volcanic plumes of Calbuco (2015) and Raikoke (2019). EGU General Assembly 2020, May 2020, Online, Germany. 10.5194/egusphere-egu2020-10651. insu-03018470

HAL Id: insu-03018470

https://insu.hal.science/insu-03018470

Submitted on 6 Dec 2020

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

Distributed under a Creative Commons Attribution 4.0 International License
Measurements of HCl in the volcanic plumes of
Calbuco (2015) and Raikoke (2019)

<figure><img src="image_2.png" /></figure>

L. Clarisse, A. Deguine, T. Hultberg, N. Theys, S. Carn, K. Fontijn, L. Decoster, J. Hadji-Lazaro, D. Hurtmans, C. Camy-Peyret, C. Clerbaux and P.-F. Coheur
# Volcanic emissions of HCl

* After H₂O, CO₂ and SO₂, **Hydrogen chloride (HCl)** is the main volcanic gas species, and most important halogen halide (Symonds, Rose and Reed; 1988).

* Important effects on environment/ecosystems/soils/air quality (acidification)

* Chemical tracer of magma degassing and other subsurface processes in both syn-eruptive and quiescent degassing

* Estimated yearly emissions between 1 and 10 Tg. But very little is known on the halogen budget of large-size eruptions

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

Arc related volcanic emissions of halogens
Pyle, D. M., and T. A. Mather. "Halogens in igneous processes and their fluxes to the atmosphere and oceans from volcanic activity: a review."
*Chemical Geology* 263.1-4 (2009): 110-121.
# HCl/SO₂ ratios

* Average HCl/SO₂: ~0.3 – but 4 orders of magnitude variation: from 0.001 (Erta Ale) to 10 (Montserrat) (Pyle and Mather, 2009)

* Relative ratios vary in time, with applications to volcano monitoring

* Cl is highly soluble, and generally the more volatile gases are exsolved first (CO₂ before SO₂ before HCl) (Aiuppa et al, 2009):

→ High ratios are associated with the *concluding* stages of basaltic eruptions

→ During periods of reduced magma supply

→ HCl from silicic systems harder to interpret

* Deposition and plume chemistry adds to the complexity

* Wet deposition of HCl can be very significant (uptake in clouds, dissolution in condensed water vapour when RH is large; see Aiuppa et al. 2007, Burton et al. 2001)

* Dry deposition

* Uptake by (volcanic) ice and ash (see next slide)

* Heterogeneous (gas-aerosol) reactions (see next slide)
# Stratospheric emissions and role

* HCl is the most important Cl reservoir species. In the stratosphere can be transformed to reactive forms, leading to the destruction of ozone.

* Presence of bromide in volcanic plumes leads to “explosion” of reactive halogens (BrO and OCIO) via heterogeneous reactions

* Documented stratospheric injections are modest, e.g.
  Augustine 1976: 0.08-0.18 Tg (Johnston, 1980); El Chicon 1982: 0.04 Tg (Mankin et al., 1983); Hekla 2001 (Rose, 2006); MLS ratios ~0.03, a factor 10 lower than what is measured in degassing/smaller tropospheric eruptions

* Direct stratospheric effect of HCl difficult to disentangle from the contribution of volcanic induced heterogeneous reactions that activate Cl reservoir species (ClONO2, HCl).

* Uptake and removal processes

* Scavenging by **liquid supercooled water** unimportant (<1%, Textor et al, 2003)

* Scavenging by **ice particles** important. Textor et al. (2003) : removes 75% of all initial HCl within the hour. Leaves 25% that reaches the stratosphere but in majority incorporated in those particles.

* Scavenging of HCl on **volcanic ash** may or may not important (Gutiérrez et al, 2016; Delmelle et al., 2018)

* Large uncertainty on stratospheric injections!
# Satellite measurements of gases in volcanic plumes

<table><thead><tr><th rowspan="2">Sensor<sup>a</sup></th><th colspan="10">Volatile species</th><th rowspan="2">Timespan</th><th rowspan="2">Reference(s)<sup>b</sup></th></tr><tr><th>H<sub>2</sub>O</th><th>CO<sub>2</sub></th><th>CO</th><th>SO<sub>2</sub></th><th>H<sub>2</sub>S</th><th>HCl</th><th>BrO</th><th>OCIO</th><th>CH<sub>3</sub>Cl</th></tr></thead><tbody><tr><td>TOMS*</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>1978–2005</td><td>1, 2</td></tr><tr><td>SBUV* (P)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>1978–present</td><td>3, 4</td></tr><tr><td>HIRS*</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>1978–present</td><td>5</td></tr><tr><td>GOME</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>1995–2003</td><td>6, 7, 8</td></tr><tr><td>MODIS*</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>1999–present</td><td>9, 10</td></tr><tr><td>ASTER</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>1999–present</td><td>11, 12, 13</td></tr><tr><td>MOPITT</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>1999–present</td><td>14</td></tr><tr><td>SCIAMACHY (L)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>2002–2012</td><td>8, 15, 16</td></tr><tr><td>MIPAS (L)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>2002–2012</td><td>17</td></tr><tr><td>AIRS</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>2002–present</td><td>18, 19</td></tr><tr><td>ACE (L)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>2003–present</td><td>20</td></tr><tr><td>SEVIRI</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>2004–present</td><td>21</td></tr><tr><td>OMI</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>2004–present</td><td>16, 22, 23, 24</td></tr><tr><td>MLS* (L)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>1991–2001; 2004–present</td><td>25, 26, 27, 28</td></tr><tr><td>TES (P)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>2004–present</td><td>29</td></tr><tr><td>GOME-2*</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>2006–present</td><td>16, 30, 31</td></tr><tr><td>IASI*</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>2006–present</td><td>14, 32, 33</td></tr><tr><td>OMPS*</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>2011–present</td><td>34</td></tr><tr><td>VIIRS</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>2011–present</td><td>35</td></tr><tr><td>CrIS</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>2011–present</td><td>36</td></tr><tr><td>AHI</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>2015–present</td><td>37</td></tr><tr><td>GOSAT (P)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>2009–present</td><td>38</td></tr><tr><td>OCO-2</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>2014–present</td><td>39</td></tr></tbody></table>

HCl only observed from Limb measurements (UTLS)

<table><caption>**Table 7**
HCl and SO₂ mixing ratios measured by Aura/MLS in volcanic clouds.</caption><thead><tr><th>Volcano</th><th>Eruption Date</th><th>HCl (ppbv)</th><th>SO<sub>2</sub> (ppbv)</th><th>Pressure (hPa)</th><th>HCl/SO<sub>2</sub></th></tr></thead><tbody><tr><td>Manam</td><td>Jan 27, 2005</td><td>4–6</td><td>279</td><td>68–100</td><td>0.01</td></tr><tr><td>Anatahan</td><td>Apr 6, 2005</td><td>3.5</td><td>133</td><td>100</td><td>0.02</td></tr><tr><td>Soufriere Hills</td><td>May 20, 2006</td><td>3</td><td>200</td><td>68</td><td>0.01</td></tr><tr><td>Chaitén</td><td>May 6, 2008</td><td>1.6</td><td>28</td><td>147</td><td>0.03</td></tr><tr><td>Okmok</td><td>Jul 12, 2008</td><td>5</td><td>212</td><td>147</td><td>0.01–0.02</td></tr><tr><td>Kasatochi</td><td>Aug 7, 2008</td><td>5–6</td><td>392</td><td>68–215</td><td>0.01–0.014</td></tr><tr><td>Redoubt</td><td>Mar 26, 2009</td><td>4–5</td><td>175</td><td>100–215</td><td>0.02</td></tr><tr><td>Sarychev Peak</td><td>Jun 15, 2009</td><td>7–9</td><td>529</td><td>32–215</td><td>0.03</td></tr><tr><td>Merapi</td><td>Nov 5, 2010</td><td>6–7</td><td>172</td><td>100–215</td><td>0.03</td></tr><tr><td>Cordón Caulle<sup>1</sup></td><td>Jun 4, 2011</td><td>2–3</td><td>77</td><td>147–215</td><td>0.03</td></tr><tr><td>Nabro</td><td>Jun 15, 2011</td><td>9</td><td>306</td><td>46–215</td><td>0.03</td></tr><tr><td>Paluweh</td><td>Feb 2, 2013</td><td>2.2</td><td>129</td><td>100–215</td><td>0.01</td></tr><tr><td>Kelut</td><td>Feb 14, 2014</td><td>7</td><td>398</td><td>32–147</td><td>0.01</td></tr><tr><td>Sangeang Api</td><td>May 31, 2014</td><td>2–3</td><td>53</td><td>146</td><td>0.03</td></tr></tbody></table>

Ratios a factor 10 lower than what is measured in-situ – in degassing/smaller tropospheric eruptions
Hydrogen chloride spectrum

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

Oppenheimer, C., et al. "Rapid FTIR sensing of volcanic gases released by Strombolian explosions at Yasur volcano, Vanuatu." *Applied Physics B* 85.2-3 (2006): 453-460.
Location of the HCl SWIR band

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

<figure><img src="image_6.png" /></figure>

http://vpl.astro.washington.edu/spectra/hcl.htm

* Its spectral band is located unfavourably in terms of source radiation:

* Thermal emission too low to be useful

* Solar reflected radiation weak -> measurement possible in daytime

* Its spectral band is located favourable in terms of competing absorbers:

* A few water and methane interferences
# Satellite measurements of HCl using its SWIR band

Currently only IASI covers this band, but only partially (645-2760 cm⁻¹)

But retrieval will be challenging:

* weak background signal (daytime only)

* doesn't cover the strongest lines

* low signal to noise

<figure><img src="image_7.png" /></figure>

<figure><img src="image_8.png" /></figure>
First IASI observations of HCl

<figure><img src="image_9.png" /></figure>

Unambiguous identification of HCL in the volcanic
plumes of Raikoke and Calbuco
# Raikoke

**Where:** Kuril Islands

**Type:** (basaltic) arc volcano

**Elevation:** 551 m

**Eruptions:** VEI ≥4 eruptions in 765, 1778, 1924 and 2019

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

Source: wikipedia

## 21 June 2019 eruption

* Start of eruption around 1750 UTC (Himawari-8 +infrasound)

* Duration ~15h

* 1-2 Tg SO₂

* Injection altitudes >15 km

<figure><img src="image_11.png" /><figcaption>Figure 100. Raikoke Volcano. Photograph by R. Bulgakov. 10.3133/sir20135213</figcaption></figure>

<figure><img src="image_12.png" /></figure>
(a) SO2 column

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

(b) HCl column

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

No HCl detected!
(neither at low or high altitude)

(c) SO2 altitude

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

(d) Ash detection confidence

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

IASI-MetopA between 21-Jun-2019 22:26:36 and 22-Jun-2019 00:07:11 UTC
(a) SO2 column

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

(b) HCl column

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

(c) SO2 altitude

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

(d) Ash detection confidence

<figure><img src="image_20.png" /></figure>
(a) SO2 column

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

(b) HCl column

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

HCl detected below 6km, up to 100 DU!

(c) SO2 altitude

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

(d) Ash detection confidence

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

IASI-MetopA between 22-Jun-2019 22:03:20 and 22-Jun-2019 23:46:47 UTC
Two example spectra, in either part of the plume

<figure><img src="image_25.png" /></figure>
HCl/SO₂ ratios

<figure><img src="image_26.png" /></figure>

Large variability in ratios, from <0.05 (estimate) to > 50
# Calbuco

**Where:** southern Chile

**Type:** (basaltic) andesitic arc volcano

**Elevation:** 2,015 m

**Eruptions:** History of moderately explosive to sub-plinian eruptions throughout the Holocene. 13 eruptions in 20th century, last one in 1972

## 22-23 April 2015 eruption

* <3h precursory seismic activity

* Triggered by continued crystallisation of a cooling magma, which led to second boiling and (over)pressurisation of the system, and rapid onset of the eruption (Arzilli et al 2019).

* Two eruption pulses (of 1.5 and 6 h duration)

* 300 – 400 kt SO₂

* 0.3 – 0.9 km³ erupted tephra (sub-plinian, VEI 4)

* Injection altitudes >15 km (twice)

* Caused measurable destruction of ozone (Solomon et al., 2015)

<figure><img src="image_27.png" /><figcaption>Wikipedia/Marcelo Utreras</figcaption></figure>

<figure><img src="image_28.png" /></figure>

Van Eaton, Alexa R., et al. "Volcanic lightning and plume behavior reveal evolving hazards during the April 2015 eruption of Calbuco volcano, Chile." *Geophysical Research Letters* 43.7 (2016): 3563-3571.
Calbuco

(a) SO2 column

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

(b) HCl column

<figure><img src="image_30.png" /></figure>

Nighttime

(c) SO2 altitude

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

(d) Ash detection confidence

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

IASI-MetopA between 23-Apr-2015 02:33:48 and 23-Apr-2015 02:34:44 UTC
Calbuco

(a) SO2 column

<figure><img src="image_33.png" /></figure>

(b) HCl column

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

(c) SO2 altitude

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

(d) Ash detection confidence

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

IASI-MetopA between 23-Apr-2015 13:53:57 and 23-Apr-2015 13:55:40 UTC
Calbuco

(a) SO2 column

<figure><img src="image_37.png" /></figure>

(b) HCl column

<figure><img src="image_38.png" /></figure>

(c) SO2 altitude

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

(d) Ash detection confidence

<figure><img src="image_40.png" /></figure>

IASI-MetopA between 24-Apr-2015 02:12:23 and 24-Apr-2015 02:15:38 UTC
Calbuco

(a) SO2 column

<figure><img src="image_41.png" /></figure>

(b) HCl column

<figure><img src="image_42.png" /></figure>

(c) SO2 altitude

<figure><img src="image_43.png" /></figure>

(d) Ash detection confidence

<figure><img src="image_44.png" /></figure>

IASI-MetopA between 24-Apr-2015 11:53:43 and 24-Apr-2015 13:33:22 UTC
# HCl/SO₂ ratios

In large part of the plume, no SO₂ is detected!

**Possible explanation:** Gas that was scavenged (e.g., by ice or ice-ash mixtures) at higher altitudes in the eruption column fell out to lower altitudes where it was released upon sublimation. The high ratio would reflect the 'scavenging efficiency' which is higher for HCl than for SO₂.

<figure><img src="image_45.png" /></figure>

<figure><img src="image_46.png" /></figure>
# Conclusions

* Large HCl plumes observed in both eruptions at low altitude near the final stages of the eruptions

* Some very high HCl/SO₂ ratios measured, 10 and above

* No HCl is observed in the high altitude parts, leading to a low upper bound on the (gaseous) HCl/SO₂ ratio (<0.05).

* Relative low stratospheric ratios as measured by MLS confirmed

* A combination of scavenging, plume chemistry, uptake by ice particles and variable emission ratios likely explain the observed variations.

* The large Calbuco HCl plume is likely the result of sublimation from ice fall