Nitrogen oxides in the firn air at Summit, Greenland

Measurements of NOx within the snowpack at Summit, Greenland were carried out from June 2008 to July 2010, using a novel system to sample firn air with minimal disruption of the snowpack. These long-term measurements were motivated by the need of improving the representation of air-snow interactions in global models. Results indicated that the NOx budget within the snowpack was on the order of 550 pptv as maximum, and was constituted primarily for NO2. NOx production was observed within the first 50 cm of the snowpack during the sunlight season between February and August. Presence of NOx at larger depths was attributed to high speed wind and vertical transport processes. Production of NO correlated with the seasonal incoming radiation profile, while NO2 maximum was observed in April. These measurements constitute the larger data set of NOx within the firn and will improve the representation of processes driving snow photochemistry at Summit.

MODELING DYNAMICS OF OZONE AND NITROGEN OXIDES AT SUMMIT, GREENLAND WITH A 1-D PROCESS-SCALE MODEL

This work presents a 1-D process scale model used to investigate the chemical dynamics and temporal variability of nitrogen oxides (NOx) and ozone (O3) within and above snowpack at Summit, Greenland for March-May 2009 and estimates surface exchange of NOx between the snowpack and surface layer in April-May 2009. The model assumes the surface of snowflakes have a Liquid Like Layer (LLL) where aqueous chemistry occurs and interacts with the interstitial air of the snowpack. Model parameters and initialization are physically and chemically representative of snowpack at Summit, Greenland and model results are compared to measurements of NOx and O3 collected by our group at Summit, Greenland from 2008-2010. The model paired with measurements confirmed the main hypothesis in literature that photolysis of nitrate on the surface of snowflakes is responsible for nitrogen dioxide (NO2) production in the top ~50 cm of the snowpack at solar noon for March – May time periods in 2009. Nighttime peaks of NO2 in the snowpack for April and May were reproduced with aqueous formation of peroxynitric acid (HNO4) in the top ~50 cm of the snowpack with subsequent mass transfer to the gas phase, decomposition to form NO2 at nighttime, and transportation of the NO2 to depths of 2 meters. Modeled production of HNO4 was hindered in March 2009 due to the low production of its precursor, hydroperoxy radical, resulting in underestimation of nighttime NO2 in the snowpack for March 2009. The aqueous reaction of O3 with formic acid was the major sync of O3 in the snowpack for March-May, 2009. Nitrogen monoxide (NO) production in the top ~50 cm of the snowpack is related to the photolysis of NO2, which underrepresents NO in May of 2009. Modeled surface exchange of NOx in April and May are on the order of 1011 molecules m-2 s-1. Removal of measured downward fluxes of NO and NO2 in measured fluxes resulted in agreement between measured NOx fluxes and modeled surface exchange in April and an order of magnitude deviation in May. Modeled transport of NOx above the snowpack in May shows an order of magnitude increase of NOx fluxes in the first 50 cm of the snowpack and is attributed to the production of NO2 during the day from the thermal decomposition and photolysis of peroxynitric acid with minor contributions of NO from HONO photolysis in the early morning.

Dynamics and kinematics of eruptive activity at Fuego volcano, Guatemala 2005-2009

Volcanoes are the surficial expressions of complex pathways that vent magma and gasses generated deep in the Earth. Geophysical data record at least the partial history of magma and gas movement in the conduit and venting to the atmosphere. This work focuses on developing a more comprehensive understanding of explosive degassing at Fuego volcano, Guatemala through observations and analysis of geophysical data collected in 2005 – 2009. A pattern of eruptive activity was observed during 2005 – 2007 and quantified with seismic and infrasound, satellite thermal and gas measurements, and lava flow lengths. Eruptive styles are related to variable magma flux and accumulation of gas. Explosive degassing was recorded on broadband seismic and infrasound sensors in 2008 and 2009. Explosion energy partitioning between the ground and the atmosphere shows an increase in acoustic energy from 2008 to 2009, indicating a shift toward increased gas pressure in the conduit. Very-long-period (VLP) seismic signals are associated with the strongest explosions recorded in 2009 and waveform modeling in the 10 – 30 s band produces a best-fit source location 300 m west and 300 m below the summit crater. The calculated moment tensor indicates a volumetric source, which is modeled as a dike feeding a SW-dipping (35°) sill. The sill is the dominant component and its projection to the surface nearly intersects the summit crater. The deformation history of the sill is interpreted as: 1) an initial inflation due to pressurization, followed by 2) a rapid deflation as overpressure is explosively release, and finally 3) a reinflation as fresh magma flows into the sill and degasses. Tilt signals are derived from the horizontal components of the seismometer and show repetitive inflation deflation cycles with a 20 minute period coincident with strong explosions. These cycles represent the pressurization of the shallow conduit and explosive venting of overpressure that develops beneath a partially crystallized plug of magma. The energy released during the strong explosions has allowed for imaging of Fuego’s shallow conduit, which appears to have migrated west of the summit crater. In summary, Fuego is becoming more gas charged and its summit centered vent is shifting to the west - serious hazard consequences are likely.

Ultraviolet digital imaging of volcanic plumes : implementation and application to magmatic processes at basaltic volcanoes

Magmatic volatiles play a crucial role in volcanism, from magma production at depth to generation of seismic phenomena to control of eruption style. Accordingly, many models of volcano dynamics rely heavily on behavior of such volatiles. Yet measurements of emission rates of volcanic gases have historically been limited, which has restricted model verification to processes on the order of days or longer. UV cameras are a recent advancement in the field of remote sensing of volcanic SO2 emissions. They offer enhanced temporal and spatial resolution over previous measurement techniques, but need development before they can be widely adopted and achieve the promise of integration with other geophysical datasets. Large datasets require a means by which to quickly and efficiently use imagery to calculate emission rates. We present a suite of programs designed to semi-automatically determine emission rates of SO2 from series of UV images. Extraction of high temporal resolution SO2 emission rates via this software facilitates comparison of gas data to geophysical data for the purposes of evaluating models of volcanic activity and has already proven useful at several volcanoes. Integrated UV camera and seismic measurements recorded in January 2009 at Fuego volcano, Guatemala, provide new insight into the system’s shallow conduit processes. High temporal resolution SO2 data reveal patterns of SO2 emission rate relative to explosions and seismic tremor that indicate tremor and degassing share a common source process. Progressive decreases in emission rate appear to represent inhibition of gas loss from magma as a result of rheological stiffening in the upper conduit. Measurements of emission rate from two closely-spaced vents, made possible by the high spatial resolution of the camera, help constrain this model. UV camera measurements at Kilauea volcano, Hawaii, in May of 2010 captured two occurrences of lava filling and draining within the summit vent. Accompanying high lava stands were diminished SO2 emission rates, decreased seismic and infrasonic tremor, minor deflation, and slowed lava lake surface velocity. Incorporation of UV camera data into the multi-parameter dataset gives credence to the likelihood of shallow gas accumulation as the cause of such events.

USING AUTO- AND CROSS-CORRELATIONS FROM SEISMIC NOISE TO MONITOR VELOCITY CHANGES AT VILLARRICA VOLCANO, CHILE

We used the Green's functions from auto-correlations and cross-correlations of seismic ambient noise to monitor temporal velocity changes in the subsurface at Villarrica volcano in the Southern Andes of Chile. Campaigns were conducted from March to October 2010 and February to April 2011 with 8 broadband and 6 short-period stations, respectively. We prepared the data by removing the instrument response, normalizing with a root-mean-square method, whitening the spectra, and filtering from 1 to 10 Hz. This frequency band was chosen based on the relatively high background noise level in that range. Hour-long auto- and cross-correlations were computed and the Green's functions stacked by day and total time. To track the temporal velocity changes we stretched a 24 hour moving window of correlation functions from 90% to 110% of the original and cross correlated them with the total stack. All of the stations' auto-correlations detected what is interpreted as an increase in velocity in 2010, with an average increase of 0.13%. Cross-correlations from station V01, near the summit, to the other stations show comparable changes that are also interpreted as increases in velocity. We attribute this change to the closing of cracks in the subsurface due either to seasonal snow loading or regional tectonics. In addition to the common increase in velocity across the stations, there are excursions in velocity on the same order lasting several days. Amplitude decreases as the station's distance from the vent increases suggesting these excursions may be attributed to changes within the volcanic edifice. In at least two occurrences the amplitudes at stations V06 and V07, the stations farthest from the vent, are smaller. Similar short temporal excursions were seen in the auto-correlations from 2011, however, there was little to no increase in the overall velocity.