THE ATMOSPHERE OF CRYSTAL

CAVE
Alex Jarnot, Stacey Hughes, Don R. Blake
Dept. of Chemistry and Physics, Hood College, Frederick, MD
Dept. of Chemistry, University of California-Irvine, Irvine, CA

Introduction

Sequoia National Park

Marble karst

Formed by
dissolution of rock

Ambient temperature
remains at about
50 F (10 C)

Introduction

Traditional volatile organic compound (VOC) removal

by OH or h
Lack of sunlight affects VOC lifetimes, no OH
formation

Some air exchange with outside due to changes in

pressure
There should little to no difference in trace gas
concentration between the inside and outside

Methods

Ground sample taken using

a vacuum canister from the
Whole Air Sampler
Taken at ~8 ft from the floor
of the cave

Results

27 of the 99 measured gases were abnormally low in

concentration
Significant CO enhancement
Large differences in concentrations between the
outside and inside indicate non-traditional removal
process(es) for VOCs within the cave

Very low concentrations of several trace gases in cave

Air is well-mixed, sample was not contaminated

Carbonyl sulfide is extremely low, CO is elevated

Isoprene is 50 - 100 ppbv in human breath

CO2 spike is not from mammal influence

Cowan, B., et al. J. of Cave and Karst Studies, 2011

Compound

Avg. Outside
Concentration

Inside
Concentration

Percent
Change

Carbon
Dioxide (CO)

448 ppbv

753 ppbv

+168%

Benzene
(CH)

42 pptv

5 pptv

-826%

Methyl
Nitrate
(CHONO)

11 pptv

0.9 pptv

-1229%

Methyl
Chloride
(CHCl)

724 pptv

46 pptv

-1576%

Methanol
(CHOH)

34475 pptv

2165 pptv

-1593%

Carbonyl
Sulfide (OCS)

568 pptv

35 pptv

-1614%

-Pinene

387 pptv

10 pptv

-3687%

Context

Average concentration of carbonyl sulfide measured

in ice cores from Antarctica dated 1616 to 1694 AD
was 373 pptv

Carbonyl sulfide inside the cave was -1067% of the ice

core

Aydin, M., et al. Geophys. Res. Lett., 2002.

Discussion

Possible degradation
mechanisms:

Bacteria (e.g. Pseudomonas

spp.)

Kleinheinz, G., et al., Arch. Environ. Contam. Toxicol.,

1999

Discussion

Possible degradation
mechanisms:

Inorganic sources (e.g.

hydrolysis)

Elliott, S., et al., Environ. Sci. Technol. 1989

Significance

VOCs lead to ozone production

Negative health and environmental effects

Some trace gas sinks are still not well understood

A better understanding of sinks makes for a better
understanding of global VOC budgets

Future Plans

Collect more samples

Outside the entrance, and throughout the cave to

interior
Develop a profile for VOCs as depth increases
Calculate air exchange rates

Future Plans

CO2 14C analysis

Determine if CO2 is produced from biological or inorganic

process
14C has a half-life of 5,730 years

Soil/Water sample

Flux chamber analysis

Acknowledgements

Don R. Blake, Ph.D.

Stacey Hughes, Ph.D. Candidate
Rafe Day
WAS Group
Pusede Group
Rowland-Blake Lab
Emily Schaller, Ph.D.
KORUS-AQ Scientists
NASA
NSERC

Questions?

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Discussion

Lack of sunlight inhibits photochemistry