water, gas, and phylogenetic analyses from sulfur springs in cueva de villa luz, tabasco, mexico...

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Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup University of New Mexico, Albuquerque, NM H.J. Turin Los Alamos National Laboratory, Los Alamos, NM Penelope J. Boston New Mexico Inst. of Mining and Technology, Socorro, NM

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Page 1: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Water, Gas, and Phylogenetic Analyses from Sulfur Springs in

Cueva de Villa Luz, Tabasco, Mexico

Michael N. Spilde, Tobias P. Fischer, and Diana E. NorthupUniversity of New Mexico, Albuquerque, NM

H.J. TurinLos Alamos National Laboratory, Los Alamos, NM

Penelope J. BostonNew Mexico Inst. of Mining and Technology, Socorro, NM

Page 2: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Villahermosa

Cueva de Villa Luz

El Chichon

Page 3: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Photos by Kenneth Ingham © 2004 Kenneth Ingham

Elemental sulfur on ceilingElemental sulfur on ceilingSnottites

Phlegm balls

© 2004 Kenneth Ingham

© 2004 Kenneth Ingham

Page 4: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Phlegm balls in hydrogen sulfide springsPhlegm balls in hydrogen sulfide springs

Nearest Relative Clone # Similarity

Lower Kane Cave Epsilonproteobacteria C4,C6,D10,D12 94.4-98.7%

Hydrothermal vent Endosymbionts D1 92.4-92.6%

Unclass Bacterioidetes Hydrothermal Vent Symbiont/SRB

C7 78.0%

© 2004 Miichael Spilde

Page 5: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Sulfur IsotopesH2S Hose et al. 2000 -11.7‰

So “ -23.7‰

Gypsum “ -23.5 ‰H2S (El Chichón) Taran et al. 1998 +4.6 ‰

So (El Chichón) “ +4.5 ‰ Photo by Kenneth Ingham Photo by Kenneth Ingham © 2004 Kenneth Ingham© 2004 Kenneth Ingham

Sulfur Spring in Cueva de Villa Luz

Page 6: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Photos by Kenneth Ingham © 2004 Kenneth

Ingham

Perched Pool

ORP(mV) -250 -222 -216

pH 7.01 7.13 7.4

ORP(mV) -250 -222 -216

pH 7.01 7.13 7.4

-193 -193 -117 -117 –82–82 7.7 7.7 7.63 7.63 7.777.77-193 -193 -117 -117 –82–82 7.7 7.7 7.63 7.63 7.777.77

Oxidation-Reduction Potential Measurements

© 2004 Kenneth Ingham

Page 7: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Research Question:• What is the source of the hydrogen sulfide gas?

• H2S from Campeche oil and gas fields

• Magmatic gas from El Chichon

• Sulfate reduction in Campeche platform evaporites

Page 8: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Map by Jim Pisarowicz & Louise Hose© 1999 National Spleleological Society

Main Entrance

MidwaySprings

SulfurSpring

Perched Pool BoulderSpring

ResurgenceCueva de Villa Luz, Tabasco, Mexico

0 30

PhlegmaPhlegmaSpringSpring

26 groundwater inlets: 200-300 l/s

Sampled spring: waterSampled spring: gasSpring

Page 9: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Villa Luz Gas Chemistry

El Chichon & Agua Caliente data from Taran et al. 1998

• Not atmospheric gas

© 2004 Miichael Spilde

Page 10: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Villa Luz Gas Chemistry

El Chichon & Agua Caliente data from Taran et al. 1998

• Not atmospheric gas• Not thermogenic (not

derived from heating of sediments by intrusive bodies)

© 2004 Miichael Spilde

Page 11: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Villa Luz Gas Chemistry

El Chichon & Agua Caliente data from Taran et al. 1998

• From He isotopes, calculated magmatic component = 22%

© 2004 Miichael Spilde

Page 12: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Villa Luz Gas Chemistry

El Chichon & Agua Caliente data from Taran et al. 1998

• From He isotopes, calculated magmatic component = 22%

• Gas derived from mixing of mantle and crustal sources

© 2004 Miichael Spilde

Page 13: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Perched Pool

MidwaySprings

BoulderSpring

SulfurSpring

AguaCaliente

(El Chichonspring)

El Chichon Crater

Water Sampling

X10

Water samples:• 4 springs sampled in cave

•2 with low/no H2S gas•2 exhaling H2S

• Compared to El Chichon crater & spring (from Taran et al. 1998)

© 2004 Miichael Spilde

Page 14: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Perched Pool

MidwaySprings

BoulderSpring

SulfurSpring

AguaCaliente

(El Chichonspring)

El Chichon Crater

Water Sampling

X10

Water samples:• 4 springs sampled in cave

•2 with low/no H2S gas•2 exhaling H2S

• Compared to El Chichon crater & spring (from Taran et al. 1998)

© 2004 Miichael Spilde

Page 15: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Perched Pool

MidwaySprings

BoulderSpring

SulfurSpring

AguaCaliente

(El Chichonspring)

El Chichon Crater

Water Sampling

X10

Water samples:• 4 springs sampled in cave

•2 with low/no H2S gas•2 exhaling H2S

• Compared to El Chichon crater & spring (from Taran et al. 1998)

Results:• Little variation between

cave springs• SO4 & Cl nearly equal in

cave water• Low HCO3

• El Chichon water saline, dominated by Cl, low SO4

© 2004 Miichael Spilde

Page 16: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Villa Luz Water Chemistry

Met

eoric

Wat

er L

ine

Li

B• Trace elements elevated in Villa Luz

water

•B & Li high

•Hg about 10x EPS standard

* data from Taran et al. 1998

Villa Luz

El Chichon*

Agua Caliente*

Cold Spring*

Rainwater*

Mixing?

© 2004 Miichael Spilde

Page 17: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Villa Luz Water Chemistry

Met

eoric

Wat

er L

ine

Li

B• Trace elements elevated in Villa Luz

• Fall slightly off meteoric water line

* data from Taran et al. 1998

Villa Luz

El Chichon*

Agua Caliente*

Cold Spring*

Rainwater*

Mixing?

© 2004 Miichael Spilde

Page 18: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Villa Luz Water Chemistry

Met

eoric

Wat

er L

ine

Li

B• Trace elements elevated in Villa Luz

• Fall slightly off meteoric water line

• Suggests mixing of magmatic and

meteoric water

•Using Cl, we calculate 6% mix

* data from Taran et al. 1998

Villa Luz

El Chichon*

Agua Caliente*

Cold Spring*

Rainwater*

Mixing?

© 2004 Miichael Spilde

Page 19: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Villa Luz Water Modeling

PHREEQC Program (USGS) used to calculate mixtures of solutions.

Scenario 1: Simple dilution.Mix meteoric & magmaticEquilibrate with calcite.

© 2004 Miichael Spilde

Page 20: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Villa Luz Water Modeling

PHREEQC Program (USGS) used to calculate mixtures of solutions.

Scenario 1: Simple dilution.Mix meteoric & magmaticEquilibrate with calcite.

Scenario 2: Mixture of equilibrated fluids.

Equil. magmatic w/ CaSO4

Mix with meteoricEquilibrate with calcite.

© 2004 Miichael Spilde

Page 21: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Schematic Model of Water & Gas Sources at Cueva de Villa Luz

Eq CaS

O 4

Eq CaCO3

34S=+4.6

34S=-11.7

MW=4000 mm/yr

faul

t

D

SR

Gas

Water

Degassing

Sulfate reduction

SR

D

10 km

2 km

W E

© 2004 Miichael Spilde

Page 22: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Gases are predominately crustal gases

• No atmospheric signature

• Slight amount of CH4 not thermogenic

• Approximately 22% magmatic gases, based on He isotopes

• Water is predominantly meteoric

• Slightly elevated trace elements indicative of hydrothermal water

• Around 6% hydrothermal water mixed with meteoric

• SO4 in water derived from middle Cretaceous evaporites underlying cave

• H2S probably derived from bacterial sulfate reduction fueled by CH4

• BSR can occur in water column anywhere below the cave

Conclusions

© 2004 Miichael Spilde

Page 23: Water, Gas, and Phylogenetic Analyses from Sulfur Springs in Cueva de Villa Luz, Tabasco, Mexico Michael N. Spilde, Tobias P. Fischer, and Diana E. Northup

Water modeling assistance from Laura Crossey, UNM

Gas analysis by Tobias Fischer, UNM

Water analyses by Jake Turin, LANL

Phylogenetic analysis by Diana Northup, UNM

Gas sampling by Doug Soroka & Penny Boston

Photographs by Kenneth Ingham, Albuquerque, NM

Partial funding from National Geographic Society to

Penny Boston & Louse Hose

Acknowledgements