AN EXPERIMENTAL STUDY OF THE FLUXES
OF REDUCED SULFUR GASES FROM A SALT WATER MARSH
by
Mary Anne Carroll
B.A., University of Massachusetts, Boston
(1978)
Submitted to the Department of
Earth and Planetary Science
in Partial Fulfillment of the
Requirements of the Degree of
DOCTORATE IN SCIENCE
at the
MASSACHUSETTS INSTITUTE OF TECHNOLOGY
May 1983
o Mary Anne Carroll 1983
The author hereby grants to M.I.T. permission to reproduce and to
distribute copies of this thesis document in whole or in part.
Signature of Auth or
a
Earth and Planietary Science
men"
March 18, 1983
I
Certified by
4onald G. Prinn,.Thesis Supervisor
by
Accepted
.v
... . . .
Theodore R.
Madde
, Chairman,
MASSfp
LBRI
LIBRARIES
Deptihent
Committee
ACKNOWLEDGMENTS
I would like to express sincerest gratitude to Ron Prinn, my
thesis advisor at MIT, for his perpetually helpful advice, enthusiasm,
support, and wit.
I am thankful for the opportunity extended to me by the Advanced
Study Program at NCAR to develop my research interests as a UCAR
Fellow (1978-79) and to conduct my thesis research as a Graduate
I am deeply grateful to Ralph Cicerone
Research Assistant (1981-83).
for the opportunity to pursue research under his guidance and for his
It has also been a
continued support throughout my tenure at NCAR.
pleasure to work closely with Leroy Heidt, and I have benefitted
tremendously by this association.
I would also like to thank Ed Boyle at MIT for his continued
Special thanks go to Kevin Brown, Ken
interest and sound advice.
Koehlert and Rich Freeman who participated in this research as Student
Opportunities
Research
Undergraduate
MIT
the
under
Assistants
Program.
like to
I would
Biological Laboratory in
to share his laboratory
access to his field site
Steudler at the Marine
acknowledge Paul
Woods Hole, Massachusetts for the opportunity
and instrumentation as well as for providing
at the Sippiwissett Salt Marsh.
I would like to express my appreciation to Dr. Keller of the
NASA/GSFC Wallops Flight Facility for the opportunity to conduct my
I am especially grateful to Arnold
field work at Wallops Island.
Special
Torres for generously sharing his laboratory and equipment.
thanks to Rob Frostrom for facilitating my research requirements while
I was a visitor at NASA/Wallops, to George Brothers for loaning
equipment, to Bob Barnes for bringing me dinner during overnight
analysis sieges, and to Rob Huey for being tremendously helpful and
wonderously good-natured.
I would like to acknowledge Rich Lueb and Russ White at NCAR for
lending their expertise during the developmental stages of this
Thanks also to Electrical and Machine Shop, Graphics and
research.
Photographics personnel for their technical support, and to my ACAD
colleagues for helpful conversations and equipment generously loaned.
Thanks to Walt Pollack and Bruce Henry for being great lab-mates and
Special thanks
to Med Medrud and Betty Wilson for all of their help.
to Mary Nuanes for secretarial support during my stay at NCAR and to
both Mary and Ursula Rosner for typing this thesis.
I would like to express my gratitude to the Danforth Foundation
I am grateful not only
for their support during my graduate studies.
2
for their financial support but also for the opportunity to participate in several Danforth Conferences.
Support for this research was
also provided by NSF grants to MIT.
And, finally, it is with total appreciation that I acknowledge
the extraordinary patience and support of my dear friends who have
gifted me with the joys of humor, comfort, and love.
Dedicated to Pat
ABSTRACT
In recent years there have been several attempts to model the
Two major categories of sources have
earth's global sulfur cycle.
been identified as anthropogenic and biogenic, and they are thought to
Interest in the natural or
contribute equally to the global cycle.
"background" sulfur cycle is in part motivated by a desire to underBoth local
stand the perturbations caused by anthropogenic sources.
the
flux of
caused
by
effects such as acid rain and global effects
Most modelers
carbonyl sulfide to the stratosphere, are of concern.
have attributed a major role to biogenic sources due to an inability
to otherwise balance their models. All have underlined the importance
of experimental studies which will help to quantify the contribution
of biogenic sources of sulfur.
The primary goals of this research were to determine the role of
a salt water marsh in the global carbonyl sulfide (OCS) cycle, and to
establish the diurnal and seasonal behavior of OCS from such a
Secondary goals included the quantification of as many gases
source.
as could be resolved given the analytical instrumentation (optimized
for OCS) and the constraints of sample storage and analysis requirements. Thus, the diurnal flux behavior of both OCS and hydrogen sulfide (H2 S) were determined along with normalized concentration informThe influence of light intensity,
ation for carbon disulfide (CS 2 ).
soil moisture, and soil temperature on the rates of emission of these
three gases was also monitored.
equipped with a Flame PhotoA TRACOR Gas Chromatograph (GC),
and a SPECTRA PHYSICS programmmetric Detector and a sulfur filter,
KINTEK and
able integrator comprised the analysis instrumentation.
gas
standards.
sulfur
generate
to
were
used
A.I.D. permeation devices
Separation of the various sulfur gases was accomplished using a column
A flux
made of specially treated Porapak-QS-packed Teflon tubing.
chamber was used to determine the rates of emission of OCS and H2 S
from the marsh surface, and samples of chamber air were collected.
After calibrating the GC response, sample loops were connected to the
GC sample valve and desorbed by rapid transfer from liquid argon to
A composite calibration curve, made up of curves run
boiling water.
before and after sample analysis, was used to determine sample concenThe fluxes of OCS. and H2S were then calculated from the
trations.
the
difference between input and output chamber concentrations,
and
area,
surface
chamber
the
height,
the
chamber
rate,
flow
chamber
mechanically
by
as
estimated
time
with
of
concentration
the changes
fitting curves to the concentration plots.
The major data collection effort involved a field study conducted
at Wallops Island, Virginia, a barrier island off the eastern shore of
The island is a part of the NASA/Wallops
the Delmarva Peninsula.
Flight Facility, and the northern part of the island consists primarily of isolated marsh and beach. The field experiment was limited
to studying the emissions of OCS, H2 S, and CS 2 from mixed stands of
Spartina-Alterniflora and Spartina-Patens found in the high marsh.
Field experiments, each of 25-hour duration, were conducted weekly
from mid-July through September 1982.
The mechanically-stirred, polycarbonate flux chamber was continually flushed with scrubbed ambient air.
Ambient air was pulled
through a carbon vane pump and its exhaust entered a regulating rotameter or was vented.
The regulated flow was passed through a series
of Drierite-filled plastic cylinders before the air passed through a
series of two -50' lengths of copper tubing coiled and immersed in
liquid argon. Next, the air was warmed somewhat as it passed through
tubing immersed in a warm water bath.
The air then flowed through a
second rotameter, used to identify any changes in the flow through the
series of traps and driers and to confirm the flow rate before it
entered the chamber.
After an initial equilibrium period, the air
entering and exiting the chamber was then collected simultaneously and
stored for laboratory analysis to determine the amount of OCS, H2 S,
and CS2 generated within the chamber.
Sample loops made of Teflon
tubing and housed in aluminum tubing were equipped with Teflon plug
valves. A drier consisting of strands of Nafion (DUPONT) tubing with
helium counterflow was employed on chamber exit samples.
Liquid argon was used to cryogenically trap and store samples
which were pulled through the loops by FMI pumps.
The pumping rate
was constant and routinely checked to assure accuracy in the sample
volume collected.
Sample collection was conducted for 50-60 minutes
every other hour over a period of 25 hours.
Typical sample volumes
were 1.5 to 2 liters of air. Light intensity and air and soil temperatures, both inside and outside the chamber, were also monitored.
During the later six studies, a loosely-woven, lightweight, white
cloth was used to shade the chamber which helped to reduce surface
evaporation and thus condensation on interior chamber walls without
significantly reducing the light which reached the chamber interior.
Diurnal variation in fluxes and the strong influence of soil moisture
upon the rates of emission of OCS and H2 S were routinely observed.
While the flux behavior of OCS and H2S followed similar patterns, CS2
fluxes were routinely low except during some tidal flooding episodes.
Individual flux calculations during hot and wet conditions were
For
often found to be very high but taken alone are misleading.
example, one could conclude that up to 12% of global OCS may be
accounted for by salt water marshes from such measurements. Diurnally
averaged flux values, however, show that high marsh mixed-Spartina
stands are insignificant global sources of H2 S or CS2 and insigniThis research suggests
ficant contributors to the global OCS cycle.
determined
from measurethat it is erroneous to extrapolate fluxes
ments made in low marsh or coastal areas to regions of the high marsh
in calculations of global sulfur fluxes for H2S, OCS, or CS2.
TABLE OF CONTENTS
Chapter
Page
Acknowledgments
. . . .
Dedication . . .
. .
Abstract . . .
. . . . .
. . . .
. . . . .
. . . . .
. . .
List of Tables . . . .
. . . .
2
ANALYTICAL INSTRUMENTATION . . .
3
SAMPLING TECHNIQUES
4
5
6
. . .
8
.
13
. .
14
. . . .
24
39
. . . . . . . . . .
Trapping Tests
Sample Collection . . . . . . . . .
Sample Analysis . . . . . . . . . .
39
46
. . .
. . . .
. . . .
. . . . .
53
.
66
66
66
71
107
Dissolved Oxygen and pH Measurements
A Micrometeorological Flux Study .
Wallops Island Flux Studies . . . .
Aircraft Measurements . . . . . . .
. . .
112
Analytical Developments . . . . . .
Field Studies . . . . . . . . . . .
The Global Sulfur Budget
. . . . .
112
114
117
SUMMARY AND CONCLUSIONS
5.1
5.2
5.3
.
. .
FIELD STUDIES
4.1
4.2
4.3
4.4
4
. . . .
INTRODUCTION . .
. . . .
. . .
. . . .
1
3.1
3.2
3.3
. . . . . .
3
. . . .
. . .
List of Illustrations
1
.
. . . . .
. . . . . .
Table of Contents
. . .
. . . . .
Bibliography . .
. . . . .
. . . . .
. .
I
Curriculum Vita
. . . . .
. . .
II
Analytical Instrumentation Used at the
Scripps Institution of Oceanography
129
Appendix
III
IV
Analytical Instrumentation Used at the
Marine Biological Laboratory . . . . . . . .
138
140
.
142
SP4100 Program and Rotameter and Thermocouple
Calibrations . . . . . . . . . . . . . . . . .
143
7
Appendix
Page
V
Empty Teflon Sample Loop Efficiencies . ......
157
VI
Mechanical Fits to Plots of Concentrations to
Determine C(t i ) for Wallops Island Flux Studies
and Concentration and Flux Results, Reported With
Their Errors, for H2 S and OCS . ..........
160
VII
Reproducibility Studies
. ............
VIII
Wallops Island Field Studies: Light
Intensities and Air and Soil Temperatures
.
. ....
189
191
LIST OF ILLUSTRATIONS
Figure
Page
1
Earth's global sulfur cycle
2
VALCO 10-port sampling valve . ...........
3
Automatic sampling valve controller circuit
diagram
...................
. ...........
15
30
...
31
. .......
4
Photograph of modified sample valve
5
KINTEK cell diagram
6
Standard dilution system .
7
Flow meter calibration system
8
Photograph of sample loop in
9
Water vapor addition apparatus schematic
. ...........
32
.
....
.............
.
34
36
........
cryogen
. .
. .......
37
43
. .....
45
10
NAFION drier schematic . .......
11
Sample collection schematic
12
Polycarbonate flux chamber . ............
51
13
OCS standard chromatogram
. ............
57
14
H2S standard chromatogram
. ............
58
15
CS2 standard chromatogram
. ............
59
16
Sample chromatogram
17
Composite OCS calibration curve
18
July 1979 Panesquitos Marsh field studies results
19
April 1980 Sippiwissett Salt Marsh field study wind
speed measurements . ................
69
April 1980 Sippiwissett Salt Marsh field study
average wind speeds
. ...............
69
21
Map describing location of Wallops Island, Virginia
72
22
Photographs of Wallops Island field site . .....
73
23
August 5-6, 1982 field study:
20
......
.
. ...........
48
. ...............
.
60
.........
OCS fluxes
47
62
. ....
.
67
76
Page
Figure
24
August 5-6, 1982 field study:
25
August 5-6, 1982 field study: OCS, H2S and CS
2
concentrations . . . . . . . .
H2S
fluxes
.
.
August 13-14, 1982 field study:
OCS f luxes
August 13-14, 1982 field study:
H 2 S fluxes .
August 13-14, 1982 field study:
concentrations
OCS, H2S,
and
.
77
.
CS2
1982 field study:
OCS fluxes
August 18-19,
..
1982 field study:
H2S fluxes .
August 18-19,
1982 field study:
OCS, H2
August 18-19,
concentrations
S
, and CS2
1982 field study:
fluxes
OCS
August 26-27,
1982 field study:
H2 S fluxes
August 26-27,
1982 field study:
OCS, H2S,
August 26-27,
concentrations
and CS 2
.
1982 field study
September 3-4,
:
1982 field study
September 3-4, 1982 field study
37
:
OCS fluxes
H2 S fluxes
September 3-4, 1982 field study:
0 CS
concentrations
. . . . . . . . . .
,H2 S , and CS 2
38
September 9-10, 1982 field study:
OC S fluxes
39
September 9-10, 1982 field study:
H 2 S fluxes
40
September 9-10,
concentrations
.
.
1982 field study:
OCS, H2S, and CS 2
. . . . . . . . . . . . . . . .
96
41
September 14-15, 1982 field study:
OCS fluxes
.
.
97
42
September 14-15, 1982 field study:
H2 S fluxes
. . .
98
43
September 14-15, 1982 field study: OCS, H2 S, and CS2
concentrations . . . . . . . . . . . . . . .
.
.
44
September 23-24, 1982 field study:
OCS fluxes
. ..
45
September 23-24, 1982 field study:
H2S fluxes
.
.
99
101
.
102
Figure
Page
46
September 23-24, 1982 field study: OCS, H 2 S, and CS2
concentrations
. . . . . . . . . . . . . . . . . . . 103
47
September 28-29, 1982 field study:
OCS fluxes
104
48
September 28-29, 1982 field study:
H2 S fluxes
105
49
September 28-29, 1982 field study:
OCS, H 2 S, and CS2
106
concentrations . . . . . . . . . . . . . . . . . . .
50
Aircraft sample collection schematic . . . .
51
Dissimilatory sulfate reduction
.
125
52
Primary standard generation by dilution method . . .
141
53
Rotameter calibrations . .
. . .
.
156
54
Mechanical fits to OCS concentrations
for August 5-6, 1982 field study . . . .
.
161
Mechanical fits to H2 S concentrations
for August 5-6, 1982 field study . . . .
.
161
Mechanical fits to OCS concentrations for
August 13-14, 1982 field study . . . . . .
162
Mechanical fits to H2 S concentrations for
August 13-14, 1982 field study . . . . . .
162
Mechanical fits to OCS concentrations for
.....
August 18-19, 1982 field studies
163
Mechanical fits to H2 S concentrations for
August 18-19, 1982 field studies
.....
163
Mechanical fits to OCS concentrations for
August 26-27, 1982 field study . . . . . .
164
Mechanical fits to H2S concentrations for
August 26-27, 1982 field study . . . . . .
164
Mechanical fits to OCS concentrations for
September 3-4, 1982 field study
165
Mechanical fits to H2 S concentrations for
September 3-4, 1982 field study . . . . .
165
Mechanical fits to OCS concentrations for
September 9-10, 1982 field study . . . . .
166
55
56
57
58
59
60
61
62
63
64
. . .
. . . .
. . . .
. . . . . .
108
Figure
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
Page
Mechanical fits to H2S concentrations for
September 9-10, 1982 field study . . . . .
.
166
Mechanical fits to OCS concentrations for
September 14-15, 1982 field study . . . . .
167
Mechanical fits to H2S concentrations for
September 14-15, 1982 field study .....
167
Mechanical fits to OCS concentrations for
September 23-24, 1982 field study . ....
168
Mechanical fits to H2 S concentrations for
September 23-24, 1982 field study . . . . .
168
Mechanical fits to OCS concentrations for
September 28-29, 1982 field study . . . . .
169
Mechanical fits to H2 S concentrations for
September 28-29, 1982 field study . . . . .
169
August 5-6, 1982 field study: Light
intensities . . . . . . . . . . . . .
.
192
August 5-6, 1982 field study: Air and Soil
temperatures
. . . . . . . . . . . . . . .
192
August 13-14, 1982 field study:
intensities .
193
August 13-14, 1982
temperatures
1982
August 18-19,
intensities .
1982
August 18-19,
temperatures
1982
August 26-27,
intensities .
1982
August 26-27,
S ..
temperatures
field study:
. .
Light
Air and Soil
193
field study:
Light
194
field study:
Air and Soil
194
field study:
Light
195
field study:
. . .
. . . .
Air and Soil
. .
September 3-4, 1982 field study: Light
intensities . . . . . . . . . . . . . . . .
. .
September 3-4, 1982 field study: Air and Soil
..
. ...
. . .
temperatures
.
195
196
196
Figure
82
83
84
85
86
87
88
89
Page
September 9-10, 1982 field study:
intensities . ..................
Light
September 9-10, 1982 field study:
temperatures . ..................
Air and Soil
September 14-15, 1982 field study:
intensities . ..................
.
197
197
Light
. .
198
September 14-15, 1982 field study: Air and Soil
. ..
..........
temperatures
. ......
198
September 23-24, 1982 field study:
intensities . ..................
Light
199
September 23-24, 1982 field study:
. ..................
temperatures
Air and Soil
September 28-29, 1982 field study:
intensities . ..................
Light
September 28-29, 1982 field study:
. ..................
temperatures
Air and Soil
. .
199
.
200
200
LIST OF TABLES
Page
Table
1
Chromatographic Retention Times . .........
2
Aircraft Sample Collection
3
Aircraft Measurements of OCS and CS2
4
Summary:
5
Annual Global Fluxes of Sulfur from Biogenic
Sources ...............
...
....
.
56
...........
109
.
.
.
.
Wallops Island Flux Studies . ...
6
SP4100 Program
7
SP4100 Program Variable List
8
Main Program (Comments) .
9
Plotting Subprogram (Comments)
.
.
.
. .
.
. .................
. ..........
.............
110
116
.
118
143
147
149
. .........
10
Tracor Rotameter Calibrations
11
Chromel-Alumel Thermocouple Calibration . .....
155
12
Empty Teflon Sample Loop Trapping
. ................
Efficiency Tests
158
Concentration and Flux Results for Wallops Island
Flux Studies of OCS and H2 S . ...........
171
13
14
Reproducibility Studies .
. ..........
153
.............
154
190
CHAPTER 1
INTRODUCTION
The research described here was motivated by the desire to better
understand
mental
the earth's
interest
sulfur cycle.
due
to
current
The sulfur
concerns
cycle is of environ-
about
regional
pollution
effects such as acid rain and possible global climatic effects such as
those
induced
"Junge"
layer.
tribute
almost
al.,
1972;
1981).
by
an
increase
Anthropogenic
equally
to
Friend,1973;
Anthropogenic
application
of
Thus
cation.
new
it
in
stratospheric
and natural
its
global
Granat
et
sources
of utmost
sources
atmospheric
al.,
could
technologies
is
the
1976;
increase
for
coal
importance
sulfuric
of
sulfur
budget
Moss,
(Kellogg
due
liquefaction
that
we
may con-
1978;
rapidly
learn
acid
et
Ivanov,
to
and
future
gasifi-
the magnitude
of the contribution of the natural sources of sulfur and its compounds
to
the
global
sulfur
cycle
so
that
which anthropogenic sources perturb
A
Fig.
of
and
schematic
In
1.
sulfur
of
the
earth's
many of
the
attempts
(Eriksson,
Kaplan,
1966;
Kellogg et al.,
and
Kaplan,
Zinder,
Robinson
1972;
1974;
1980),
substantial
1959,
Rodhe,
Cadle,
we may understand
and
sulfur
to describe
1963;
1975;
et
authors
generally
oceanic
source.
For
example,
with
170 Tg
atmospheric
the
ocean,
sulfur
Junge
budget
(1963a)
requires
conclude
a
1960,
1970;
al.,
to
Eriksson
balancing
presented
(Tg
in
circulation
1963a,b;
Holser
Georgii,
1970;
1974; Goldhaber
1976;
that
S yr-1
is
natural
1973; Levy,
the
his
the
1968,
Friend,
Granat
cycle
Junge,
Robbins,
1972;
degree
this cycle.
global
1960,
the
there
must
(1963)
be
a
balances
= 1012
oceanic
and
Zehnder
g)
source
from
of
LAND-OCEAN TANPOR
ATMOSPHERE
OCEAN-LAND TRANSPORT
Fig. 1
Earth's global sulfur cycle (modified from Zehnder and Zinder, 1980)
160
Tg
with
S yr-1,
a
much
and
(89
Robinson
smaller
Kellogg et al.
source
and
(1972),
and
oceanic
source
of
(1968)
30
Tg
balance
their
yr-1 .
S
model
Similarly,
while they do not arrive at a separate oceanic
Tg S yr-1 land-ocean),
the ocean surface
Robbins
as possible
suggest marshy areas,
atmospheric
sulfur
tidal
sources,
flats,
Friend
(1973) assigns an oceanic source of 59 Tg S yr-1 to balance his sulfur
budget,
Cadle
87 Tg S yr-1,
(1975)
balances
Granat et al.
in
27 Tg S yr-1 outstanding
and Zinder (1980)
In
contrast,
Ivanov
79 Tg
S
yr-1
than
(1976)
Tg
S
with
suggest
the
budget,
source
a
sulfide
value
total
sulfur
(H 2 S)
of
for the
and Zehnder
of 48 Tg S yr-1.
balancing
yr - 1 of marine
12 Tg S yr-1 of biogenic hydrogen
land-ocean
an oceanic source
oceanic
calculates
a
sulfur
their overall
attribute
specifically
(60
model
assign a balancing
rather
(1981)
his
role
oceanic
with
sea
to
oceans,
source
spray
from coastal
of
plus
shallow
sediments plus 7 Tg S yr-1 of reduced sulfur emitted from the ocean's
surface)
based upon geochemical data
for sulfur compounds and in
situ
experimental studies.
In spite
of
work by Ostlund
and
Alexander
that H2 S could not survive diffusion through
(1963) pointing out
an aerobic water column,
authors continued to attribute to H2S the role of the missing oceanic
link required
al.,
1972;
to balance
Friend, 1973).
the global
sulfur budget
Lovelock
et
al.
(e.g.,
(1972)
also
Kellogg
state
et
that
oceanic surface waters are too oxidizing to allow the emission of H2 S
in
the amounts required to balance
and they suggest that dimethyl
this role.
the aforementioned
sulfide
((CH 3 ) 2 S)
sulfur budgets,
might replace
H2 S in
Lovelock (1974) reports observations of carbon disulfide
is
unlikely
that
oceanic
CS2
is
a significant
sulfur based upon discussions with Liss,
1974)
he concludes
and open ocean waters; however,
coastal
(CS 2 ) in
regarding gas fluxes across
that it
source of atmospheric
Broecker and Peng (Lovelock,
the atmosphere-ocean
interface.
At
the same time, he maintains the importance of (CH3 )2 S as a significant
oceanic source of atmospheric sulfur.
of
measurements
H2 S
emitted
reported.
He questions
quantities
required
to
from
the
balance
aerobic surface
H2 S evolution.
Rasmussen
aerobic
naturally
to
released
in
fresh waters
and
suggesting
habitats,
the
of
the
H2 S
from
dation
marshes,
by
Chen
and
and
that
swamps
and
1978;
of
intertidal
several
from
land
and
waters
zones
et al., 1978; Aneja et al.,
1981; Goldberg et al.,
)2 S2 )
ocean
both
con-
to
Several
this
1968; Jaeschke
over
merfrom
are
and
sulfide oxiflats,
tidal
salt
anaerobic
investigators have
salt
water marshes,
research effort
et al.,
to
source of atmospheric
suggest
gases
in
Granat et al.
(which often experience
sulfur
prior
3
sulfides
organic
that of H2 S.
they
(1972),
reduced
Hansen et al.,
the calculated
((CH
disulfide
conditions) as possible oceanic sources.
made measurements
budgets,
a study of the kinetics of aqueous
shallow marine
muds
analyses of H2 S, methyl
dimethyl
atmosphere
Morris
been
waters act as a physical barrier
amounts which well exceed
Referencing
sulfur.
have
anaerobic
sulfur
also discuss the role of H2 S as a marine
(1976)
al.,
environments
postulated
reports his
(CH3 ) 2 S,
(CH3 SH),
anaerobic
emission
tending that the
captan
Rasmussen (1974) states that no
1978;
(Hill et
Schwarzenbach
1979a,b,c, 1980; Adams et al.,
1979, 1980,
1981; Ingvorsen and Jorgensen, 1982).
However,
emission rates for CS2 span three orders of magnitude,
those
for
carbonyl
and
(CH3 ) 2 S
sulfide
those
for
ranges of
span
four
(OCS),
orders
of
and (CH 3 ) 2 S 2
six
CH3 SH span
magnitude,
span five
orders
orders
of magnitude!
undoubtedly represent
emission rates
those
for
H2 S,
of magnitude,
In
part,
seasonal
these
variations.
However, they may also be due to differences in measurement techniques
and
local
conditions
(e.g.,
soil
moisture,
tidal
influence,
light
environments,
soils
intensity, soil temperatures).
In
(Bremner
1979,
addition
to
the
and Banwart,
1981),
animal
(Kellogg et al.,
Robbins,
1968,
aquatic
1974; Banwart and Bremner,
waste
and
(Bremner
1975a; Adams et al.,
Banwart,
1975b),
1970;
spray (Eriksson, 1960,
sea
Kellogg et
al.,
1976; Moss,
1978),
al.,
1974),
and forest
al.,
1979)
complete the
al.,
geothermal
1972;
1963;
Friend,
fields
areas and oil
of natural
Robinson
1973;
fires (Hartstein and Forshev,
list
volcanoes
1976; Moss, 1978),
1972; Friend, 1973; Granat et al.,
decay and
biological
aforementioned
and
Granat
et
(Graedel et
1974; Crutzen et
sources suspected or observed
to emit sulfur gases.
Three of the
CS2 ,
(CH 3 ) 2 S,
troposphere.
apparently
and H2 S,
In
one or two days.
are
important
particular,
They react
H2 S
and (CH3)
short-lived
2
S have
Sandalls, 1974; Atkinson et al.,
(SO
2
)
(Hales
gases,
species
namely
in
lifetimes of
hydroxyl radical
with tropospheric
to ultimately form sulfur dioxide
1980; Hatakeyama et al.,
as
recognized
sulfur
reduced
et al.,
1978; Davis et al.,
1974;
the
only
(OH)
Cox and
1979; Sze and Ko,
1982; Grosjean and Lewis, 1982) while CS2 may
react with hydroxyl radicals to form OCS (Kurylo, 1978a,b; Atkinson et
al.,
1978;
Sze
and Ko,
1979;
Sze and Ko,
1980,
1981;
Bandy et
al.,
1981;
Jones
et al.,
Rowland (1980)
so low that
et
lifetime
Wine et al.
(1980)
and Iyer and
reacts with OH to be
this cannot be considered a viable sink for tropospheric
variability
(Bandy
However,
have shown the rate at which CS2
(Maroulis
al.,
of
1981)
CS2
is
and
Bandy,
found
for
1980)
CS2
short.
quite
and
the
suggests
They
corresponding
vertical
that
speculate
photo-oxidation of CS2 may provide a considerable
lifetime of no more than one or
temporal
the
of both
size
that the
comment
(1981)
et al.
Wine
CS2 .
1982).
gradient
the
tropospheric
that
tropospheric
sink for CS2 with a
two
weeks.
S02, the
common oxidation product, may remain in the atmosphere or be
oxidized
to sulfuric
of the concentrations
acid aerosol
of both
particles.
the
reduced
further
Therefore, measurements
and
oxidized
primary pre-
cursors of tropospheric sulfuric acid aerosols are needed to determine
the formation and distribution of these aerosols.
the phenomenon of acid
aerosol
particles
in
studied
since
resulting
the
pollution
supplies, marble antiquities, etc.,
to
The role of these
is being
rain
forests,
actively
water
farmlands,
is of major concern.
Turco et al. (1980) have summarized the identified annual sources
Their estimated emission values
of OCS.
fossil fuels,
refining and combustion of
chemical
natural
decay
processes,
0.2
1-5 Tg yr- I from the photo-
and manmade
conversion of natural
Tg
yr-1
from the
include 1-9 Tg yr-1
from
CS2
to OCS,
and
natural
1 Tg yr
- I
from
agricultural
fires,
and smaller contributions from gasoline consumption, cigarette
smoke,
kraft
global
estimate
mills,
and
volcanoes,
of 1-10
Tg
yr-1
action of CS2 with OH and the
fumaroles.
of OCS assumes,
lack of any
This
total
however,
significant
ation in the fluxes of OCS from natural environments.
annual
rapid
diurnal
re-
vari-
The tropospheric lifetime of OCS is uncertain and estimates range
a
from
few
1978;
Atkinson et al.,
et
Turco
1980;
al.,
to
months
1978b;
Kurylo,
1978b; Ravishankara et al.,
1978 and Kurylo,
debate (Atkinson et al.,
The most recent
1980) over the reactivity of this compound with OH.
by OH
attack
to
inert
1980)
(Ravishankara et al.,
measurements
in
relatively
imply that OCS is
Once
troposphere.
the
been
has
There
1981).
Johnson,
1981;
al.,
et
Ravishankara
1980;
Sze and Ko,
1970;
Taube,
and
(Breckenridge
years
nine
OCS
reaches
the
stratosphere, however, it becomes susceptible to photodissociation by
solar
readily
are
dissociation
to
formation of the massive sulfuric
and
later
suggested
to be
on
large
increases
important
atmospheric
in
enhancement of the Junge layer.
in
the
Crutzen
OCS
would
oxygen,
to
OH,
lead
1973)
particular
to
a
the
the Junge
formation of
in
or
acid
sulfuric
on Venus (Prinn,
noted
this
by
to explain
suggested
first
acid clouds
1976).
(Crutzen,
earth
layer
molecular
ultimately
and
SO2
This process was
particles.
aerosol
(HO2 )
radical
hydroperoxyl
by
oxidized
produced
atoms
sulfur
The
radiation.
ultraviolet
that
significant
A thickening of this layer would have
important implications for the earth's radiation balance (Junge, 1963;
SCEP, 1970) and thus for the global climate.
Therefore, it is obvious
that measurements of the concentrations of OCS are required to help us
understand
the
formation
of
stratospheric
sulfuric
acid
aerosols
caused by the flux of this gas from the troposphere.
The first step in
understanding
the contribution of a particular
sulfur gas to the global sulfur cycle is
sources and sinks.
The
and
sinks
these
sources
second step is
to identify and quantify its
the further
investigation of
to understand their detailed mechanisms
and
thus
to understand
sources,
it
their sensitivity to perturbations.
is expected
that
anthropogenic
sources
In
are
studying
more
easily
analyzed than biogenic sources.
In particular, the detailed chemical
and physical
processes
in
steps in
industrial
many cases already fully analyzed.
more complicated.
occurring,
often
There
are
are
readily definable
Natural
sources, however, are
chemical and microbiological
simultaneously,
and
not
all
of these
processes
processes
their spatial and temporal variability are well understood.
lation of a finding
vironments
in
the
on a global
natural
scale
environment
therefore
and
or
Extrapo-
to other
similar en-
a more
quantitative
requires
understanding of the chemical and microbiological processes involved.
Quantitative studies of the natural sources of CS2 , OCS, (CH3 ) 2 S,
and H2S are in their infancy.
emission
from
a
salt
Goldberg et
al.
using
laborious
more
Gas chromatographic measurements of H2 S
water
(1979).
marsh
of,
for
wet
example,
collection of H2 S as
mentioned earlier in
involved
required.
accurately
global
are
chemical
silver
this
Measurements
the
sulfur cycle.
and
1978).
been
filter
reported
matte
by
While
filters
complex
that
date
simply
are
contribution
of
identified sources for these gases.
many
the
the environments
more
too
reduced
There may exist very
for
these studies and those
section are all important,
to
techniques
These techniques involve the
nitrate-impregnated
silver sulfide.
sufficiently
define
recently
Previous measurements of H2 S were obtained
(Jaeschke, 1978 and Slatt et al.,
use
have
few
in
sulfur
important
studies
number
gases
and as
are
to
to
the
yet
un-
For example, Hanst et al. (1975),
Maroulis et al. (1977), and Torres et al.
(1979) have established the
ambient tropospheric distribution of OCS, but there has been no systematic
study of potential
gas.
These gaps
natural
and
anthropogenic
sources
of
in our knowledge are of sufficient extent
this
and
im-
portance that a clear need exists to continue to initiate new experimental studies.
Consideration of these needs was foremost during the planning of
the
research
reported
marsh to determine
OCS and H2 S,
here.
The
systematic
study of a salt
the diurnal and seasonal behavior of the
and thus their
contribution
ducted
gases.
specifically
and
generation
Institution of Oceanography,
to monitor
several
for field studies which were con-
the measurement
standard
1979-January 1980).
1979
for
Analytical tech-
of
these
two
reduced
sulfur
In cooperation with Dr. Ralph Cicerone, preliminary instrument
development
Scripps
and optimized
fluxes of
to the global sulfur cycle,
was identified as the central goal of this research.
niques were developed
water
studies
UCSD,
were
carried
La Jolla,
at
California
the
(June
Field studies were-conducted during the summer of
pH and
the diurnal
variation
of dissolved oxygen
shallow salt water environments near La Jolla,
micrometeorological
out
California.
in
A
flux study using adsorption traps and in situ wind
measurements was proposed to intercompare with a chamber method used
by
investigators
at
Hole, Masschusetts.
of
1980
included
the Marine
Laboratory
(MBL)
in
Woods
Field studies conducted at MBL during the summer
exploratory
and simultaneous measurements
above the marsh surface.
further
Biological
developed and
measurements
of OCS,
H2 S,
of wind speed profiles in
and
(CH3 ) 2 S
the first 2 m
Instrumentation and sampling techniques were
finally completed
at
the
National
Center
for
Atmospheric Research (NCAR) in Boulder, Colorado (October 1980-October
1982).
The
field
studies
through
the
courtesy
of
Wallops Island, Virginia.
reported
the
in
this
NASA/GSFC
thesis
Wallops
were
Flight
The diurnal behavior
of the
conducted
Facility
at
fluxes of OCS
and H2 S from a Wallops Island salt water marsh was determined through
experiments
conducted
weekly
in
August
and
1982;
relative
(but not absolute) CS2 concentrations were also determined.
The in-
fluence of light
the
intensity,
soil
rates of emission of OCS,
September
temperatures,
and soil moisture
upon
H2 S and CS2 were
also monitored.
Air-
craft measurements of OCS and CS2 mixing ratios (20-26 kft) were conducted
1982,
San Juan,
between
through
NASA/Wallops
the
Flight
courtesy
Puerto
Rico
of the
Facility.
and
Albany,
NASA/Langley
Chapter
2,
Research
which
description of the analytical instrumentation.
New York
follows,
in
Center
July
and
contains
a
Chapter 3 contains a
description of the field sampling techniques and the sample collection
and analysis procedures which were developed and routinely employed to
determine the fluxes of OCS and H2 S.
studies conducted are presented
sulfur
cycle
is
discussed
in
in
The results of the various field
Chapter 4 and,
Chapter
5
in
light
finally,
of
from the experimental work described in this thesis.
the global
the conclusions
CHAPTER 2
ANALYTICAL INSTRUMENTATION
A TRACOR 560 Gas Chromatograph (GC) equipped with a Flame Photofilter, along with a
metric Detector (FPD) and a 394 ±5 nm band pass
integrator, comprised the analy-
SPECTRA PHYSICS SP4100 programmable
tical instrumentation employed to identify and quantify concentrations
of hydrogen sulfide (H2 S),
carbonyl sulfide (OCS), and carbon disul-
fide (CS2 ).
Separation of these sulfur gases was accomplished using a
column made
of
(Thornsberry, 1971;
tubing
was
Pearson and Hines,
80/100 mesh
on
composed of
polymer
is a porous
Porapak-Q
Porapak-QS.
(6' x 1/8")
5% DC QF-1
acid-treated,
packing with acetone-washed, phosphoric
prepa-
oven-dried before
and
serially washed with acetone and methanol
(DUPONT)
Column
1977).
FEP Teflon tubing
following steps:
ration included the
Teflon
Porapak-QS-packed
treated
specially
ethylvinyl benzene cross-linked with divinyl benzene to form a uniform
structure
of a distinct
pore
(Dow Chemical
work with highly reactive
surface
support
the
compounds
sulfur
chemisorption.
surfaces;
acetone
Acetone
wash
is
Silanization or treatment with phosphoric
enhance
material.
silicone
used
to
followed
is
silanization re-
because
clean
by
the
column
treatment
with
acid to minimize adsorptivity caused by the acetone wash.
phosphoric
to
Company, Freeport,
Porapak-QS, the silanized version of Porapak-Q, is chosen for
Texas).
duces
size
the degree
silicone
to which
acid is routinely employed
oil
adheres
to the support
The Porapak-QS was then coated with 5% 2-1098 DC
oil.
QF-1
was
used
as
improved H2 S/OCS peak resolution.
the
stationary
phase
and
QF-1, a
provided
Following chromatographic separation, eluting compounds are combusted at
the
FPD.
molecular sulfur,
Sulfur-containing
S2 *.
samples
give rise
to excited
Theoretically, it is only the light given off
by the decay of S2 * which is monitored
by the
photomultiplier
tube
(PMT, EMI-GENCOM #9924A) abutting the detector cell:
.
S2 * + S 2 + hv (394 +5 nm)
If
this were universally true,
a square
law relationship would always
be observed between concentration and GC response.
560 GC provides
a "square
root" mode option,
the use of which impli-
citly assumes that such a relationship exists.
fur
photometric
priate
for
the
response
response versus
law.
Use of the TRACOR sul-
linearizer was however
analysis of OCS or
CS2 because
concentration curves
Indeed, the TRACOR
did not
shown to be inapprothe
slopes of
follow an exact
these
square
Use of this "square root" mode may be appropriate for H 2 S, which
was observed
to routinely yield calibration
mately
However,
2.0.
reliable
analysis
curve
should
slopes
only be
of approxiperformed
in
the "+ polarity" rather than the "square root" mode.
It is reasonable
to speculate that
for OCS
the deviation from a slope of 2.0
and CS2 ,
or for very low concentrations of H2S results from flame kinetics considerations or from column adsorption or conditioning effects.
temperature
and carrier
and flame gas mixtures
Column
were both observed
to
influence this relationship for OCS.
The PMT's signal (anode current)
is
relayed to the GC's electro-
meter where it is converted to a voltage; the GC response is then out-
put to the SP4100 integrator.
is
that the GC response is
the
electronic
signal
limited by the GC attenuation setting.
exceeds
the electrometer saturates
an artifact.
in
the
This
range
(and
be
trations.
and
over the
Thus,
appropriate
to
and,
in
lyses.
The
GC calibration
sponse
versus
fact,
standard
with
the
concentrations.
sample
concentrations
chamber
were,
of
adequate
This
resulted
values
enabled
than
routinely
in
sample
often
for
at
chosen
concen-
are
unre-
following
generation
ana-
of GC
re-
various
attenuation
to
span
anticipated
in
calculating
interpolation
extrapolation
possible.
wherever
the air which entered the
obtained
by
extrapolation
of the TRACOR
controlling
devices
changes
carrier
in
changes in laboratory temperature.
over typical
of con-
flux
due
to
See Chapter 4.)
serious limitation
flow
involved
curves
of the sulfur gases in
however,
is
of the GC
settings)
approximate
GC's stability
procedure
rather
calibration
concentrations
concentration
their extremely low values.
Another
the
This
signal
Consequently, initial samples must
high
concentration
sample
(Concentrations
disturb
recorded
attenuation
determine
unexpectedly
solved,
settings
the corresponding
for samples.
sacrificed
If
the capacity of a particular setting,
limitation requires careful
centrations expected
routinely
A serious drawback of the TRACOR 560 GC
laboratory temperature
for
and
560 design
carrier
flame
and
gas
is
flame
flow
the
lack
gases.
rates
with
The GC response was fairly stable
variations
between
18 and 23"C.
However, when temperatures deviated from this range, particularly when
temperatures rose above 24°C, the GC response changed.
the
response decreased
with increasing
retention
time,
In particular,
indicating
a
reduction in
During
sensitivity due
initial
significant
to a change
in
the flame gas mixture.
instrument calibration *studies, this
difficulties.
Because
the
GC
behavior
demonstrated
caused
such
poor
response stability, it made little sense to proceed to sample concentration prediction until establishing, with confidence, the detector's
response to various standard concentrations.
No clues were found upon
examining
The
change was
the
instrument's
electrometer.
in species retention
time.
primary
It became clear
observable
upon closer
examination that the GC response varied although the standard concentration did
laboratory
not.
A recording
temperature
changes
injection of the standard.
and
record
thermometer was
chromatograms
simultaneously
with
to document
the
continuous
The GC was automated and programmed to run
continously
While a 2-3*C change did not cause
(>1%
employed
standard deviation) when
over
several
significant
24-hour
response
periods.
instability
temperatures remained lower than 23"C,
the instrument did demonstrate instability with the same 2-3C temperature variation at temperatures higher than 23"C.
modifications
should include housing carrier and
Future instrument
flame gas
flow con-
trollers to assure thermal isolation.
The GC detector response was optimized by regulating carrier and
flame
gas
flows
to
maximize
signal
to
minimizing peak tailing and peak width.
noise
Once
(S/N),
simultaneously
the response was opti-
mized, column temperature could be set to enhance peak resolution and
response, S/N improving with
increasing oven temperature.
The
oven
temperature was selected to resolve H2 S and OCS peaks which coelute at
temperatures >90*C on this column, and partially overlap at 700C < T
< 900 C.
After running
samples
Changing gas
standards with demonstrated
temperature of 700 C, it was
lution with an oven
field
laboratory
were
not
completely
flows did not
resolved
found that
at
this
reso-
desorbed
temperature.
significantly reduce H2 S peak tailing,
so
gas flows were returned to their previously optimized settings and the
column was routinely temperature programmed starting at an oven temperature
of
65°C rather
700 C.
than
This
allowed
for
excellent
peak
resolution.
The
TRACOR
560/Porapak
Doping with a
effects.
QS
small,
column
system
continuous
showed
permeation
conditioning
flow of sulfur
hexafluoride (SF6 ) helped to keep the column conditioned.
However, as
calibration
were
cally
curves
required
were
before
begun,
an
seven
standard
equilibrated
injections
response
(response with a standard deviation of <1%
was
typi-
established
being defined as equili-
brium).
Power interruptions which caused
significant
previous
reduction
response
in
detector
levels
required
flameout episodes resulted
S/N and stability.
a minimum of
without continuous standard injections.
directly onto the column in
four
days,
a
return
to
with
or
It was found that this return
to previous response levels could be hastened
of SF6
The
in
slightly by injections
large amounts.
The major benefit
of this procedure was the improved response stability following bakeout.
During
followed
the
field
for the two
study
at
Wallops
Island
this
procedure
flameout episodes with a significant
was
improvement
in stability.
This allowed sample analysis within 30 hours of instru-
ment
rather
startup,
than
the
previous
equilibrium
period
of
four
days.
The
S/N
remained
relatively
low,
but
the
stability
reasonable estimates of sample concentration to be made.
allowed
The maximum
standard deviation of the GC response was 10%.
When the GC was running without interruption within a laboratory
temperature range of 18-22°C, the stability was enhanced by using an
"instrument bake" mode between periods of instrument use.
lity
achieved
curves
via this procedure was excellent,
being essentially
identical
week
after
The stabi-
with OCS calibration
week.
This
assured
a minimal uncertainty for the predicted sample concentrations.
The TRACOR 560 FPD exhaust
port is
unheated;
consequently con-
densing water vapor causes pressure perturbations to appear in the GC
response.
This problem was eliminated by wrapping
with heating tape.
the exhaust
port
A Variac was employed to maintain heat tape tempe-
ratures to prevent condensation droplets at the port exhaust.
A
Valco
teflon-lined,
10-port
above column entry to minimize
sampling valve
dead volume.
was
mounted
The "injection
point of column entry with the GC was maintained at 65*C.
valve facilitated
sample
sample valve rotor
drive
The
The 10-port
(see Fig.
shaft and
2).
the
A motor was
electronic
mounted
components
capacity
to
Physics
SP4100
operate
external
integrator
functions.
written to control this automated
bration
or
the
sample
with comments
and
is
analysis
programmable
Therefore,
required
to
3 and 4).
and
a
to the
on the GC
the motor were laterally mounted on the GC (see Figs.
Spectra
along
port" or
switching from the standard/calibration mode
analysis mode
just
has
the
program
was
sampling valve in either the calimodes
(the
variable definitions
Spectra
is
Physics
listed
in
program
Appendix
GC SAMPLE VALVE
Carrier
POSITION 1
Sample Loop
Connect Option
Valve
Loop
Sample Out"O
Sami
Standard Out
Carrier
POSITION 2
Sample Loop
Connect Option
Sample Out
Standard Out
Fig. 2
VALCO 10-port sampling valve
wL
t(I
II0
Fig. 3
Automatic sampling valve controller circuit
diagram
yI
rpap~~
1
...
..
..
. ..
--
.
.
..
I
Fig. 4
Photograph of modified sample valve
(Charles Semmer)
. : TT
IV).
This program was utilized
to run calibration
trials,
to perform
linear regressions on the GC response and standard concentration data,
to graph
calibration curves,
ciencies,
and to predict sample concentrations.
A.I.D.
and KINTEK permeation
standards.
in
to calculate
tubes
sample
(PT's)
PT's are constructed by sealing
aqueous
form inside a Teflon tube.
tube at a precise
temperature is
were
used
as primary
the compound of interest
Careful
required
loop trapping effi-
thermostatting of the
to ensure a constant
perme-
ation rate through the Teflon (tubes were refrigerated at 8-10°C when
The PT's were maintained
not in use).
at a constant
temperature of
30°C with continuously flowing diluent (dry, compressed air).
The PT
weight loss over time was monitored using a microanalytical balance to
check the manufacturer's
reported permeation rate whenever
(this
however
was
not
possible
during
the
Wallops
possible
Island
field
KINTEK standard generators were used as secondary standards.
study).
KINTEK markets
a
stainless
cell
with
an
operational
the reverse of a permeation tube
essentially,
which is,
steel
concept
(see Fig.
5).
These devices were used as secondary standards because the permeation
rate, although very stable, cannot be measured directly.
the
absolute
is
level
determined
standard calibration curves
an excellent,
used to calibrate
could
25-1500
be
the GC response.
ppbv
(parts
by
per
the
with
the
primary
OCS cell permeation
However, these standard generators pro-
constant standard
generated
comparison
(the KINTEK-reported
rate was high by about 30%).
vide
by
Therefore,
source and
The range
KINTEK
OCS
billion by volume).
thus were routinely
of mixing ratios
cell
was
which
approximately
Teflon-lined
stainless
TRACE SOURCE m 57S
1IW EMISSION RATE
AS SOURCE PERMEATION DEVICE
maMwuwrrTSWuT-*
(
-S~
le
t**
low a,embly me
shke. )
ASSENBLT
UAIALSS S12 L
ONTAHMDANT
OAS NTA Nr
WsRWUDS MERANE
Fig. 5
KINTEK cell diagram
steel
cylinders
ratios less
were
used
dilution chambers
as
than 25 ppbv.
FMI-type pumps
through the GC sample valve's
system
Fig.
described
7)
in
Fig.
sample
6.
to
generate mixing
were used
to pull samples
loop as well as in
Calibrated
HASTINGS
the dilution
flow meters
(see
and bubble flow meters were used to determine diluent gas and
pump flow rates.
sieve,
Molecular
charcoal
traps
routinely employed
were
in
liquid
At NCAR,
and flame gases.
carrier
gel,
silica
indicator-treated
line
activated
and
with
for
regulators
nitrogen (N 2 ) vent gas was
used as the N2 carrier gas while zero-grade N2 was used in
field.
the
Hydrogen (H 2 ) sources included an AADCO H2 generator or zero-grade H2 ,
sources.
cc
min -
1
.
1300C in
High
counterflow
vapor
water
loops
Sample
1200C < T <
and
(hospital grade)
or breathing
while compressed
were
routinely
with
oven
an
as
a purge gas
from
sample
in
air
conditioned
N2
zero-grade
(He)
helium
ultra-purity
the
was
Nafion
(Nafion
the
air comprised
for
flowing
used
hour
at
used
are
to
at
10-15
alternately
driers
driers
one
air
for
remove
discussed
in
Chapter 3).
In
the
field,
air
and
thermometers or a calibrated
soil
temperatures
were
monitored
using
system consisting of an OMEGA Miniature
Cold Junction, a battery powered, automatic cold junction compensator,
and
four
Chromel-Alumel
thermocouple
Light
circuits.
intensity was
monitored in arbitrary units which could be converted to foot candles
of
incident
meter.
and
to
visible
radiation,
a
using
simple
Liquid argon was used to cryogenically
"scrub"
ambient
air
before
it
photographic
light
trap and store samples
entered
the
flux
chamber.
STANDARD DILUTION SYSTEM
VENT
VENT
SAMPLE
LOOP
VENT
Fig. 6
Standard dilution system
C O = concentration exiting standard generator
fl = flow drawn from generator exhaust
Fl = primary diluent flow
Fj = secondary diluent flow
F = F2 + fl
C = (Co)(fl)/(F 1 )
Regulator
GAS
, I
3int~rIU
itUK
metering
valve
Fig. 7
Flow meter calibration system
Soap -bubble
flowmeter
Standard glass Dewars were used
to contain the
liquid argon used
in
the cryotrap and for sample collection while a larger stainless steel
Dewar was used for sample loop storage.
prior
to its
used
to
regulate
primarily
heaters
entering the cryotrap.
and
controlled
were
temperature
used
monitor
by
a
to bring
the
carbon
the
Drierite was used to dry air
Rotameters
chamber
vane
water
were calibrated and
air
flow rate
which was
pump.
Electric
immersion
to boil
and to ensure
uniform
throughout the Dewar for the water used in desorbing the
frozen samples.
Due
tubing
to
highly reactive
of
nature
and fittings were used wherever
sulfur
the
analytical
components
collection
and
analysis.
Sample
"bendable"
Teflon
tubing
(NACOM)
housed
equipped with Teflon plug valves (GALTEK)
in detail in Chapter 3).
compounds,
or standard
sample
with
into contact
sample
the
used
gases
came
for calibration
were constructed
loops
in
Teflon
aluminum
(sample
tubing
or
of
and
loops are discussed
CHAPTER 3
SAMPLING TECHNIQUES
Tests
of
various
and
adsorption
trapping
cryogenic
techniques
were conducted, and procedures were established for sample collection
and
These
analysis.
three
components
of
the
techniques
sampling
employed in this research are described in this chapter.
3.1
Trapping Tests
atmospheric
Ambient
20 less
the
than
of OCS
levels
limit,
detection
Tracor FPD's
tested
including
trapping
Sieve, Molecular Sieve and
using
nitrogen,
liquid
temperatures
at ambient
Tenax-GC in series,
followed with desorption by heating to 250*C.
trapping
response)
and log
Several methods of sample enrich-
detectable and reproducible signal.
cular
of
Sample enrichment is therefore required to produce a
(concentration).
were
factor
factor of 200
and a
below the range of proven linearity between log (GC
ment
a
pptv,
-500
are
liquid
on Mole-
and Porapak QS
Enrichment by cryogenic
oxygen
or
and
argon
liquid
Teflon shavings of Teflon chips,
Teflon loops containing
glass beads,
were also tested before
the empty Teflon loop was chosen as the most
reproducible enrichment surface.
glass
Tests using Molecular Sieve in Pyrex
tubing with Pyrex wool plugs at room temperature
adsorption efficiency
indicated 100%
over many hours
with no breakthrough
term
(the
"breakthrough" here denotes the presence of the test sulfur gas in the
air stream exiting the trap after an initial
this
air
when
efficiencies
Porapak-QS
Desorption
stream).
in
traps
Teflon
were
tubing
tests,
heated
with
to
period of its absence in
however,
250 0 C.
Teflon 'wool
low
demonstrated
using
While
tests
plugs
resulted
in
breakthrough at room temperature, trapping under cryogenic conditions
demonstrated
100%
adsorption
efficiency.
However,
developed with desorption, possibly due to
Porapak substrate beginning to
high
decompose
Flow studies
temperatures.
the Teflon
after
indicated
problems
again
tubing or the
extended
exposure to
a congealing
effect
from
such exposure.
Sample enrichment
logical
Laboratory
traps.
These
glass tubing,
Molecular
silanized
tests were also
using
P.
traps were
21.3 cm in
Sieve
5A
Pyrex wool
Steudler's
constructed
length,
and
11.5
plugs
conducted at the Marine
Sieve/Tenax-GC
of 6 mm O.D.,
packed
cm
Molecular
with 9 cm
(0.2
(Steudler,
g)
private
4 mm I.D.
(0.8
60/80
Bio-
mesh
g)
Pyrex
60/80 mesh
Tenax-GC
communication).
with
Traps
were preconditioned at 325C for 12 hours with a continuous N2 purge
After sampling, traps were stored in an ice box or in a freezer
flow.
at
-20°C
until
desorption oven
injected
onto
at
analysis,
250°C
at
the
for
which
15
chromatographic
time
s before
column
for all
H2 S,
OCS,
(1980) had reported -80%
the sulfur
CS 2 ,
(CH 3 ) 2 S)
studies
traps.
Calibration
however,
did not
produce
through
indicated
that
suggested
that
sample
for
analysis
(see
the
often
a
were
contents
Appendix
used at MBL).
his sulfur flux study (e.g.,
Molecular
these
the
during
results.
While
the
Sieve/Tenax-GC
resulting
in
reproducibility of
no
of
summer
1980,
lack of break-
adsorptivity was highly efficient,
studies were disappointing,
Tests
for
in
conducted
similar
the
into
placed
adsorption/desorption efficiencies
gases of interest
(CH3 )SH,
were
instrumentation
III for a description of the analytical
Steudler
they
desorption
detectable
the overall
signal.
method
was
±40% at
predicted concentrations with overall trapping
for the
best
(adsorption plus desorption) efficiencies estimated at <2%.
along with
routinely
the
species
caused
FPD
of
The
abundance
of
trapped
desorption
upon
episodes
02
the
onto
This problem was avoided by the use of liquid
were
tests
enrichment
cryogenic
Preliminary
Ar.
liquid
or
interest.
flameout
chromatographic column.
02
caused 02 to be trapped
cryogenic enrichment
Use of liquid N2 in
Switching to liquid Ar in accordance with
conducted using liquid 02.
cause a
however,
an NCAR safety decision did not,
significant
change
in test results.
The
use
of
tubing
Teflon
packed
or Teflon shavings proved to be reproducible
packed
relative
day
best
the
strated
with
Teflon chips
efficiencies
desorption
rather
water vapor:
adsorption
than
repeated conditioning,
loops
<100% efficiencies
The
appeared
to be especially
trapping efficiencies
initially demon-
appeared
to be
However,
fell off drastically
sensitive
-95%
±5%
with good day-to-
inefficiencies.
reproducibility
Teflon sample
(typically
standard deviation for an individual loop)
reproducibility.
These
(-3.8 cm substrate)
trapping
overall
beads
to +7-15% for an indivi-
dual loop, with even greater variability between loops.
loops
glass
unpassivated
with
the
to
due
to
after
with use.
presence
of
fell off by 20 to 30% when H2 0(g)
was present.
The use of empty Teflon tubing was then tested and found to have
much
greater
only
-60-75%
reliability
for
OCS
although
overall
H 2 S.
Again,
and
trapping
these
efficiencies were
<100%
trapping
effi-
ciencies appeared to be due to retention on the loop after desorption
because
tests
showed
no
various
in
for
adsorption
evidence
of
tubing lengths
the attempt
however,
were
efficiencies
breakthrough
(3-25"
(loops
during
immersed in
placed
trapping.
in
series)
Tests
the cryogen)
using
were conducted
to verify the theory of surface effects.
The results,
not
to
significantly
different.
Attempts
clean
up
ambient air for chamber-purging purposes later showed that utilization
of
greater
residence
However,
lengths
time
flow
of
of
tubing
surface
rates
and
varying
flow
does
indeed
-10-250
cc
exposure)
ranging
from
rates
(and
make
min -1
a
in
thus
the
difference.
the
12-25"
tubing lengths showed no significant trapping behavior variance (empty
Teflon tubing sample loop test results are given in Appendix V).
Loop
contents were desorbed simultaneously with sample loop transfer
from
cryogen to boiling water since tests showed
and
peak
broadening
desorption, however,
occurred
with
routinely
resulted
peaks (see Fig. 15 in Section 3.3).
stored
Dewar
without
top-off,
loss
in
liqud
for extended
any
02
that sample decomposition
length
in
of
sharp
heating.
and
Rapid
well-resolved
After trapping, samples could be
or Ar,
periods
(<48
with
hours
-1.5"
flexibility
tested).
Storage
on
in
liquid N 2 resulted in flameout episodes upon desorption presumably due
to leaks at the sample loop Teflon plug valves which allowed room air
to
be
trapped.
Storage
configurations
which
put
the
Teflon
plug
valves in close proximity with Dewar cryogen also resulted in flameout
episodes
extending
(apparently due to leaky plug valves).
the
loop tubing
3"
outside
Teflon plug valves (see Fig. 7).
the Dewar
This was avoided by
before
attaching
the
I'Y!I/L~j
""1;'!"1
1 "18
1:11W
i :iii/li~~:
llS83~1
~il
Fig. 8
Photograph of sample loop in cryogen
(Charles Semmer)
!
Interference
with
H2 0(g),
tests
were
conducted
trichlorofluoromethane
by
(CFC1
3
doping
),
standard mixtures
dichlorodifluoromethane
(CF2 C12), 1,1,2-trichloro-1,2,2-trifluoromethane (CFCl 2 CF 2 CI), nitrous
oxide
(N 2 0),
methane
hydrocarbons
(CH),
listed were
non-methane hydrocarbons
tested
are
soil and grass surfaces.
flame quenching,
Mixtures
air
were
ppmv
and used
(C 2 H6 ),
and
propane
because CH4 and
also thought
(C 3 H8 ).
low-molecular
to be emitted
interference
studies
further
to test
diluted
for
quenching was observed
flame
-10-15
each
quenching,
ppmv
N2 0,
(LINDE))
flame
to
test
mixing
quenching.
quenching was observed
Introducing
for either
so
CFC1
were
weight
from various
for
analysis
containing 0.5% each of CH4 , C2 H6 , and C3 H8
ratios
3
,
gas.
interference
CF2 C12
conducted
Fluorocarbons
studies
(diluted
for
OCS
of
in
-4-7.5
Calibration curves were
run for OCS and H2 S followed by doping with hydrocarbons,
FPD
The
Typically, coeluting hydrocarbons cause FPD
thus necessitating
techniques.
(LINDE)
ethane
with
can also
mixing
from mixtures
and
H2 S.
and no flame
cause
ratios
containing
Again,
no
of
1%
flame
for either gas.
water vapor (see
streams caused significant
sample
Fig.
9)
to standard OCS or H2 S gas
decomposition
for H2 S.
Low levels
of humidity did not cause large losses in OCS or in OCS trapping efficiencies.
Relative humdity values >20%, however, caused almost im-
mediate sample loop icing.
Sample loops were marked
so that the flow
direction during trapping and desorption was the same to minimize loss
during desorption due to moisture.
However,
samples which had begun
to ice still routinely displayed irreproducible behavior.
To elimi-
AO H20 Addition
Option
Tef Ion Tubing
1
I
~
1 0 Gas Stream
..
::
::..........
:::
::::::::::::
................
:...............
:: :::::::::::~
:::................
::: :
:::::::::::::::::.
.................
~tii~~rrtrrt
................
.................
ii~~~i.:~~.ii~,~i
:......... i~~iii~~~ii
........
:::::
:::::..................
Fig. 9
Water vapor addition apparatus schematic
nate
this problem,
used in
Nafion (DUPONT)
tubing driers were constructed
line with sample loops (see Fig. 9).
and
Nafion is a copolymer of
tetrafluoroethylene
and
selective membrane.
To effectively dry ambient air, ultra high-purity
He
was
These
flowed
countercurrently
Nafion driers were
and OCS.
air
fluorosulfonyl
monomer
around
tested
13 strands
acts
as
a perma-
of Nafion
tubing.
for adsorption or desorption of H 2 S
No enrichment or loss was observed from standard mixtures of
containing
ambient
levels
containing -1 ppm of H2S.
of OCS
(-500
be enriched in its sulfur content.
effectively
pptv)
or
from
standards
After considerable use, however, residual
effects became obvious when air run through
be
and
reconditioned
the traps was
found to be
It was found that the driers could
between
samples
by
purging
the
Nafion
tubes with He.
Tests were routinely conducted to check for OCS losses
on
driers:
the
Nafion
evidence of
loss,
and
loss;
tests
tests
run
Tests
run
after
run
after
an
after
-150
with
considerable
use,
Nafion
hours
use
hours, however,
additional
this had increased to a loss of -45%.
>100
-75
hours
use
showed
no
showed
-40%
showed
that
This research suggests that,
tubing does
not
remain
inert
to
OCS.
Reconditioning efforts to restore the driers to their initial troublefree behavior were unsuccessful.
3.2
Sample Collection
The
sample
followed during
salt water
marsh
collection
the
procedure
field study of the
(conducted
at Wallops
in the block diagram in Fig. 11.
which
was
developed
for
fluxes of OCS and H2 S
Island,
Ambient
Virginia)
air was
pulled
is
and
from a
outlined
through
a
carbon vane pump and its exhaust entered a regulating rotameter or was
Nafion
Sample Gas Stream
t
I
Helium
Counterf low
Fig.
10
NAFION drier schematic
SAMPLE COLLECTION
AMBIENT
AIR
CHAMBER
VENT
PUMP
VENT
SAMPLE LOOP
ROTAMETER
DRIER
DRIERITE
I
Fig. 11
IC
Sample collection schematic
Aa
a, a ^100
The regulated
vented.
flow (4-5 X min -1 ) was passed through a series
of Drierite-filled plastic cylinders before the air passed
through a
copper tubing coiled
series of two approximately 50' lengths of 1/4"
and immersed in liquid argon.
Drierite
vapor
from
(anhydrous
the
the
entering
stream
air
sulfate)
calcium
was
were
in
cylinders
primary
and
air
each
parallel,
The Drierite-filled
stream
the
of
each
over
passed
three
dry
a
air
flow was
of
series
streams
to
connected
was
which
three
flow entered
regulated
the regulated
Thus,
secondary cylinder.
the
that
so
configured
this
Without
cryotrap.
precaution, the cryotrap iced up within minutes.
cylinders
remove water
to
used
split into
a
thirds
Drierite-filled
two
to
rejoined
enter
the
cylinders
before
cryotrap.
The three "primary cylinders" contained both indicating and
non-indicating Drierite for ease in establishing when the Drierite was
exhausted.
However, this process was not
water vapor
from ambient
up
about
after
"primary
-14
hours
100% efficient
in removing
as. the cryotrap routinely began to ice
air,
-4 £ min-1.
at
The used
Drierite
in
the
cylinders" was replaced with fresh Drierite, and the "icing"
cryotrap was replaced with dry lengths of copper tubing before total
icing occurred.
It took approximately
15 minutes
to exchange fresh
for used materials, and the chamber entrance was sealed during this
brief purge flow interruption.
After
passed
air
exiting
the cryotrap,
the air
through tubing which was immersed
then
flowed
through
a
second
was
warmed
somewhat
as
in a warm water bath.
rotameter,
used
to
identify
it
The
any
changes in the flow through the series of traps and driers and to confirm the flow rate before it entered the chamber.
Soda
(Adams
lime
et
al.,
1980)
Drierite and the cryotrap in order
was
in
put
line
between
gases,
to strip sulfur
the
primarily
This resulted in the cryotrap icing up
OCS and CS2 , from ambient air.
Although the soda lime
in about 5 hours with a 4 p min-1 purge flow.
used alone was fairly quickly exhausted, it was able to scrub ambient
normal
of its
-10%
of all but
air
The use of soda lime
OCS level.
was discontinued because it caused cryotrap icing, it did not remove
enough OCS when used alone, and it required the use of a Nafion drier
on chamber inlet samples.
The chamber dimensions were 0.41 m x 0.41 m x 1.37 m, with an inThe chamber was open-bottomed and was
ternal volume of 230.2 liters.
constructed of 1/8" sheets of abrasion-resistant TUFFAK CM-2 polycarand
bonate
12).
Fig.
non-volatile,
The
material
polycarbonate
RTV
#3145
CORNING
DOW
chosen
was
adhesive
(see
it,
like
since
Teflon, has been shown to be relatively inert to sulfur gases (Adams
et
al.,
1980)
and
since
preliminary
chamber proved to be unsuccessful.
suitably-sized
exit
a
through
the ground which becomes
with
thin-film
a
Teflon
(These initial tests showed that,
port,
without
tests
the
chamber
path
purge
of least
air
will
exit
resistance when
positive pressure conditions dominate inside the Teflon chamber.)
The
polycarbonate material is clear, like glass, and sturdy, which facilitated sealing the chamber in the marsh soil.
Tests were conducted to
ensure the absence of leaks around the chamber-soil
ensure
that
purge air exited
through
the chamber
interface and to
exit.
A
smaller,
four-sided polycarbonate chamber was constructed in a similar fashion
for
laboratory tests
to determine
the degree to which the materials
Fig. 12
Fig. 12
Polycarbonate
flux chamber
Polycarbonate
flux chamber
used in
chamber construction
adsorbed or desorbed the sulfur gases of
After a curing and equilibration period,
interest.
this
test chamber
was purged with an air standard containing -10 pptv OCS and a small
amount of CS2 .
A portion of the air leaving the chamber was trapped,
and analysis showed no significant change in either the GC response or
the
concentrations
predicted.
This
confirmed
an
absence
of signi-
ficant outgassing from or adsorption onto the chamber materials.
addition,
there
no
unidentified
As noted, Adams et
quenching.
flux
were
chamber
in
their
field
al.
peaks
or
indications
In
of flame
(1980) also used a polycarbonate
studies,
and
their
surface
reactivity
tests agree with these findings.
Fan blades (3.25" x 4.75") and a rotor shaft were machined from a
block of Teflon and attached with #3145
RTV adhesive.
A metal shaft
connected the Teflon fan to a motor mounted on an aluminum frame over
the chamber.
Teflon washers
around the Teflon rotor shaft
were
so
used
that
to
seal
all internal
consisted either of Teflon or polycarbonate.
was to circulate chamber air.
were made
inside
the
chamber,
the
chamber
opening
chamber surfaces
The purpose
of the
fan
Although no wind velocity measurements
typical
daytime
winds
were
reasonably
well imitated as evidenced by comparing grass-top motion both inside
and outside the chamber.
With an
4.2 X min-1,
internal
volume
of 230.2
£
and a typical purge
the chamber residence time was 54.8 minutes.
flow of
Once set in
the
soil with all connections made, the chamber, mechanically stirred
and
continuously
equilibrate
flushed
with scrubbed
ambient
air,
was
allowed
for 2-3 hours at a purge flow rate of 4-5 X min - 1 .
to
After
this
initial
chamber
equilibrium
was
collected
period,
the
air
simultaneously
entering
and
and
stored
exiting
for
the
laboratory
analysis to determine the amount of OCS, H2 S, and CS2 generated within
the chamber.
the
Liquid
argon was used
samples which were
pumping rates were
to cryogenically trap and store
pulled through
constant
the loops by FMI pumps.
and were routinely checked
with a bubble
flow meter to ensure knowledge of the sample volume collected.
collection was
conducted
period of 25 hours.
air.
Light
50-60 minutes
Sample
every other hour over
Typical sample volumes were 1.5
the
studies,
a loosely-woven,
chamber,
were
also
monitored.
light-weight
which helped to reduce
During
the
white cloth was used
surface
evaporation
densation on the cooler interior chamber walls without
a
to 2 liters of
intensity and air and soil temperatures, both inside
outside
the chamber
for
The
last
to
and
six
shade
and thus
con-
significantly
reducing the light which reached the chamber interior.
3.3
Sample Analysis
A description of the analytical instrumentation which was used to
analyze samples was given in Chapter
cluded
calibration
analysis.
H2 S.
The
of
the
GC response
GC
2.
response
The
both
analysis
before
was initially calibrated
Using the KINTEK Standard Generator,
ppbv
and after
sample
for both OCS and
an OCS standard was gener-
ated by regulating the diluent air flow rate:
=
procedure in-
(P + P)(PR)(0.975)(1000)
c
P - PH20
273
(F)
760
T
=
Pc
where
cell
pressure
= laboratory pressure
(read
pressure
converted
psi,
(torr);
T
=
torr);
P
(my min-1 ); PH20 = water
flow rate
temperature
laboratory
to
(nZ min-1 ), 0.975
(torr); PR = permeation rate
refers to 97.5% OCS cell gas; F =
vapor
in
(K).
All
flow
measurements made using the bubble flow meter were corrected for water
vapor pressure, and F was converted to standard cc/min, (P = 760 torr,
T = 0°C) in all calculations.
Using the A.I.D. Standard Generator to house a permeation tube,
an H2 S standard was generated by regulating the diluent air flow rate
around the tube:
(PR)(k)(1000)
P - PH2 0
273
ppbv
where
PR
permeation rate
=
molecular weight.
T
(F) (
760
(ng
min- 1 )
and
k
=
constant
throughout each
injected amounts
The flame gas flow
were recorded in the concentration units ppbvml.
were carefully monitored
22.4/
the volume of standard in the
Taking into account
GC sample valve's sample loop (0.93 x P/760 std cc),
rates
=
calibration
and ana-
lysis period. Rotameter settings were chosen as a result of responseoptimization studies:
H 2 at "85"
and air at "125"
meter calibrations in Appendix IV).
std
cc min-1
was
The carrier N2 flow rate of 30
also carefully monitored
rates appeared to be caused by changes
than actual setting changes.
during
OCS
calibrations
for
(Tracor 560 rota-
although changes
in ambient
in
flow
temperature rather
The Tracor 560 GC was run isothermally
convenience
since
tests
had
shown
no
response change with temperature programming.
temperature-dependent
demonstrated
Therefore,
the
same T-programming
H 2 S, on the other hand,
column
conditioning
regime which
was
used
effects.
for sample
analysis was required for calibration of the GC H2 S response:
temperatures
30°C min -1
were held at 65*C for
for 2 min to a final
for
9 minutes.
The
Tracor
FPD
6 min followed by a ramp rate of
temperature of
Thus, chromatographic
temperature
was
bration and analysis periods.
GC oven
125 0 C which
was held
analysis required 17 minutes.
constant
at
130*C
during
all
cali-
Retention times varied slightly between
calibration and sample analysis chromatograms due to the time sequence
used for sample desorption.
were
begun simultaneously
switched
at
0.5 min.
desorbed
onto
the
boiling water.
0.5 min in
At
column
Thus,
compound
The Spectra Physics and GC T-programming
the valve configuration
and
this point,
by
rapid
transfer
retention
(see
times
ation.
typical
from
liquid
>10,000
(at
1).
period
any particular
OCS cali-
consisted of a
of
four
GC attenuation
standard devi-
When regression analysis on the >4 calibration points showed a
<0.995,
additional
points were run to assure
GC response stability before beginning sample analysis.
min.
to
standard
each run an average
GC response reproducibility was (fl%
correlation coefficient
OCS
argon
Typical
13 through 16.
run at the start of an analysis
For a GC response
setting),
Table
Figs.
minimum of four standard concentrations,
trials.
loop contents were
sample chromatograms reflected this additional
and sample chromatograms are shown in
bration curves
the sample
automatically
standards were run
The
entire
As mentioned,
isothermally, and each chromatogram took 4.5
calibration
curve
therefore
required
2-3
hours.
Table 1
Chromatographic Retention Times
Gas
Standard Retention Time
(min)
Sample Retention Time
(min)
H2 S
2.02
2.79
OCS
3.08
3.86
CS2
13.30
13.79
OCS STANDARD
INJECT TIME 29
17:57:29
mmmmmmm
2.98
PK#
RT
Area
Height
BC Code
1.
2.98
137152.
4157.3333
1.
INJECT TIME 29 18;02:04
.(_
2.97
PK#
RT
Area
I.
2.97
137964.
INJECT TIME 29
Height
4164.
BC Code
1.
18 :06:38
2.97
PK#
1.
RT
Area
Height
2.97
138888.
4197.3333
Fig. 13
OCS standard chromatogram
BC Code
1.
H2 S STANDARD
INJECT TIME 29
20:40:14
.1.97
PK#
RT
Area
Height
I.
1.97
152352.
6330.6667
INJECT TIME 29
BC Code
1.
21:02:10
1.93
PK#
1.
Area
RT
155386.
1.93
INJECT TIME 29
Height
BC Code
1.
6485.3333
21:25:09
1.96
PK#
RT
Area
1.96
157083
Fig. 14
Height
6528.
H 2 S standard chromatogram
BC Code
CS 2 STANDARD
INJECT TIME 27
19=16 17
13.31
PK#
1.
RT
Area
13.31
48007.
INJECT TIME 27
Height
842.66667
BC Code
1.
19,34:02
13.30
PK#
RT
Area
1.
13.3
46149.
Fig. 15
Height
82.0.
CS2 standard chromatogram
BC Code
LOOP # 33
REM
INJECT TIME 25 06:34:01
2.79
-3.86
AT= I
9.33
13.79
Pk#
RT
Area
1.
2.
3.
4.
2.79
3.86
9.33
13.79
6237.
98673.
7903.
51390.
Height
228.
2882.6667
162.66667
764.
GAS
H2 S
OCS
CS 2
average of
points, each run an
analysis
required
to various
standard
the Wallops
For
"Air in"
fol-
Island weekly flux study,
which
they were
this
typically
At approximately 20 minutes per sample, analysis
involved 26 samples.
Occasionally "air out"
8.5 hours.
the baseline to drift,
an
necessitating
bakes
Column
column.
the order in
also run in
lowed by "air out" samples,
the
the samples
which they were collected,
the order in
samples were analyzed in
took about
H2 S concentrations,
some-
the GC re-
After determining
OCS and
When GC
were
curves
H2 S
Typically, samples were analyzed as follows:
were analyzed.
collected.
stability,
points.
with only three
times checked
sponse
week-to-week
demonstrated
response
took a minimum of one hour.
each point
took about 3 minutes,
re-equilibration
and
oven cooling
and
17 minutes
Since chromatographic
trials.
three
four
of
of a minimum
consisted
also
curves
calibration
H2 S
Initial
were
sample contents caused
interruption
conducted
at
an FPD
to recondition
temperature
of
165"C and an oven temperature of 150*C for 1-2 hours as required.
After
sample
analysis
of 4 points
bration curve
had
was run to determine
observed
However,
was
this
when
the
not required
agreement with
curves
was
followed
GC response
as
run before
by a
and
after
the
second
H2 S
was highly stable,
repeated tests
the first.
a
showed
Composite
sample
sample concentrations (see Fig. 17).
OCS
cali-
GC response
drift
second
When a change in the GC response
during the >8.5 hr analysis period.
was
completed,
been
it
calibration
a second H2 S curve
would be
calibration curves,
analysis,
were
curve.
used
in excellent
made
up of
to determine
Composite OCS calibration curve
Fig. 17
SEPTEMBER 23-24, 1982
FIELD STUDY
COMPOSITE OCS CALIBRATION CURVE
+
2.0
I
me
I
I
j
I
I
III
I
+
I
I
a
_m
+
2.5
+
+
mm
I
3.0
3.5
7. 3
I
'
' I 1
1
7.5
8.0
8.5
LOG R* GCAT
CALIBRATION CURVE
Pt#
Conc
1.
2.
3.
4.
5.
6.
7.
8.
847.2
540.4
297.9
104.3
432.9
174.3
82.1
823.2
R*GCAT
Log C
Log R
198198326
84004003
29702977
5598865
52650194
11945380
3561230
183992444
2.928
2.7327
2.474
2.0182
2.6364
2.2414
1.9143
2.9155
8.2971
7.9243
7.4728
6.7481
7.7214
7.0772
6.5516
8.2648
Curve: R*GCAT = 1940.0071*conc** 1.6995984
Corr. Coeff.: 0.9990345
Concentrations
was
performed
on
were
the
predicted
log
(GC
as
follows:
response
x
A
GCAT)
linear regression
and
log
(standard
concentration) data, giving the relationship
Log R
=
a + b log C
or
10aC b
=
R
and, thus
R =
where
(GC response)(GC
Next,
ppbvml.
this
/b
(R/l0a)lI
=
C
attenuation)
C = concentration
and
initial concentration value must be adjusted
in
for
sample loop trapping efficiencies (e) and sample volume (v):
Cppbvml/(e)(v)
Oppbv
where e = % efficiency/100
from
the
trapping
rate
and
and
the
the
sample volume
trapping
closely monitored during sample collection.
to
the
tration
fact
that
during
this
the
concentration
trapping
measurement of concentration.
period,
time,
(ml)
is
calculated
both
of
which
are
The bar over the C refers
represents
rather
the
than
average
an
concen-
instantaneous
CO was used to denote the concentration
in the air which entered the chamber, while C refers to the concentration in the air which exited the chamber.
to the amount of gas generated
within
Thus, C - C0 = AC refers
the chamber.
The
calculated from the concentrations measured as follows:
fluxes
were
d(C-C )
u(C-C o)
E
AH
AH
dt
H
H
where C and CO refer to the instantaneous concentrations,
t = time,
= chamber purge air flow rate, A = chamber
surface area,
H = chamber
height;
instantaneous
flux of gas
AH = chamber
volume,
from the marsh surface.
in the chamber
and E = the
The concentration
(C O ) of OCS,
CS 2 , and H2S
thus dC0 /dt = 0.
purge air was essentially constant,
Defining AC = C-C0,
dC
dt
I
dC
uAC
AH
t
tI
uAC (t
uAC
AH
2
C 2 - Ct 1
E
H
uAC + AH
H
=
dt
tl ) + E (t
-t
1
H
2
1
)
where E refers to the average flux of gas during the trapping period.
Defining AC = Ct 2 - Ctl
and At = t 2 - tl,
,
E
The errors involved in
R
=
dC
dR
aCx
S(a
-
HAC
At
+ uAC
A
the calculation of E are as follows:
C=
;
(a
/x
(2)a
- l
/x
/x)
(/x)
R
R
=
a-1/x R/x
x-1)
x
u
C
R
65
dC
da
dC
dx
=(-1/x)(a
n
-
1 C
x a
)(R 1/
R R
)(-)
1/x
- -
In(-R)
-
dC
AC
C
((
(da
I C
xR
C
)2 )I /2
dC
d C
dC
2
2
1/2
((
SAR)
1/2
Ax
(I
x
x R
C±AC
=
a
x
AC/C
(C±AC)/(e±Ae)(v±Av),
=
)
AC/C + Ae/e + Av/v
and
C0 AC
AC0/C 0
= (Ct0 AC0)/(e+Ae)(v±Av),
((Z± AC) - (c
E ± AE
sample
AEc 0 )) (u
+ Ae/e+Av/v
± Au)
A
2
2
((Ct2 ± At 2 ) -
The
±
= AC /CO
concentrations
and
1
t
1
At C ))
1
the corresponding
values are presented with their errors in Appendix VI.
calculated
flux
CHAPTER 4
FIELD STUDIES
The results of the
chusetts,
and
field studies conducted in
Virginia,
along with
the results
California,
of
aircraft
Massa-
measure-
ments of ambient atmospheric OCS and CS2 concentrations, are presented
in this chapter.
4.1
Dissolved Oxygen and pH Measurements
Preliminary work conducted at the Scripps Institution of Oceano-
graphy, La
Jolla, California, included
diurnal variations in
salt-marsh
monitored
dissolved oxygen in
and a diurnal
dissolved oxygen
(see Fig.
18).
concentrations with sunlight was
several
In
and mud-flat environments.
Penasquitos Marsh
field studies
to monitor
the
Southern California
particular,
cycle was
pH values
identified
in
were
the
This variation of dissolved oxygen
also observed in the
Bataquitos Mud
Flat and the Mission Bay Marsh.
4.2
A Micrometeorological Flux Study
In
Massachusetts,
measurements
trations above regions of the
of
reduced
Institution were planned.
systems
the
of
Marine
gas
Sippiwissett Salt Marsh near
Hole Oceanographic
Center
sulfur
Scientists
Biology Laboratory
at
concen-
the Woods
at the Eco-
Woods
Hole
had
expressed an interest in this investigation, and collaborative studies
with
P.
Steudler
at that
laboratory were conducted
during the
summer
of 1980.
A
preliminary
conducted on April
profiles,
micrometeorological
11,
1980.
gas
sampling
experiment
was
Measurements taken included sample gas
wind speed to a height of 2 m above ground,
wind direction,
I
I
I
'
- 30
29
- 28
- 27
/
I
- 26
-
D02
I
25
- 24
S23
22 4
- 21 C
--20
22
21
TWATER.......
-'I
-
TAIR
//
6
7
July 1979 Panesquitos Marsh field studies results
8
TIME
9
I0
(7/13/79)
-
20 -g
19 o
18
7/12/79
7/52 /79
Fig. 18
/
"
- 18
- 12
7/11/79
7/55I/ 79
I
'
light
intensity, air and peat
Reduced sulfur gases were trapped using three
vations.
"60/80
Molecular
Tenax-GS"
5A-60/80
Sieve
traps
sampling
and 2.0 m on a
from 0900 to 1800,
Measurements were taken
3 m tower.
foil-wrapped
1.5 hr
per
1.25 m,
The traps were positioned at 0.75 m,
period.
sky obser-
and
and tide
temperatures,
permitting the
study of gas and wind data in conjunction with light intensity, tempeSample collection and gas ana-
rature, and hydrological differences.
#41
had been calibrated
anemometers
Generator
the Aeronautics
in
and
Fluxes were cal-
wind tunnel at MIT.
Department's 5'x7'
Astronautics
The three Maximum
Appendix III.
lysis was carried out as described in
culated using the following general equations:
=
- K[M]af./az
K
-
FS
u,
where
i,
-
[M]
2.56
(2)
ku*z
(3)
k(z + z0 ) au/az
molecules/m 3 ,
fi
mixing
of
ratio
species
k = 0.4 (Von Karman's constant), u* = friction velocity, u = mean
wind speed,
z = height above ground,
order of magnitude
20
E25
=
(1)
cm grass
cient,
K,
is
< actual
-2 cm).
and z0 = roughness length (-one
height of roughness
elements,
which
for
Determination of the eddy diffusion coeffi-
by use of the logarithmic wind profile
(Eq.
3)
included the
neglecting
buoyancy.
Variation of wind speed as a function of time and height is
presented
assumption
graphically
of
(see
neutral
Figs.
stability
19 and 20).
conditions,
Gas data for the reduced
sulfur
Anemometer 2, i.25m
.
O
5 -
*
.*
:'nAmometer
E
E
,0.75m
5-
.
4 -"4
/ Anemometer 3, 2.Om
-
..
..*
....
'Anenomeler 3, 2.0 m
3 -
.**
o
-
2
I
00
0. 1400
1000
1200
1400
5600
80
I
I
1600
1800
1000
1200
TIME
Fig. 19
April 1980 Sippiwissett Salt Marsh
field study wind speed measurements
,
1400
1600
1800
TIME
Fig.
20
April 1980 Sippiwissett Salt Marsh
field study average wind speeds
gases carbonyl sulfide, hydrogen sulfide, and dimethyl sulfide are not
presented here due to outstanding questions about the enrichment techof
discussion
(see
used
nique
au/az was poorly determined
Chapter 3) and because it was found that
vertical
a
within
(1974)
Priestley's
spatial
resolution
formula
to estimate
of
2
only
convective
use
The
m.
of
fluxes by equating
eddy diffusivity with the eddy diffusion coefficient
sulfur gas
in
traps
Sieve/Tenax-GC
Molecular
for
sensible heat was also explored:
KH
(aT/az + r)
However, the
hz 2 (g/T 3T/z + rf)
=
-(H/hp
atmospheric
the
is
r
where
=
lapse
1 / 2
c )2 1 3(Tg)1/3
rate
(4)
(5)
4/3
and H represents
instrumentation to determine
flux.
aT/az accurately within a
spatial resolution of even 10 m does not exist.
vertical
heat
It was con-
cluded that the use of Bellamy's triangulation method (1949) to determine
the
flux of
sulfur
gases
salt
from a
water marsh
the only
was
micrometeorological option available where poor vertical spatial resolution
of wind
and
speed
culties.
This
method,
intensive
than
chamber
method was
developed
from the marsh surface.
to
air
temperature
however,
flux
is
even more
studies.
determine
would
the
not
equipment
Consequently,
fluxes
of
diffi-
present
a
these
and
flux
labor
chamber
sulfur
gases
Wallops Island Flux Studies
4.3
major
The
involved
a
study
field
at
conducted
the
using
Wallops
technique
chamber
Virginia,
Island,
21 and 22).
The
is
island
of the NASA/Wallops
a part
a
(see
island off the eastern shore of the Delmarva Peninsula
barrier
Figs.
effort
collection
data
Flight
Facility, and the northern part of the island consists primarily of
isolated
marsh
studying
the
beach.
and
emissions
Grass
and
height
tidal
during
of
and
Spartina-alterniflora
OCS,
H2 S,
experiment
CS2
and
from mixed
the
found
in
the
lower
marsh
were
to which
the
limited
was
Spartina-patens
the degree
episodes
field
The
stands
high
areas
considerations
primary
to
of
marsh.
flooded
in
involved
confining field studies to high marsh regions.
Instrumentation
(described in
was set
Chapter 2)
the
through
conducted
were
instrument
After
1982.
week
in
studies
calibration
equilibration,
first
a labora-
Flight Facility in
tory located on the main base of the NASA/Wallops
mid-May
up in
Three
June.
field
These preliminary studies helped
experiments were conducted in June.
to identify changes required in the sample collection setup such as
sized
(1) the use of He to transfer cryogen from large to hand-held
dewars was excessive;
-30
hr
twice
reduce
field
that
period
plus
initially
cryogen
to cover the
the amount of cryogen required
(2)
sample
estimated;
boil-off;
(4)
the
up
storage
(3)
wind
initial
to
-30
hrs
was
almost
barriers
were
required
to
flow
ambient
plan
:
to
air
through the chamber would not work because the difference between two
similarly-sized numbers
thin-film
Teflon
(C - CO) was lost in
chamber
did
not
seal
the errors;
easily,
and,
and (5)
once
the
properly
72
Fig. 21
Map describing location of Wallops Island, Virginia
73
Fig. 22
--
....
Photographs of Wallops Island field site
__
_I_
..
..-
_li
_
-i
..
I-
_
~P
_,.
_
Fig. 22
Photographs of Wallops Island field site
-t
sealed,
pushed
the
port
sizes were
too small
the air
through the ground due to pressure buildup
following the June field studies,
Therefore,
was designed and built and revisions
dure
to prevent
(the
final
3).
The
Chapter
twenty-five
hour
inside the chamber.
the polycarbonate chamber
were made to the sampling proce-
collection
sample
procedure
duration
is
field
the July
conducted
20-21
field
well as a flux
study.
when the
noise in
GC
analysis
in July
study
also
resulted
consisted
Unfortunately,
was handled
in method
the
were
adjustments:
study
as
flux information was lost
improperly
(a contaminant
created
should have been uti-
The last study in July showed evidence of
lized to clean the column).
Thus the values cal-
residual OCS and CS2 on the Nafion driers used.
For these reasons the results for the five
culated then were suspect.
preliminary
in
The two field
of a reproducibility
and a bakeout period
the GC response,
discussed
experiments
conducted weekly from mid-July through September 1982.
experiments
from being
studies conducted
in
June and July are not included here.
However, the following points concerning these early studies are worth
(1) the
noting:
results
of
the
two
reproducibility
studies
(see
Appendix VII) demonstrated good overall method agreement loop-to-loop;
(2)
CS 2 values
later
nine
increased
field
studies
during
tidal
conducted
in
episodes.
August
The results
of
the
September
are
the
and
ones specifically included in this thesis and discussed below.
Field studies were conducted on August 5-6, August
18-19,
August
26-27,
September 3-4,
September
September 23-24, and September 28-29, 1982.
9-10,
13-14, August
September
14-15,
The August 5-6 field study was conducted in a
August 5-6, 1982.
region of high marsh adjacent to a sandy mud flat.
inside
chamber
the
consisted
primarily
of
The marsh surface
with
Spartina-patens
Spartina-alterniflora growth present in smaller amounts. Soil temperatures
ranged
tide.
from
Maximum
tested
and
to
in
32°C,
minimum
The use
respectively.
being
-25
line
air
and
the
temperatures
of soda lime
between
the
site
was
were
-30
and
purge
to scrub chamber
Drierite-filled
at high
covered
23°C,
air was
cylinders
and
the
However, the cryotrap became totally iced up after a period
cryotrap.
of -5 hours (a 2-hour equilibration period plus two sampling periods
1 hour apart).
and
oven-dried.
The
cryotrap was
Once
transported back to the laboratory
the cryotrap had
been
replaced
equilibration period begun using fresh soda lime,
that
it
was the soda
was removed
lime
halted early because
lime would clean the air
short
the
supply and
could be collected.
second
it became apparent
icing.
it
sufficiently,
the moist
inlet
was
not
clear
The
cryotrap
The
that
the
soda
and because Nafion driers were
air
required drying
before
it
Fortunately, the resulting CO values (-50 pptv)
were low enough to distinguish a difference from C.
Figures 22 and
24 present the results of this flux study for OCS and H2 S.
shows
a
and the air was scrubbed by the soda lime trap only.
experiment was
in
that was causing
and
the behavior of the concentrations measured
Figure 25
for OCS, H2 S, and
CS2 .
August 13-14, 1982.
The August
13-14 field study was conducted
at the same site as the August 5-6 experiment, with rain daily during
the previous week (a total of
1.4" of rainfall).
Soil
temperatures
AUGUST 5-6,1982 FIELD STUDY
SOIL TEMPERATURES, LIGHT INTENSITIES, AND TIME-AVERAGED
OSC CONCENTRATIONS AND EMISSIONS VS. TIME
I
I
I
I
I
I
1000
800
-e---
900
700
a
800
600
700
_
I
I
I
I
I
I
I
120
35
EOCS
~ OCS
110.
34
Co OCS
I00
33
90
32
80
31
30
Light Intensity
a-- -Chamber Soil
Temperature
o---o
500
E
' 600
cn 400
70
10
0 500
z
Kj 300
60
400
200
50
300
100
40
27
200
0
30
26
20
25
10
24
0
23
o
l
6D
100
29
x
"-
28
~do
0
(TIDE)
I
1200
-
I
1600
8/5/82
I
I
I
2000
1*-
- *-I
I
0000
0400
8/6/82
TIME
v *1
I
0800
I
1200
AUGUST 5-6,1982
FIELD STUDY
SOIL TEMPERATURES, LIGHT INTENSITIES, AND TIME-AVERAGED
H2 S CONCENTRATIONS AND EMISSIONS VS. TIME
S
1000 -
800
900 -
700
800 -
600
700 -
500
E
a
' 600 - n400
o
a
z
500
I
I 1
I
I
I
--
I
I
I
H2 S
*----
H2 S
a
-7
/
I
I
Co H 2 S
o----o Light Intensity
-6,Chamber Soil
Temperature
1k
/
- M 300
120
35
110
34
100
33
90
32
80
31
70
30
60
x
29
t5_
N_
Iu 400 -
200
300 -
100
40
27
200 -
0
30
26
20
25
10
24
0
23
50
100
0
o
0
I
I
I
1200
1600
8/5/82
0
28
(TIDE)
I
I
2000
0000
I
__
- I
0400
8/6/82
TIME
r,
I
0800
I
I
1200
FIELD STUDY
TIME-AVERAGED CONCENTRATIONS
OF OCS, H2 S, AND CS2 VS TIME
AUGUST 5 - 6, 1982
900
_
I
I
I
I
I
I
I
I
I
I
Cocs ppt
800
A--A
700
F
I
I
&l
I
160
-
CHaS ppt
C
140
600
u)
180
120
500
400
so
300
60
10( 200
40
100
20
aP
0
I
I
1200
8/5/82
0
I
I
1800
i (TIpE)
I
I
0000
8/6/82
TIME
I
I
0600
I
I
___
I_
_
1200
0
ranged
30
0
C.
29 0 C,
from
-21
Soda
lime was
to
not
equilibration
period
samples
collected
were
at
and
air
temperatures
used to scrub
a chamber
chamber
purge
as described
flow
in
fluxes for OCS and H2S are presented in
ranged
air.
rate
Chapter
Figs.
from
After
of
3.
-16
26 and 27.
a 3 hr
Z min - I
4.2
The
to
calculated
The patterns
of OCS, H2S and CS2 concentrations are shown in Fig. 28.
August 18-19,
over
a mixed-stand
1982.
The August
18-19 field study was conducted
of S. alterniflora
and
S. patens,
in an area of
organic-rich soils (evidenced by the very dark soil color).
of the field studies were also conducted at this site.
heavy rainfall (.15")
(-5")
during
-35"C
and
high
air
the
previous night,
tide.
Soil
temperatures
and
the
temperatures
ranged
from
-18
There had been
site
ranged
to
The rest
29C.
was covered
from
A
-22
to
chamber/
marsh equilibration period of 3 hrs with a chamber purge flow rate of
4.2 2 min-1
was
allowed before
sample
results for OCS
and H2 S are presented
havior
H2S ,
of
OCS,
and
CS2
collection
in Figs.
concentrations
is
was
begun.
29 and 30.
shown
in
Flux
The beFig.
31.
Diurnal variations with nighttime loss except after site flooding were
observed for all three gases.
August 26-27,
August 26 and 27 were clear and warm days.
1982.
There had been a total of
week, and
tides did not
influence
for three or
tures
were -28
from -18
a chamber
inundate the site.
four days.
within
the previous
There had been no
Maximum and minimum air
and
and 14°C, respectively,
to 300C.
purge
.1" of precipitation
soil
tidal
tempera-
temperatures ranged
This week the equilibration period was 2 hrs with
flow of -5 X min-1.
A
loosely-woven,
light-weight
AUGUST 13-14, 1982
FIELD STUDY
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
OCS CONCENTRATIONS, AND OCS EMISSIONS VS. TIME
0'
120
32
1000 -
800
110
30
900 -
700
100
29
O0
Go
800 -
600
90
28
m
700 -
500
80
27
I
00
70
26
4l-
o?
I0
0
z
600
-
4ft
500
60
25
24
I< 400 -
200
50
300 -
100
40
200 -
0
30
1
j
23
22
100
20
0
10
20
0
19
1200
1600
8/13/82
2000
0000
0400
8/14/82
TIME
0800
1200
21
-. ,
AUGUST 13-14, 1982
FIELD STUDY
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
H2 S CONCENTRATIONS, AND H2S EMISSIONS VS. TIME
120
32
800
110
30
900 -
700
100
29
800 -
600
90
28
700 - ~ ~00
80
27
400
70
1000
OQ
OQ
C
Pt
w
(1)
-
o0
o 500
,
26
Ki 400 -
200
25
60 6o,
24
50
300 -
100
40
23
200 -
0
30
22
100
20
21
0
10
20
0
19
z
- W 300
1200
1600
8/13/82
2000
0000
0400
8/14/82
TIME
0800
1200
,4
-4
AI IGU r-
r
900
Il
I
iA
S.
u
- 4I, 1982 FIELD STUDY
TIME-AVERAGED CONCENTRATIONS
OF OCS, H2 S, AND CS2 VS TIME
180
800
r:
160
700
140
600
120
Io
z
500
01
400
o
eo o2
3
Iu) 300
2:
8n
10
60
200
40
100
20
0
m
.CD
O0
II
0
0(n
r
8/13/82
0000
8/14/82
TIME
0600
1200
"3
w
lb
En
FIELD STUDY
AUGUST 18-19, 1982
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
OCS CONCENTRATIONS, AND OCS EMISSIONS VS. TIME
120
r
1000
34
- 110
33
900
700
-100
32
800
600
90
31
500
-0
30
70
29
700
JE
600
u) 400
'u
60
0
r u30
2w
400
50
-
300
-
200
800
- 40
Q
28 .4
N_ -_
27
51 26
-30
I
25
100
- 20
-,
24
0
- I0
200
0
1600
8/18/82
2000
0000
0400
8/19/82
TIME
0800
1200
-0
1600
23
22
FIELD STUDY
AUGUST 18-19,1982
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
H2S CONCENTRATIONS, AND H2 S EMISSIONS VS. TIME
1500
1400
1300
1200
-
1000
-
900
900
I 100
1000
.a900
10
wo
o
-
500
- 120
34
- 110
33
-00
32
90
31
so
30
29
400
0600 -
K60 rI
x
soo
26
go_
300
100
40
200
0
30
r25
100
20
24
0
10
23
1600
8/18/82
2000
0000
0400
8/19/82
TIME
0800
1200
-0
1600
22
AUGUST 18-19, 1982
FIELD STUDY
TIME-AVERAGED CONCENTRATIONS
OF OCS, H2S, AND CS2 VS. TIME
1500
300
1400
280
1300
260
1200
240
1100
220
0
r_
rt
0a t
1000
200
900
180
800
160
700
140
4
600
120
10
500
100
400
80
300
60
200
40
100
20
o
10-
aCL
CL
to
mrt .0
'1a
z
0
0
1600
8/18/82
2000
0000
0400
8/19/82
TIME
0800
1200
1600
0.
r?
0
rn
0O
0-r
white cloth was used
during
the
Appendix
inside
remaining
IV)
were
The
the
trend
the chamber
experiments.
used
and outside
studies.
to shade
to measure
air
light
intensity
chamber
appears
to
between E and soil temperature.
fall to zero with light
~23*C,
whereas
under
and
chamber during this
of OCS
this experiment
Calibrated
outlet
values -CO at night was again observed.
and
during
be
thermocouples
(see
temperatures
both
soil
and
all
field
going
to
The correlation between E
stronger
than
the
correlation
For example, here E was observed to
intensity equal to zero and soil temperature
daytime
conditions
at
the
same
are presented
in Figs.
soil
tempera-
Soil moisture appears
to be as highly correlated with E as light intensity.
results
remaining
concentrations
ture, E was observed to be greater than zero.
flux
and
32 and 33;
The OCS and H2 S
H2S and OCS concen-
trations followed similar patterns as shown, with CS2 concentrations,
in Fig. 34.
September 3-4, 1982.
after
one
ranged
34°C.
week without
from
-19
to
The September 3-4 field study was conducted
rain
35°C,
or
and
tidal
air
coverage.
Soil
temperatures
ranged
temperatures
from
~15
to
This experiment's equilibration period consisted of 2.8 hrs at
a chamber purge flow rate of 4.2 X min - 1 .
presented
in
Figs.
35
and 36.
The OCS and H2 S fluxes are
OCS , H 2 S, and CS2 concentrations are
shown in Fig. 37.
September
9-10,
1982.
field study were a prior
hot,
sunny
weather.
The
conditions
for
period of 13 days without
There had been
no
tidal
the
September
precipitation
coverage of
the
9-10
and
site
within the last two weeks until this date when the site was covered by
AUGUST 26-27,1982
FIELD STUDY
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
OCS CONCENTRATIONS, AND OCS EMISSIONS VS. TIME
800
1000
900
- 600
600
700 - ~500
.00
-
t
400
500
120
30
110
29
100
28
90
27
80
26
70
25
60
X
24
"
400 -
200
50
300 -
100
40
22
200 -
0
30
21
100
20
20
0
10
19
0
1s
1600
2000
8/26/82
0000
0400
8/27/82
TIME
0800
1200
1600
23
AUGUST 26-27,1982
FIELD STUDY
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
HZS CONCENTRATIONS, AND H2 S EMISSIONS VS. TIME
30
0'E
1.4
1000 -
800
110
29
900 -
700
100
28
800 -
600
90
27
500
80
26
400
70
25
S500 - Ui 300
60
24
700 -
Oq
09
W
W
rt
E
C-
CL 600
z
120
-
N
p.
Ch
N
I.
O0-
1 400 -
200
50
23
300 -
100
40
22
200 -
0
30
21
100
20
20
0
10
19
0
18
ba
1600
2000
8/26/82
0000
0400
8/27/82
TIME
0800
1200
1600
CA
m
r
,.
,e
AUGUST 26 - 27,. 1982 FIELD STUDY
TIME-AVERAGED CONCENTRATIONS
OF OCS, H2 S, Al ID CS2 VS TIME
900
I
I I
¢0--
800
I
I
"'
"
Cocs ppt
0o
CH2S ppt
140
600
120
500
01
100 N
O
8002
0
90
400
x0
180
160
Scs (Normalized)
700
10.
I
II
300
60
40
200
20
100
0
ITIpE)
i
l
1800
8/26/82
I
I II
( I )
I
1I
I(T9D)
1
0000
0600
8/27/82
TIME
I
I
I
1200
I
I
1800
W
SEPTEMBER 3-4, 1982
FIELD STUDY
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
OCS CONCENTRATIONS, AND OCS EMISSIONS VS. TIME
1000 -
800
900 -
700
700 -
600
120
42
110
40
38
90
- 80
34
32
600 - N0 400
o 500 - j 300
70
400 -
200
50
300 -
100
40
4
200
-
0
I00
5,I-
a -
30
28
26
-30
24
l 20
22
20
0
10
1600
9/3 /82
2000
0000
0400
9/4/82
TIME
0800
1200
1600
18
SEPTEMBER 3-4, 1982
FIELD STUDY
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
H2 S CONCENTRATIONS, AND H2S EMISSIONS VS. TIME
01
1000 -
800 -
900 -
00
o -
oo
0--o
o
600
400
500 --j
00-
0oo
Ioo
38
Light Intensity
Chomber Soil
90
36
Temperature
o
- 34
I400 -
70
200
300 -
SO
T60
50
200
400
100
-40
200 -
30
100 -
20
o -
0
0
9/3/82
0
0
ITIDE)
1600
2000
- 42
- 40
40
o H2 S
b-
700 -
120
110
.-- a- [ H2S
SC HS110
0000
IM)
0400
9/4/82
TIME
0800
1200
o
1600
-
32
"_ 28
,30.0
2 8
-26
-24
22
-a 20
o.
SEPTEMBER 3- 4, 1982
FIELD STUDY
TIME-AVERAGED CONCENTRATIONS
OF OCS, H2 S, AND CS2 VS TIME
900
.
I
I
II
I
1
I
0-aa-0
800
0
I
I
I
o
160
CHZS PPt
140
600
0I
180
Cocs Ppt
0 Ccs, (Normalized)
c
700
I
120
100
500
I)
0
400
z
IU)
300
60
40
40
ItJ 200100
20
0
I
1800
9/3/82
I
I
(TI DE)
I
0000
9/4/82
I
i
0600
TIME
I
(TIDE)
1200
I
I
I
1800
1"-1.5" of water during high tide.
with
a
X min-1
-5
collection
-29
and
28°C.
was
chamber
begun.
and
flow
was
allowed
and minimum
soil
air
activity
the
S-
which
formed
S04=
reduces
is
before
oxidized by
It
the
from
were
-12
to
is not known if the
S=
to
sample
temperatures
temperatures ranged
soil was dry and highly porous.
bacterial
moisture,
purge
Maximum
9C respectively,
The
An equilibration period of 2 hrs
halts
aerated
with
soil,
low
or both.
The OCS and H2S flux results are presented in Figs. 38 and 39.
OCS,
H2S , and CS2 concentrations are shown in Fig. 40.
September
14-15,
1982.
The
September
14-15
field
study was
conducted 5 days later and reflects the influence of soil moisture on
E.
Although there had been no precipitation for a total of 18 days,
the
site had been flooded daily during high
tide since September 9.
The nighttime peak demonstrates the behavior routinely observed during
tidal
episodes.
where
the
maximum
ively,
tide
and
and
Similar
behavior
was
influenced
the site
during
minimum
soil
air
temperatures
temperatures
were hot and hazy.
ranged
observed
were
the
in
25-hour
-29
from -15
all
to
and
experiments
study.
12°C,
32°C.
The
respect-
Conditions
Chamber equilibration consisted of 2 hrs with a
chamber purge flow rate of "5 £ min-1.
The OCS and H2S flux results
are presented in Figs. 41 and 42, and OCS, H2S, and CS 2 concentrations
are shown in Fig. 43.
This type of behavior for CS 2 , concurrent with
standing water inside the chamber, was observed during several but not
all tidal episodes.
September 23-24, 1982.
ducted
immediately
following
The September 23-24 field study was cona
four-day
"nor'easter,"
a
storm
that
SEPTEMBER 9-10,1982
FIELD STUDY
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
OCS CONCENTRATIONS, AND OCS EMISSIONS VS. TIME
120
1000
800
I10
900 K
700
100
800
90
700
E
6w
a
U) 400
70
500
60
Iu 400 -
200
50
300 -
100
40
0
30
200
-
100
20
0
10
0
1200
9/9/82
1600
2000
0000
0400
9/10/82
TIME
0800
1200
0-
r~J
r
ct
FIELD STUDY
SEPTEMBER 9-10,1982
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
H2 S CONCENTRATIONS, AND H2S EMISSIONS VS. TIME
120
27
1000 -
800
I10
26
900 -
700
100
25
800 -
600
90
24
700 -.
500
80
23
600 -
400
70
22
c
z
60
500
6-N
21 -
S400 -
200
50
20
300 -
100
40
19
200 -
0
30
18
100
20
17
0
I0
16
0
15
1200
9/9/82
1600
2000
0000
0400
9/10/82
TIME
0800
1200
SEPTEMBER 9 -10, 1982
FIELD STUDY
TIME-AVERAGED CONCENTRATIONS
OF OCS, H2 S, AND CS2 VS TIME
0
z4
900
180
800
160
700
140
600
120
0
500
400
300
60
200
40
100
20
IU0
0
0
1200
9/9/82
1800
0000
9/10/82
TIME
0600
1200
go
SEPTEMBER 14-15,1982
FIELD STUDY
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
OCS CONCENTRATIONS, AND OCS EMISSIONS VS. TIME
120
1000 -
800
I10
34
900 -
700
100
32
800 -
600
90
30
00
so
20
-
700
a 600 - u 400
z
4[
K) 400
26
60
r &1300
300
200 -
X-. 24
o
200
50
100
40
20
0
30
18
20
16
10
14
100
0
1200
1600
9/14/82
2000
0000
0400
9/15/82
TIME
0800
1200
22
FIELD STUDY
SEPTEMBER 14-15, 1982
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
H2 S CONCENTRATIONS, AND H2 S EMISSIONS VS. TIME
09
120
ha
1000 -
800
110
34
900 -
700
100
32
800 -
600
90
30
80
28
70
26
700 -
oo500
E
a 600 - u) 400
(;
tr
€0
co
I
IU
S500 -
1 300
60
24 -I
400 -
200
50
22
300 -
100
40
20
o
30
18
100
20
16.
0
I0
14
r
0
12
r3
ta
0
200
I'
0
3
rlr
En
1200
1600
9/14/82
2000
0000
0400
9/15/82
TIME
0800
1200
SEPTEMBER 14-15, 1982
FIELD STUDY
TIME-AVERAGED CONCENTRATIONS
OF OCS, H2 S, AND CS2 VS. TIME
Cn
a
z
Oq
1100
2400
1000
2200
900
2000
800
1800
700
1600
cn
0
"o
rv
a.
00
'1-
L
N
I
600
1400
t="
b,
500
1200
Ut
400
1000
300
800
200
600
l,4
r_
a.
,'2
N•
r
pa
,w
100
400
0
200
0
('J
CL
ciE
1o
1200
1600
9/14/82
2000
0000
0400
9/15/82
TIME
0800
1200
O
100
washed channel waters into
from
-. 25"-4"
of
water
the marsh and left the marsh inundated by
during
the
Standing water receded gradually,
been during this
coverage,
yet
experiment.
the
emissions
entire
25-hour
sampling
period.
leaving the marsh the wettest
There
did
was
not
no
fall
obvious
to
high
it had
tide
zero overnight.
site
Once
again, this reflects the dramatic response of E to soil moisture and
to
tidal
soil
influence.
temperatures
consisted
Results
As
of
Air
temperatures
ranged
1 hr
from
with
-12
to
a chamber
for the OCS and H2 S fluxes
seen
in Fig.
46,
all
ranged
from -9 to
25*C.
Chamber
purge
are
flow
presented
23*C,
and
equilibration
10 X min-1.
rate
of
in
Figs.
44 and 45.
three gases were emitted continuously with
concentration values never approaching Co.
CS2 values were high and
followed the patterns displayed by both OCS and H S.
2
September 28-29, 1982.
The September 28-29 field study was con-
ducted two days after a second storm had washed channel waters
the
marsh.
The
marsh
was
standing water at the site.
noticeably
soggy
though
there
into
was
no
Fluxes were high, apparently due to the
influence of high soil moisture, and possibly due to the origin of the
moisture
example).
(channel
Soil
ratures ranged
water
is
much higher
temperatures ranged
from -10
to 30°C.
in
SO04
from -13
Chamber
2 hrs with a chamber purge flow of -5
than rain water,
for
to 29°C, and air tempe-
equilibration consisted
£ min-1.
of
The OCS and H2 S flux
results are presented in Figs. 47 and 48, while OCS, H2 S, and CS2 concentration information for this field study is shown in Fig. 49.
FIELD STUDY
SEPTEMBER 23-24,1982
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
OCS CONCENTRATIONS, AND OCS EMISSIONS VS. TIME
120
1000
800
110
900
700
100
800
600
90
500
80
V) 400
U
70
1L 300
60
700
N
E
49600
X500
Z
400
200
50
300
100
40
200
0
30
100
20
0
I0
0
1200
1600
9/23/82
2000
0000
0400
9/24/82
TIME
0800
1200
--'
p,
d
N.
SEPTEMBER 23-24, 1982
FIELD STUDY
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
H2 S CONCENTRATIONS, AND H2 S EMISSIONS VS. TIME
120
25
1000
800
I10
24
900
700
100
23
800
600
90
22
700
500
80
21
CL 600
- c 400
70
20
300
60
19
(I)
En
00
rtI
4-
ioo
f
o
z
500 - Il
m
uj
N_
18
400
200
50
300
100
40
200
0
30
16
20
15
CD
4i,.
r)
00
100
.
t--&
U,
1200
1600
9/23/82
2000
0000
0400
9/24/82
TIME
0800
1200
I0
14
0
13
SEPTEMBER 23- 24, 1982 FIELD STUDY
TIME-AVERAGED CONCENTRATIONS
OF OCS, H2 S, AND CS2 VS TIME
900
I
I
I
I
I
I
I
I
180
I
800
160
700
140
600
120
500
o
00
'-1.
rt
H.
01
0
400
so
.4
300
"0
K)
200
40
100 -
20
I (TIPE) I
1200
9/23/82
1
1800
I
I
I
I
TIDE)
1TD~I
0000
9/24/82
TIME
I
0600
II
II
II
1200
"
0
U:
CA
SEPTEMBER 28-29, 1982 FIELD STUDY
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
OCS CONCENTRATIONS, AND OCS EMISSIONS VS. TIME
1100
34
1000 -
800
110
32
900 -
700
100
30
800 -
600
90
28
80.
26
700
a 500
" 600
- 400
0
z
I
120
500
-
70
24
rl
22
60
300
01
400
200
50
20
300
100
40
18
200
0
30
16
100
20
14
0
I0
12
0
I0
1200
1600
9/28/82
2000
0000
0400
9/29/82
TIME
0800
1200
SEPTEMBER 28-29, 1982 FIELD STUDY
TIME-AVERAGED SOIL TEMPERATURES, LIGHT INTENSITIES,
H2 S CONCENTRATIONS, AND H2S EMISSIONS VS. TIME
120
1000
-
800
110
-
900 -
700
100
-
800 -
600
90
700
- 500
ckj
80
c 600
(n 400
70
24
22
0
c 500
I)
- It
300
400
200
60 X
0
50
300
100
40
200
0
30
z
100
20
0
I0
1200
1600
9/28/82
2000
0000
0400
9/29/82
TIME
0800
1200
-
SEPTEMBER 28-29, 1982
FIELD STUDY
TIME-AVERAGED CONCENTRATIONS
OF OCS, H2S, AND CS2 VS. TIME
1200
I
I
I
I
I
1100
I
I
I
I
I
I
-
240
o cn
:3 V
220
CocSPPt
0--
1000
I
CS
2 (Normalized)
rt
200
'10
rt
900 -
0CH
2
SPPt
180
0 00
800
160
700
140
.G.-
1.
00
13
cl(l)
600
120
z
500
100
a
400
80
a
300 "
60
200 -
40
100 -
20
-r
N
u
U)
0
10.
0
I
1200
(TIDE)
I
I
1600
9/28/82
I
I
2000
I
1
0000
I
I
0400
9/29/82
TIME
I
(TIDE)
I
0800
I
I
1200
CL
107
4.4
Aircraft Measurements
Samples
20-26 kft during
York on
July
Research
1982,
and
the
some prior preliminary
Virginia
from
a flight
11-12,
Center
Island,
OCS and CS2
of ambient
to
through
NASA/GSFC
San Juan,
cryogenically
San Juan,
Wallops
Puerto
San
at
New
NASA/Langley
Facility.
During
flight
and a July
to
For example,
accommodate pressure changes.
Flight
Rico)
were designed
procedures
of the
on a July 8-9
to South America
collected
Puerto Rico to Albany,
the courtesy
tests conducted
(San Juan, Puerto Rico
sample collection
were
(Wallops
10-11
flight
Juan, Puerto
Rico),
primarily to
and revised,
was found that the FMI
it
pumps, used to trap samples at ground level, were incapable of pumping
with and without
tests
A trapping period of 10 min was chosen after
against a vacuum.
in line showed
Nafion driers
this would allow
that
The
trapping without the driers in line with a minimal risk of icing.
procedure
collection
sample
described
in
50 worked
Fig.
at
well
The
range of pressures encountered during sampling (322 to 246 torr).
mixing
OCS
-520
ppt
within
lysis methods
on the
ratios,
did
ratios
the
vary
not
analytical
spatially
uncertainty
but
(517 -+12.6% relative standard deviation).
other
hand,
showed
that these are the
considerable
ana-
CS2 mixing
variability
ambient OCS
at
(concen-
It is believed
at these
alti-
Since these OCS values are similar to those measured by others
tudes.
lower
inert
first measurements of
and
of collection
tration values for OCS amd CS2 are listed in Table 3).
at
constant
were
the
altitudes,
they
in the troposphere.
support
Therefore,
the well-mixed portion of the
estimated using
the
belief
a minimum
troposphere
is
relatively
lifetime
for OCS in
OCS
that
of about
two months can be
108
AIRCRAFT SAMPLE COLLECTION
l FLIGHT DIRECTION
ZZZ
AIRCRAFT FUSELAGE
1/ TEFLON TUBING
INSIDE 1/4 SS INLET LINE
REGULATING
NEEDLE VALVE
VENT
Fig. 50
Aircraft sample collection schematic
Table 2
Aircraft Sample Collection
Loop #
Trap Time
(hrs)
2140-2146
2150-2200
2204-2211
2216-2226
2231-2240
2245-2255
2300-2307
2313-2319
2323-2333
2337-2345
2350-0000
0005-0015
0019-0029
0033-0043
0050-0100
0104-0114
0118-0128
0132-0141
0149-0159
0204-0214
0218-0228
Cabin Pressure
(torr)
655
655
655
655
657
657
657
616&+
612
611
611
611
611
611
611
611
611
611
581.5
581.5
583
Cabin Temperature
(0C)
19.2
18.5
18.5
19.8
20.5
20.5
20.6
20.2
18.5
17.5
17.0
16.5
15.7
15.0
14.65
14.9
14.5
15.0
14.5
13.5
13.7
Loop Pressure
(torr)
321-315
321.3
320
321
321
321
321
282-273
270
270-265
269
269
269-270
270
271
272.5
269
272-265
246
246
246
Comments
turbulence
climbing
turbulence
turbulence
climbing
Altitude
(kft)
20.0
20.0
20.0
20.0
20.0
20.0
20.0&t
22-24
24.0
24.0
24.0
24.0
24.0
24.0
24.0
24.0
24.0
tto26.0
26.0
26.0
26.0
Table 3
Aircraft Measurements of OCS and CS
2
Loop #
Mid-Time
(hrs)
2143
2155
2207.5
2221
2235.5
2250
2303.5
2316
2328
2341
2355
0010
0024
0038
0055
0109
0123
0136.5
0154
0209
0223
Altitude
(kft)
20.0
20.0
20.0
20.0
20.0
20.0
20.O0&t
22-24
24.0
24.0
24.0
24.0
24.0
24.0
24.0
24.0
24.0
tto26.0
26.0
26.0
26.0
Approx.
Latitude
N25*08.9'
N25"54.7'
N26051.2'
N27048.6'
N28057.9'
N30 0 07'
N31014.4'
N31 58.5'
N33 0 07.7'
N33"53.6'
N34 0 57.3'
N36'04.7'
N3709.3'
N38 0 20.7'
N39"23.1'
N40023.8'
N41"38.5'
N42031.8'
N41023.4
N40021. 1'
N39"19. 7'
Approx.
Longitude
0
W68 01.1'
W68 0 16.6'
W68"36.1'
W68°52.1'
W690 11'
W69"30.5'
W69 0 49.8'
W70 0 02.8'
W70 0 22.2'
W70°35.3'
W70 0 53.9'
W71'14.2'
W71 0 53.8'
W71"59.4'
W72"35.3'
W73'39.6'
W73"44.3'
W73 0 42'
W73 0 43.9'
W73"49.4'
W74'31.8'
OCSOCS
(ppt)*
)*
(
845.4
639.9
752.3
523.7
440.2
561.9
557.0
601.0
408.1
623.3
494.3
459.5
489.3
436.4
486.0
489.7
545.9
652.3
507.3
509.0
521.2
CS2
(100%
(ppt)
-tff)*
* .
ef
(100%
..
1970.2
554.9
298.2
141.0
55.3
95.4
96.4
99.3
9.7
23.7
25.8
19.8
27.9
18.4
12.0
14.3
22.0
39.3
51.7
11.8
13.4
CS2 (Rpt)
(70% eff)
(70% eff)
2814.6
792.7
426.0
201.5
79.0
136.3
137.8
141.9
13.8
33.9
36.8
28.3
39.9
26.2
17.2
20.4
31.5
56.2
73.9
16.8
19.2
Cabin air contamination of inlet line present in first samples, residual may be present in samples
Loop #s 5-7.
Average OCS mixing ratio Loop #s 9-38:
517.0 (±65.0) pptv (12.6% relative standard deviation).
111
T
where T
The
reported
ability.
=
=
Z 2 /2D
lifetime, Z = 10 km, and D = 105 cm 2 s-1.
CS2
in
concentrations measured
the literature
The
observed
lie within
and demonstrate
decrease
of
CS2
current belief of a short photochemical
sphere.
the range of values
significant
with
liftime
altitude
for CS2
spatial
supports
in
the
the tropo-
Sample storage and analysis procedures have already been
described in Chapter 3.
vari-
112
CHAPTER 5
SUMMARY AND CONCLUSIONS
5.1
Analytical Developments
metric
Detector
and
(FPD)
mentation.
to generate
was doped with SF6
the
H2 S,
CS2
and
to calibrate
the GC
The cause of the GC response instability was iden-
the
the
flame gas
flow-controlling devices which allowed
to vary with variation
thermally isolated.
minate
to continu-
The GC response was observed to be extremely sensitive to
tified as inadequate
concluded
instru-
A.I.D. and KINTEK permeation devices were
of OCS,
standards
flame gas makeup.
flow rates
Spectra
A specially treated Porapak-QS column was used to separate
ously condition the column.
response.
a
with
analytical
the
comprised
sulfur gases, and the N2 -carrier gas
used
along
filter,
sulfur
integrator,
programable
Physics
a
equipped with a Flame Photo-
(GC)
A Tracor 560 Gas Chromatograph
and
carrier
laboratory
in
flow-controllers
gas
flame
The Tracor FPD exhaust
of
possibility
caused by condensation in the port.
should
port was modified
perturbations
pressure
It
temperature.
in
the
was
be
to eli-
GC
signal
The GC sample valve was automated
for convenience in column conditioning and calibration studies as well
as for reproducibility
in
introducing
samples
to the GC column.
The
Spectra Physics integrator was programmed to control the sample valve,
to run
calibration trials,
sponse
and
to
perform
standard concentration
data,
linear
regressions
on GC re-
to graph calibration curves,
to calculate loop trapping efficiencies, and to predict sample concentrations.
113
Extensive tests were conducted to develop a reliable and portable
sample
collection
Tenax-GC,
technique.
Porapak-QS)
were
Various
tested
adsorbents
and
unreliable in sulfur gas desorption.
found
(Molecular
to be
Sieve,
inefficient
and
The cryogenic trapping of OCS on
The behavior of glass
Pyrex beads and Teflon chips was also tested.
beads was not reproducible, and deterioration of collection efficiency
and reproducibility was observed with extended use of the Teflon chipEmpty Teflon tubing was chosen as the most reli-
packed sample loops.
able
trapping
surface,
and
and Teflon
aluminum tubing
housed
in
were
conducted
to
consisted of Teflon tubing
loops
sample
cryogenic
determine
Extensive
plug valves.
trapping
tests
efficiencies
(adsorption plus desorption), sample integrity during storage, and the
degree
to
which
nitrous oxide,
low
molecular
and water vapor
weight
interfered with
efficiencies or sample analysis.
line
output
chamber
with
hydrocarbons,
fluorocarbons,
and
trapping
storage
Nafion tubing driers were placed in
sample
loops
sample
during
collection.
Laboratory studies were conducted to determine if an air stream containing OCS and H2 S was depleted or enhanced in these compounds after
No such loss or enhancement
it had passed through the Nafion tubing.
was
observed
during
these
initial
However,
tests.
these
driers
became less efficient at removing water vapor and demonstrated losses
of OCS as high as -45% after extended use.
A
cryotrap was made
of two -50'-lengths
which was coiled and immersed in liquid argon.
to
scrub
through
ambient
a
series
air
of
in the
field.
Drierite-filled
The
of
copper
tubing
This cryotrap was used
ambient
plastic
1/4"
air
stream
cylinders
flowed
before
it
114
entered the cryotrap.
Without this precaution, the presence of water
vapor caused the cryotrap to rapidly clog with ice.
contained
amount
undetectable
of CS2
levels
H2 S,
of
and was used as the chamber
was easily positioned
pptv
purge
OCS,
for a leak-free
and
a
air during
The polycarbonate
studies conducted at Wallops Island.
face.
-25
The scrubbed
small
the
flux
air
flux
chamber
interface with the marsh
sur-
Polycarbonate has been shown to be a relatively inert material
and was chosen to minimize surface reactivity with the sulfur gases of
interest.
The chamber design included an exit port of sufficient size
to minimize pressure buildup within the chamber, and a fan to circulate interior chamber air.
When
problem,
strated
flame-out
this
system
episodes
of
(caused
sulfur
stability and yielded
gas
by power
collection
reproducible
failures)
and
results
were
analysis
for OCS,
not
a
demon-
H2 S,
and
CS2.
5.2
Field Studies
Preliminary field studies were carried out at the Scripps Insti-
tution
of Oceanography,
dissolved
La
Jolla,
oxygen were monitored
California.
in
several
Temperature,
Southern California
marsh and mud flat environments.
In
the Penasquitos Marsh,
were
9,
and
found
to
vary
from
-7
to
pH,
a diurnal
and
salt
pH values
dissolved
cycle was identified with daytime saturation values exceeding
oxygen
14 ppmv
and nighttime values falling to zero.
Field
tory
in
work was
Woods
vertical wind
also
conducted
Hole, Massachusetts.
profile in
the
at
the Marine
Measurements
Biological
were made
Laboraof
the
first 2 m above the marsh surface along
115
with attempts
from
to determine
the
fluxes
Spartina-alterniflora-covered
Marsh.
Laboratory
and
field
of OCS,
sections
studies
H2S,
of
showed
(CH 3 ) 2 S,
the
the
and CS2
Sippiwissett
choice
Salt
of Molecular
Sieve/Tenax-GC two-stage adsorbent traps to be inappropriate for reliable
that
sulfur
gas
wind and
concentration
determination.
Field
temperature variability within a
studies
spatial
showed
resolution of
2 m was too great to reliably establish du/dz or dT/dz.
The major data
of
OCS and
collection
H 2 S from
effort
involved
Spartina-alterniflora
and
a study
of the
fluxes
Spartina-patens
stands
in a salt water marsh at Wallops Island, Virginia.
conducted weekly during August and
and H2S were
chamber
calculated
from
concentrations,
the
area, the chamber height,
as
estimated
plots.
The
by
the difference
chamber
and
mechanically
diurnally averaged
are presented in Table 4.
September
flow
fitting
The
1982.
between
rate,
the changes
Field studies were
fluxes
input
the
and
chamber
curves
flux values
to
the
calculated
with daytime
maxima
for OCS and H2 S
and nighttime
concentrations were routinely observed
for
OCS, H 2 S ,
and CS 2.
OCS
similar,
less
than
and
and
the
time
The major conclusions which have been made
Diurnal variations
The
surface
concentration
chamber concentrations falling approximately to input
2.
output
of concentration with
based upon the results of these field studies are:
1.
of OCS
H2 S
CS 2
concentration
concentrations
concentrations
of
variations
were
OCS
were
routinely
or
during periods of extreme soil moisture.
H2 S
much
except
Table 4
Summary:
Wallops
Island Flux Studies
Field Study
Diurnally Averaged
Emissions (ng S/mz/hr)
HqS
OCS
8/5-6
71.25 (8)
64.6 (8)
31.5
25.3
Site covered at high tide
(1S. Patens)
8/13-14
19.6
39.9
29.0
21.0
1 entire week of rain
(1S. Patens)
8/18-19
60.9
142.75
34.17
22.38
Heavy rain previous night
8/26-27
124.75
37.0
29.73
18.42
Recent daily flooding at high
tide
9/3-4
90.6
32.8
34.59
21.50
1 week without rain or tide
coverage
9/9-10
30.4
32.5
27.24
17.09
2 weeks without rain or tide
coverage
9/14-15
332.45
134.75
31.31
16.18
1 week of daily tide coverage
9/23-24
417.33
153.33
25.86
15.26
After 4-day storm, marsh
inundated with channel water
9/28-29
291.25
88.9
29.0
14.8
Marsh soggy from second storm
(channel water)
T
.C
TSoil C
TSoil
Maximum
Minimum
C
--- Moisture Comments
117
3.
OCS
and
H2S
following
concentrations
sodes.
observed
episodes
whereas
CS2
observed
to
during
tidal
sometimes
were
were
jump
to
jump
concentrations
epi-
tidal
Therefore, it is speculated that CS2 may have
a more important oceanic than marsh surface source.
influences
Soil moisture significantly
4.
the
of
fluxes
OCS, H2 S, and CS2 from the high marsh.
It is
surface
found
(1982)
note
to
interesting
that
ocean waters
even
to be
though
Rasmussen
in
supersaturated
et
al.
OCS,
OCS
concentrations were not observed to dramatically increase during tidal
Also, observations of increased CS2 concentrations during
episodes.
tidal episodes support Lovelock's suggestion of an oceanic
CS2
source
for
(1974).
Grab samples were collected from aircraft at 20-26 kft between
Puerto
San Juan,
atmospheric
through
Rico and Albany,
concentrations
the
courtesy
of
of OCS
the
at
and CS2
(flight
NASA/Langley
NASA/GSFC Wallops Flight Facility).
for OCS mixing ratios
New York to determine
time
Research
the ambient
was
Center
arranged
and
the
No spatial variation was observed
these altitudes
and latitudes.
CS2 values,
however, demonstrated considerable variability.
5.3
The Global Sulfur Budget
In this section, the relative importance of salt water marshes to
the global OCS cycle and as a source of H2 S to the global sulfur cycle
is discussed.
The possibility of a significant oceanic source of CS2 ,
and thus an atmospheric source of OCS, is raised, and the influence of
water movement upon volatile sulfide concentrations in salt marsh soil
pore waters is also discussed.
118
Table 5
Annual Global Fluxes of Sulfur from Biogenic
(in Tg S yr
-
1 )*
Biological Decay
Eriksson (1960, 1963)
Sources
Biological Decay
(land)
(ocean)
110
170
Junge (1963a,b)
70
160
Robinson & Robbins (1968,1970)
68
30
Kellogg et al. (1972)
Friend (1973)
Garrels et al. (1973)
Granat et al. (1976)
Zehnder & Zinder (1980)
Ivanov (1981)
*1 Tg S = 1012 g S
119
The biogenic component of the global sulfur cycle.
Many authors
have attributed a major role in their postulated global sulfur cycles
to biogenic sources of sulfur (see Table 5).
As previously discussed
in
estimated
Chapter
1, all
except
Ivanov
(1981)
have
the
biogenic
contribution to the global sulfur cycle by difference rather than from
actual
data.
fluxes
of biogenic
sulfur
rather than
studies.
Even
One
Ivanov
(1981)
sulfur
from
from
flux
calculated
the
his
atmospheric
calculations
that
and
content
derived
oceanic
of reduced
from experimental
possible problem with this approach is the assumption
that reduced sulfur is only of biogenic origin.
suggest
land
the
reaction
of
CS2
(which
has
McElroy et al. (1980)
numerous
anthropogenic
sources) with OH provides a significant source for atmospheric SH and
thus, perhaps, H2 S via the following postulated reactions:
SH + HO 2
+ H2 S + 0 2
SH + CH 2 0
+ H 2 S + HCO
SH + H 2 0 2
+ H 2 S + HO 2
SH + CH3 00H + H 2 S + CH 3 0 2
SH + SH
+ H2 S + S
SH + 03
+ HSO + 0 2
SH + 02
+ SO + OH
SH + OH
+ S + H2 0
with removal of H2 S by reaction with OH in turn regenerating SH:
+ H2 0 + SH.
OH + H2 S
A major problem associated
sions
for
result
in
H2S,
the
for
example,
with calculating global coastal
are
extrapolation of
the
substantial
limited
data
to
uncertainties
global
emisthat
environments
120
which are often dissimilar.
data available
Global
flux
for
The
the reduced
values
extent of diurnal
sulfur compounds
and seasonal
is
which have been extrapolated
extremely
from single
flux
small.
daytime
concentration measurements are most often all that is available.
This
research
are.
shows
how
completely
inappropriate
such
calculations
This research also suggests that it is invalid to attribute a significant role
H2S
to
as most
,
extrapolate
salt
of
H2S
water marshes
these
fluxes
water areas to other
global
flux.
marshes
in
It
such
global
for the primary biogenic source
models
calculated
do.
from
similar coastal
It
studies
regions
Indeed,
this
be
reasonable
of coastal
in
would be erroneous, however,
a calculation.
may
order
of
to
shallow-
to calculate
a
to include salt water
research
suggests
that
the higher regions of salt water marshes are relatively insignificant
biogenic sources of OCS, H 2 S, or CS .
2
OCS
significance calculations.
A range
orders of magnitude have been calculated
of OCS in
al.,
the stratosphere
1980).
A relative
(Crutzen,
1976;
quantification
of values
spanning -2
for the rate of destruction
Sze and Ko,
of
the
role
1978; Turco et
of
salt
water
marshes in the global OCS cycle can be achieved by equating the calculated
rate of destruction of OCS in
the stratosphere with its flux
into the stratosphere combined with a knowledge of the relative global
area of salt water marshes.
With this information, one can calculate
the
from salt
rate
of emission of
OCS
water
marshes
which
required if salt water marshes represented the only global
OCS.
The observed emissions of OCS can
then be
would
be
source of
compared with
this
121
predicted flux in order to calculate the actual relative importance of
salt water marshes in the global OCS cycle.
using
Therefore,
the various values
for
the rate of destruction
of OCS in the stratosphere calculated by the aforementioned authors,
the
relative
global
area
of
salt water
(0.0745%),
marshes
and
the
assumption that salt water marshes represent the only global source of
of OCS
OCS, the following rates of emission
are
1.5 x
1.5 x 107 to
2
to
2.0
1011
x
hr- 1 ) is
using Crutzen's
calculated
cm - 2
108 molecules
s-1
s-1
cm-2
molecules
for
the rate
3.9 x 109 molecules cm-
(2)
2
s-1
(7.2 x 103 ngS m
2
hr- 1 )
s-1
is calculated from Sze and Ko's value of 2.9 x 106 molecules cm-2
and (3) 2.15 x 1010 molecules cm
2
-1
of 1.6 x 10 7 molecules cm -2 s -
1.
2
hr-1)
is cal-
The maximum individual flux value of
OCS observed during the Wallops Island
represents
OCS
(417
12% of
field study
global
the
(864
OCS
from
0.2
to
the
the
maximum diurnally-averaged
and
stratosphere,
for
(4 x 104 ngS m
using Turco et al.'s value for stratospheric OCS destruction
culated
then
of
destruction of OCS (scaled to -500 pptv ambient mixing
stratospheric
ratio OCS),
1010
3.7 x 105 ngS m-
(3.7 x 104 to
value of
x
(1) 2.0
required:
from salt water marshes
ngS
m72
hr-1)
represents
at
most
ngS mflux
value
6% of
2
hr - 1 )
into
the
observed
global
OCS
emissions.
If one averages the nine diurnally averaged values calculated for
the flux of OCS for the August and September field studies, the result
(-160
ng
emissions.
S
m-
2
hr - 1 )
represents
no
more
than
-2% of
global
OCS
This averaged value may represent an upper limit for this
particular salt marsh for diurnally averaged OCS emissions because the
122
period studied is likely to be much more productive than winter months
when
low
temperatures
appear
to
cause
(Ingvorsen and Jorgensen, 1982).
microbial
activity
to
halt
Extrapolation of this value results
in an annual global emission of only 5.3 x 108 g S yr-1.
This is four
orders of magnitude less than even the lowest annual global flux value
in the literature attributed to biological decay on land (5 Tg S yr Granat et al.,
H9 S
H2S,
1976).
ng
H2S from
S m
2
hr -1 , translates
salt marshes of
maximum
observed
to an annual
3.3 x 109 g S yr-1.
flux
for
global emission of
This observed maximum
The maximum diurnally-averaged H2S flux
flux was an anomaly, however.
(153
The
significance calculations.
987
,
ng S m -2 hr- 1 ) represents
an annual
global
salt marsh
contri-
bution of only 5.1 x 108 g S yr- 1, and the average of the 9 August and
September
diurnally
represent
an upper
only
x
-2
2.7
x 104
(1976),
averaged
values
(80.7
yr - 1 .
than
the
Once
5 Tg
and a factor of -10
again,
ng
this
value
S yr - 1 calculated
less
m-
S
2
hr - 1 ) may
from salt water marshes of
limit of H2 S emissions
108 g S
smaller
flux
than the
12 Tg
is
a
factor
by Granat
S yr-1
of
et al.
attributed
by Ivanov (1981) to H2 S emissions from shallow coastal regions.
CS?
significance
calculations.
From
the
results
presented
in
Chapter 4, it appears that diurnally averaged CS 2 fluxes from areas of
the high marsh
are much
GC-saturation due
lower
to high CS2
than those
for H2S
concentrations
samples taken during tidal episodes.
and OCS.
sometumes
Because high CS2
only occurred concurrent with standing channel water
chamber,
this raised
the
question of a significant
However,
occurred
for
concentrations
inside the flux
oceanic
source of
123
CS2 , and thus of atmospheric OCS.
Returning to the arguments used to
calculate the relative importance of salt water marshes in the global
OCS cycle, similar arguments can be presented to estimate the relative
importance of an oceanic source of CS2
to the global OCS cycle (here
If oceans were to
oceans represent approximately 70% of global area).
represent the only global
for stratospheric
Ko's value
2
the required values
fluxes of OCS would be 4.1 x 106 molecules cm - 2
oceanic
cm-
source of OCS,
s-1
upper
(Crutzen's
rate
(Sze
and
to 2.1 x 108 molecules
OCS destruction)
limit
s-1
for the
of
of destruction
OCS in
the
stratosphere).
response
and
a three-point,
stability,
for CS2 was
curve
rough
to estimate
which
GC-saturation
2
(7
hr-1
temperature-programmed
result
in
CS 2 .
for
calibration
Preliminary
periods
observed during
fluxes
cm
2
to
of 1272
mimimum values
x 108 to 9.7 x 108 molecules
GC-
CS2 mixing ratios
absolute
estimates
CS2
maximum
calculations
caused
flux
of excellent
several weeks
run to roughly estimate
enable
to
thus
ng S m-
after
the end of September,
Near
1817
(The range
s-1).
of values results from estimating trapping efficiencies (e) for CS2 at
70% < e < 100%.)
If, as Jones et al. (1982) suggest, the atmospheric
12%
conversion of CS2 to OCS by reaction with OH is
would
molecules
CS2
during
using
comparable
a
yield
s - 1.
cm- 2
a
tidal
Crutzen's
OCS
input
of
x
8.4
this
efficient,
107
x
108
observed
for
1.2
to
The maximum
individual
flux value
then
represents
from 40-57% (calculated
episode
upper
limit)
to
-2000-3000%
(using
value) of the global OCS flux into the stratosphere!
Sze
and
Ko's
Extrapolation of
the maximum flux observed for CS2 results in an annual global oceanic
124
S yr- 1 , a factor
6 Tg
to
of -4
contribution
to 30
of -3
less
than
the values in the literature for biological decay in oceans (see Table
It must be noted that this represents the highest rather than the
5).
tidal episodes and assumes
for CS2 during
average value observed
that
CS2 is fluxed from all ocean waters at this maximum rate.
As noted in
Soil moisture and volatile sulfide concentrations.
it
1,
Chapter
such
environments
as
water
salt
and Desulfotomaculum,
Desulfovibrio
reducing bacteria,
H2 S.
and the dissimilatory sulfate-
sulfate,
are rich in
Such environments
marine
of
sources
major
are
marshes
coastal
anaerobic
that
speculated
been
has
are thought
to
be primarily responsible for transforming sulfate to sulfide in anoxic
1955)
Wood,
and
upon the carbon source
and
have
areas
also
been
found
of high marsh
1979; Linthurst
et al.,
1982).
(Postgate,
1965;
in
to
(Oshrain,
and Seneca,
from
1977; Linthurst,
coastal
1979;
to
Kaplan,
soil
marsh
salt
1980; Mendelssohn
and
and
Sivanesaw
appears
yield
Goldhaber
considerably
vary
1968;
(Gooch,
sulfide
concentrations
sulfide
volatile
The
51).
Fig.
(see
1972)
Manners,
soils
salt-marsh
in
and
Baas-Becking
1948;
and Rittenberg,
(Zobell
sediments
and
waters
pore
depend
1974),
waters
regions
to
Skyring et al.,
and Seneca,
1980:
King
Several studies have been conducted in the attempt to
determine what parameters regulate volatile sulfide concentrations and
Spartina-alterniflora productivity.
ing rates of sulfate
reduction between
soils at Sapelo Island, Georgia.
significant
Skyring et al. (1979) found vary-
differences
in
the
and short
tall
However, King et al.
rates
of
sulfate
these same types of sites at the same marsh.
Spartina marsh
(1982) found no
reduction
between
According to Cappenberg
So4
+ adenosine-5'-triphosphate
(ATP)
Jr
sulfate adenvltransferase
adenosine-5'-phosphosulfate
+
pvrophosphate
(APS)
HI
2+
APS
adenosine-5'-phosphate
+
(AMP)
SnO3
oxidized
ferrodoxin
reduced
ferrodoxin
cvtochrome-c 3
cytochrome-c
(Pe")
S03
j6e
Fig. 51
Dissimilatorv Sulfate Reduction:
the oblltate use of sulfate
as the terminal electron accentor for anaerobic resniratorv
metabolism in the snecleR of nequlfovibrio and DeRulfotomaculum.
(e'
)
126
(1974),
Winfrey
and Zeikus
(1977),
and
Ferry
and
Peck
(1977),
rates of sulfate reduction are generally associated with
methanogenesis and vice versa.
in
agreement
the
with
observations
genesis in
the same region made by King
and
(1978).
Wieke
At
same
the
low rates of
Skyring et al. (1979) suggest that the
lower rates of sulfate reduction they observed
thus
high
time,
in
the high marsh are
of high
and
(1977)
Skyring
most
of methano-
rates
researchers
and
King
agree
that
volatile sulfide concentrations are much higher in short Spartina (SS)
soils
than
in
tall
that Spartina growth
Linthurst
lated
and
concentrations
1981;
is
soils.
Several
authors
inhibited by soil anaerobiosis,
1980; Mendelssohn and Seneca,
Seneca,
transport
by oxygen
(TS)
Spartina
plants
within
and by the
speculate
per se (e.g.,
and regu-
1980),
sulfide
volatile
and redox potentials of the marsh soils (Howes
King et al.,
All of
1982).
these
have
researchers
et al.,
observed
a
strong positive correlation of Spartina growth with soil water movement,
and
significant
similarly
a
negative
correlation
of
volatile
sulfide concentration with Spartina growth and, thus, water movement.
King et al.
(1982) speculate that regions of poor soil drainage or low
water movement are observed to have much higher volatile sulfide concentrations
than marsh regions which flood regularly due
iron
interstitial
concentrations
found
to the dif-
between
these
ferences
in
regions.
According to King et al. (1982), pools of dissolved iron are
universally
related
concentrations
soils.
to
those
of dissolved
Because
iron
is
not
of dissolved
iron were
readily
sulfide,
and
highest
the
in
the
low marsh
available
for
sulfide
found
or
TS
precipi-
127
tation in high marsh or SS soils, high concentrations of volatile sulfide may accumulate in these areas.
It
is
that
however,
interesting,
low
such
of H2 S
values
observed to be emitted from the regions of the high marsh
this
research.
While
marsh may exceed
sulfide
volatile
those of lower marsh
highly aerated due to the same
soils,
considerable
sulfur
compounds
from
these
soils
in
in
the high
are much
more
Perhaps this degree of aeration
upon the
influence
SS
studied
lack of water movement which enhances
the volatile sulfide concentrations.
exerts
concentrations
were
soils.
The
flux of
H2 S or other
reduced
results
of the
studies
field
honducted at Wallops Island certainly indicate that this is true since
maximum
fluxes
of H2 S and
OCS
were only
observed
periods
during
of
high soil moisture in these regions.
Returning
global
to
the
relative
of biogenic
source
sulfur,
global
yr-1.
This
from land
salt
water
represents
(Granat
sum of the
contributions
marsh
at most
et al.,
the
the
of
observed may represent
averaged H2 S and OCS fluxes
annual
importance
high
as
marsh
average
a
diurnally
an upper limit of
x
of only-8
g
108
S
-0.02% of the global biological decay
Table
1976,
5).
are to remain of interest to the global sulfur cycle,
these
areas
appears
that
if
Therefore,
it
the primary role must be attributed to other reduced sulfur compounds,
perhaps
especially
and
example
for
(CH3 ) 2 S
(Goodwin
interesting to measure
(CH3 )2 S
concentrations
in
in
salt
et
al.,
1982).
situ volatile
marsh
soil
It
sulfide,
pore
would
OCS,
waters
be
H2 S,
simul-
taneously with the determination of their rates of emission from both
the TS and SS soils.
128
This
natural
research
sources
represents
of
currently comprise
and
amount
could
of
reduced
stagnant
emissions
above
setting.
flux
a
Although
gases.
from heterogeneous
and
to quantify
flux
environments,
the rates at which gases are
their
warned
creates
artificial
concentration
disturbs
the
perhaps halting or reversing fluxes.
that
potentially
use
emitted in
(1978) has
thus
chambers
to determine the source
Hitchcock
chambers
source
sulfur
in the effort
the only option available
significantly alter
undisturbed
a beginning
the
use
an
of
gradients
fragile
balance,
Dynamic flux chambers may not be
adequate since most do not mimic in-situ wind motions and variability,
and
increased
Another
potential
scrub ambient
of efforts
sary
humidity
and
air,
source of
such
to quantify
should
improvements
as
enhance
soda lime
are
and
surface
and Drierite.
instrument
seasonal
stability,
studies
to
and to provide the
in situ measurements wherever possible.
effects.
the compounds
used
to
The continuation
sources of sulfur compounds
multiple
settings,
losses
interferrants
natural
include
to enhance
ruption of natural
may
and
is
neces-
analytical
insure minimal
dis-
option of conducting
129
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138
APPENDIX I
Curriculum Vita
NAME:
Mary Anne Carroll
National Center for Atmospheric Research (NCAR)
P. O. Box 3000
Boulder, Colorado 80307
(303) 494-5152, Ext. 688
EDUCATION:
B.A. (Chemistry), 1978, University of Massachusetts/Boston
Doctoral Candidate (Atmospheric Chemistry), Department of Earth
and Planetary Science, Massachusetts Institute of Technology,
anticipated completion date:
April 1983.
PROFESSIONAL EXPERIENCE:
University Corporation for Atmospheric Research Fellow,
June 1978 - May 1979
NCAR Graduate Research Assistant, June 1981 - present.
RESEARCH EXPERIENCE:
Worked with Dr. Paul Crutzen and Dr. Louis Gidel on a twodimensional model of the troposphere, sunmer 1978 at NCAR as UCAR
Fellow.
Thesis research with Dr. Ronald Prinn (MIT) and Dr. Ralph
Cicerone (NCAR): Conducted an experimental study of the flux of
carbonyl sulfide from a salt water marsh (at Wallops Island,
June-October 1982); developed analytical procedures to measure
sulfur concentrations and determine fluxes of various reduced
sulfur gases. Research with Dr. Cicerone at the Scripps Institution of Oceanography, La Jolla, California, June 1979 - January
1980. Research at the Marine Biological Laboratory, June 1980 September 1980. Research with Dr. Cicerone and Mr. Leroy Heidt
at NCAR, October 1980 - present.
HONORS:
University of Massachusetts/Boston:
Graduated Summa Cum Laude
with University and Chemistry Departmental Honors, Outstanding
Senior Chemistry Award, Phi Beta Kappa Book Award, Nomination,
John F. Kennedy Award, and Nomination, Danforth Fellowship competition.
Danforth Fellow, 1978 - present.
139
PROFESSIONAL SOCIETIES:
American Association for the Advancement of Science
American Geophysical Union
Association for Women in Science (AAAS)
Sigma Xi
Society for Values in Higher Education
RESEARCH INTERESTS:
Atmospheric and Analytical Chemistry
Biogeochemical cycling of compounds: Method development and
application for measuring natural and anthropogenic source
contributions of chemical species as well as species concentrations in clean and polluted ambient air.
PUBLICATIONS:
Carroll, M. A., An Experimental Study of the Fluxes of Reduced
Sulfur Gases from a Salt Water Marsh, Doctoral Thesis,
1983.
Carroll, M. A., L. E. Heidt, R. J. Cicerone, and R. G. Prinn,
Carbonyl Sulfide Fluxes from a Salt Water Marsh, Paper No.
A22A-03, presented at the Tropospheric Chemistry section of
the Fall American Geophysical Union Meeting, San Francisco,
California, 1982.
Carroll, M. A., Sources of Reduced Atmospheric Sulfur Gases, in
"Interaction of the Biota with the Atmosphere and Sediments," Eds. M. N. Dastoor, L. Margulis, and K. H. Nealson,
Final Report, NASA Workshop on Global Ecology held October
18-20, 1979, p. 28.
Consultant to the Space Science Board, Committee on Planetary
Biology and Chemical Evolution, National Academy of
Sciences, National Research Council: "Scientific Strategy
for the Decade 1980-1990. Origin and Evolution of Life:
Implications for the Planets," 1980.
Alper, J. S., M. A. Carroll, and A. Gelb, Classical Trajectory
Study of Rotationally Inelastic Scattering of Two HF Molecules, Chemical Physics, 32, 471-479, 1978.
140
APPENDIX II
Analytical Instrumentation Used at the
Scripps Institution of Oceanography
The Tracor 560 gas chromatograph,
discussed in
Section II,
along
with a linear chart recorder comprised the initial analytical instruemployed
mentation
Institution
of
in
developmental
Oceanography.
weight
over
monitored
time,
standards
standards
Permeation rates
flowing continously.
loss
Secondary
Primary
at
were
the
were
generated
Scripps
generated
tubes in temperature-controlled
housing A.I.D. permeation
diluent-N 2
conducted
work
by
cells with
were determined by
with
a
microanalytical
balance.
by
a
routine
static
dilution
method, using a calibrated pressure gauge and a calibrated regulator.
A vacuum system was employed in
an evacuated
cylinder
(see
the transfer of the gas of interest to
Fig.
52).
This
transfer
were
and
399A/F),
(model
(model 91-005),
made
using
Orion
using
a
titration,
salinity
gel-filled
Research
lonalyzer
pH
electrode
combination
(model 97-08).
Sali-
dissolved oxygen values, were determined by
where
hydrometer.
distilled water were
test solutions.
KC1
Orion
portable
and an Orion oxygen electrode
nity, required to adjust
chlorinity
a
by
Dissolved oxygen and pH
successive dilutions with zero grade N2 gas.
measurements
followed
was
(1,80655)(o/oo
Research
grade
=
o/oo
S,
chemicals
and
C1-)
and
by
twice-
used to make the required buffer and electrode
PRESSURE
GAUGE
EVACUATED
RECEIVING
CYLINDER
Fig. 52
Primary standard generation by dilution method
142
APPENDIX III
Analytical Instrumentation Used at the Marine Biological Laboratory
The chromatographic system used at the Marine Biological Laboratory
consisted
of
model
Hewlett-Packed
equipped with a Tracor Flame
Photometric
Instrument model 3A
chromatograph
The data acqui-
Detector.
sition system consisted of a Dohrmann 1 my
Scientific
gas
5730
recorder
and a Columbia
The photomultiplier tube
integrator.
and part of the detector has been surrounded by a cooling coil maintained at 10°C to improve the signal to noise ratio (Steudler, unpubcommunication).
personal
lished manuscript,
A
6'
x
1/8"
O.D. FEP
Teflon chromatographic column packed with Chromosil 330 (Supelco) was
employed
consisted
purge
for
of
calibration
an
overnight
flow, with the
and
sample
bake
at
Column conditioning
analysis.
120"C with
column disconnected
a continuous
zero
Sepa-
the detector.
from
N2
ration of the sulfur compounds was achieved by temperature programming
the column from 25*C to 100C at 8*C/min with an
initial 4 min delay
(Steudler, unpublished manuscript, private communication).
data was
collected
junction with an
foil-wrapped
Chapter 3).
using
Maximum #41
Generator
integrating voltmeter.
60/80
molecular
sieve
Wind speed
anemometers
in con-
Samples were trapped
5A-60/80
Tenax
GC
traps
using
(see
143
APPENDIX IV
SP4100 Program and Rotameter and Thermocouple Calibrations
Table 6
SP4100 Program
5
10
20
25
30
35
40
ECHO
0:
INPUT "LOOP #" G1
!"OCS(0) H2 S(1)": INPUT 62
!"INPUT CURVE R = A*C**B?": INPUT I
IF I = 0 THEN 30 ELSE INPUT "A" G3: INPUT "B" G4
INPUT "TRAPRATE" G5; INPUT "TRAPTIME" G6; G7 = G6*G5
INPUT "LOOPEFF" G8; G9 = G8/100
INPUT "CHAMBERF" Ml; INPUT "GCAT" M2; INPUT "RESPONSE" M3
45 M4 = (M3*M2/G3)**(1/G4); M5 = M4/G9; M6 = M5/G7
85 INPUT "CONCIN" M7; M8 = M6 - M7; M8 = M8*"1.36184;
M9 = M8*M1*60/0.5574
100 !"LOOP #": G1
110 !"COMPOSITE CURVE:" G3"*C**"G4
115
!"TRAPPING RATE:" G5"Std.cc/min"
120 !"TRAPPING TIME: "G6"MIN"
125 !"VOLUME TRAPPED: "G7"ML"
130
!"LOOP EFFICIENCY:"G8"%"
135
!"CHAMBER FLOW:"M1"Stnd .cc/min"
G2 = 0 THEN 140 ELSE 141
IF
136
140
!"CONCENTRATION: "M6"ppb OCS"
141
!"CONCENTRATION: "M6"ppb H2 S"
145
!FLUX:"M9" ngS/m2-hrr"
150 END
"t
INPUT " 6hl
Ji=1: EUMtU 0: INPtIl *~H'f:
S
INUI
" [NJ " H
I NPUI
" LIEtP1 'H:
IN'U I 'UVI "H1:
A-::[NPU1'"FLTP ",:[PULT"Z..
H2'I7*:INPUr* H
[NPUI
51"
(t,
hPLEE.1": INeUI D
:
; IHNDH
N
52
[NP'uT 04
IF DI TH N ! FLDi) SI D GEN ():
7b8
IF D4 THEt
51
INPUT
536
5.7
5.S8
54 U
545
"TLAe'85:
65=85+273
PLR6"84: E4=84-86
INPUT
a: I ' :
f- 1 "
F
)
! *r IH IEr ( Ik;1
IF Li THEN :5=60 ELSE C5=34
IF Lib THEN Zb='*HID' ELSE Z6=' .INIt4E
INPUT *r UX'Ui1: UI=UL+Z;7
IF iD6 THEN INPUT "bH-s'Ci: E£LE 5t5
IF D1 THEN INPUT "fPT#'C: ELSE bS'
5t55 INPUT
5 .1. INPUT
L': *
:
-
6(1
*FLeOWS: IlU
" i'f8: IN-UT
62
625
"F't
: GUTu
6.1
t4) " :
L tt4PLI
I
L1':P
tL
144
595
!*CELL(0) PT(LiO: INPUTI Z4: IF Z4
IF Li THEN 811>.aCOS'
ELSE 8lIoH2S'
INPUT *CELL**B2
602
605
INPUT O*PR6: IN4PUT oz~aq: eq=eq*IA
INPUT OFL.OW*8: If Z4 THEN 621
E?=(8+e476E*LU*89/E4*. 3592i*B 7/85)
E8(Ji')=E?*.93*4i'6i0: GOTO 635
IF L2 THEN 6310 ELSE INPUT *PTV82: INPUT *PR88
E6=85*62358. 9?/U5*84
E?=E6*88/(87*E4*. 35921/85): E8(Ji.=E?*. 93*84/76e0
IF L4 THEm E7=E?*C8/C9 ELSE 635
E84(J1)=E7*. 93*84/760
!*FL0WIN4G0;E7jPP8*: IF D5 THEN ?84
!DBILuTIO?: INPUT *Dl?14
IF L4 THEN 561 ELISE 640i
615
6213
625
6.30
63±
632
£35
637
THtEN b015
!*INJECING";E8(J);PPvL'
645
646
650
!
OF TR IALS
1* TH IS ClUtlNC?: It4'U T
N±=e: W3=0
!OST98 CHECvK?- YvL) NwOI: IN4PUT C: If
£54 ECHO
ber
ij*fei:
I X=b
C=@ THEN 660Y
I.
I MPlUT
F*LHVE
INU Iu fM2: I NPU T
RN I R'o
INPUT0 TUVHER
I1- D5 THEN F 1=2 ELSE. F I =1
Z2=;eEEKwL.:f%49: Z - =''PE E v.* L;96
PUvN 2 6 0 m ENDl
FOR~ C~
TO 5ki: NE)U
IF Ix ImEN ?ib5
IF fit THEN ei=Cl
=3P EL
E r * C-"9 6
68,5
690
69i
T I ME: 'a; 5. Ei3Z2;*Z3
692
I b. VLH
IF
E-94
DL8fl
PH2
b 14t
4 rHEN
=
PH I:
H~L/ 82
FILLrF);::;S5
0856
0:
84," )
i:6(
t
1
TfO!S*E':E
8%=*CUS
t,*PLH?
H5, - ZERO:
:4
$5.
P pI' FlHObf'1r
p
o 'pwP,
kbPUF~E
.*-EaP*6
HE lH F IH842 BC CULDE
1PM
8f
1 :1# "IHE~l-eI'a 0? T
H;PFN
EXI
1uF' m=iru M4: !m; PSI (4)'; PS(N) PbH(i
19 U!5=1I IHEN 8125
S=QtH-LX* IF S;K:. IHEN 728
LZI-1K
b94=4-
b'4
'4
2
P:-8
1
fy~ix+t:
[F
[x=cet
''H'THLS vI CS PEPOR T ON LiS T
74 !*SrOPE
ELbE
THEN HI=N±/
DA4TH FOR CUIRVE?-:
rtieEE
INPUT
A
665
r R IALS'
145
-IF H IMEN ?40 ELSE 645
?48i
?41. !*MEN CONt4C?: INPUT *NC*L2
742 IF L2=s fTHEN 744 ELSE JI=Ji+i
7.43 IF o6 THEN4 555 ELSE 685
?44 FOR 1=2. TO Jj: FI±(I).1: NEXT
745 i rositseAL ISR14TION CURVE* : St=8: S2=0: $3=0: S4=0: S5=0
COT0647'LOG R'
?46 ,tprorit5coNcr826R*GCHrrAB3LOG
?4? FOR 1=i. TO JI: Z=yjju,[)
748 x51=LGTE8(Z): Y!5(1)=LGr(N5(Z),: X=X5u,): V=Y5(1)
749 !Z.0SI.8.2 E8(Z)*.S2 '5(Z.;$10.5 1K5UJ:,*2..5 Y5I1)
Si.=Sl+X: S2=Se2+X*X: S3=S34v: S4=S4+ Y*Y: S5=S5-.i*Y
) ((I
5= ji*5S*
t*52-S*S
S
7
(b4 i! otURVE: g
tSr=?" **LON C**j,
66
755
?58b
75 7 X2=YxlX2: VCORP.
I F m=1. rmEm '77
CLUEFF. :XZ:
?58 !'ADVHiNCE. P8PE~R TO DESIRE.D ORIGIN*: GRI1PPO,B,L: ENDJ
75 9 R!8=S 7: ZS=S6: ! TAB 26 "LOG iR*Gcicmr
!1R7 .oorfie2i a 7. 5'a rAS 358 8. o r0849 '8. 5 ' TA863 '9. 0'
7 to2.
?b2 fI.R L=210v rO Q.IosrEP *wiftiPti0, 1. L.
762
?64
?65
CiRfHti8, 2
FOR 1=2:1*
2: NEXT
1
0
,
@STEP
88
-2f8OGRRPH
I. 2.081
?b6
Fufe L.L TOI Jix=(x)f5 D-2 )2000: Y=(Y5U 1)-7 )*4(10+180
bwHPH X-5*,VY, L: bIeHptH X-58 V,
?69
LiPHPH
X. Y+i.j-, L:
GPRPHY-a
7*30
784
782
795
8101
NEXr
S7=LGT(s7.
Y=208*9-a)?S-2
ufeP2,!oi(oo,'S2
? ?2.
00i.:
GRfAPN o.o~to: !rso,832.8'
!rfisi*Lu
ukHpH22"
~
,0L
!TF4B3*2.5'
RA7S:
C": GR14PH 1.6f@,8,2L: !TA163'3.L1'
Hi=l: GUFu ?45
tt
t4vrmHER CURE?:1. INPUT J26: IF J2=8 r#HEN 781.
IN4PUT it
! oimpur # OF Po I rSO
t aINPUT Pr*i's'
FOft Ent. TO JU LNPUr 11±(121 KEX-T
60 TO 74%5
i amV i T214PPVWE3 TESTS73 TUPUT X: If 9=10 TMEN Et4D
D5=1: SOTO beS
I
A**E:INPUT
!*IPtUT CUPVE
IF 1=1 THEN 7910 ELSE INPUT d"OWB: INPUT 68Z8
FI=2: IF D4=1 THEN 665
rRfHE' TOR2: Rl=kl*E4*.3592L/85
INPUT *F2*RU.: INPUT
'R=Rl*p?2*E?l *2=P24±: Tr<5)=R2: P2=k2e. 84
TT(6)=Re2: P2=R2+2: TT.7.'=R2: k2=R-2+4: TT(8)=P2
!&C 'TEOR:'P36PPBI'IL F2C:*Ri
1B@5
R4=1/Z8: 'FOP 1=1
TO 0~4
146
82
RS=PSki
825 ! CONC=
)*C2/R)**4
P 5
C/c=
835
et.
END
RUN
6?"
END
870
9 5
871
'*PLOT FROr EXTkERNL D
!' [NPT I OF POINTS:
INPUT Ji
=1. TO Jt
910 FO
INPUT *L
915 INPUT "LOU &6CT'VY I : N5Ul=lC'**Yl:
928 GOTO 744: END
PUN 8 701
2tS2 RUH
kUN
2711 G- TU
2712 EN D
271.5
44,t
759:
900:
48' l
4k41
87t8
t7?1
LIN 8 70
EN 1.
ENi
END
NEXT
147
Table 7
SP4100 Program Variable List
Name
OV T
DET T
INJ T
RH2
RAIR
FLTR
ZERO
STD. GEN
GAS
PLAB
PH20
PLAB-PH20
TBFM
LV
GCAT
PT#(FF)
PR(FF)
MWT
TBOX(FF)
F2(FF)
FPT(FF)
VFI(FF)
VF(FF)
F2C(FF)
FPTC(FF)
Fl(FF)
F(FF)
K*1000
INIT CONC(FF)
FLOWING CONC
INJ. CONC
CONC. INDEX
CELL OR PT (KIN)
CELL#
PSTD
PR
FLOW
TUBE#
# OF TRIALS
TLAB
EXT.STD.FLAG
TIME
INJ.TIME
% DRIFT
DRIFT RATE
Variable
Al
A2
A3
A7
A8
A5
A6
D6
B1
B4
B6
E4
B5
Cl
C2
C3
C4
C5
C6
Dl
C7
08
C9
Dl
C7
C8
09
E6
E6
E7
E8(J1)
Ji
Z4
B2
B3
B8
B9
B7
Z5
E9
C6
Zi
Z2; Z3
G3
F5
F5
Units
FC
°C
°C
ML/MIN
ML/MIN
S,M,F
OFF,L,M,H
0 = KINTEK, 1 = FF
TORR
TORR
TORR
0C (converted to K)
ML
INPUT * OUTPUT
NG/MIN
G/MOL
"C
ML/MIN
VOLTS
VOLTS
VOLTS
ML/MIN
ML/MIN
ML/MIN
ML/MIN
PPB
PPB
PPBML
0 = CELL, 1 = PT
PSI (converted to TORR)
NG/MIN
ML/MIN
0C
(converted to K)
0 = NOT STD, 1 = EXT.STD.
HR:MIN:SEC
TIME BASE UNITS
%/HR
148
Name
Variable
FILENAME
ANALYST
DAY
TRIAL INDEX
# OF PEAKS
RT
AREA
HEIGHT
BL CODE
TRIAL#1 AREAS
TRIAL#2 AREAS
TRIAL#3 AREAS
MEAN
a
%RSD
ZLOG AREA
2
r(LOG AREA)
ELOG CONC
E(LOG CONC x
LOG AREA)
E(LOG CONC) 2
CORR.COEFF.
NUMBER OF VALUES
PRED. AREA
NM,NM(1) ,NM(2)
AN
A
IX
A4
PST( )
PSR( )
PSA( )
PSF( )
El( )
E2( )
E3( )
A
B
CORR FOR DRIFT
STD OR SAMPLE
STDGEN SAMP OR
FIELD
PUMPING RATE
SAMPLING TIME
TRAPPED CONC
(IF 100%)
PREDICTED CONC.
%EFF. R/R
%EFF C/C
N1(
)
N3(
N4(
)
)
Units
sl( )
S2( )
s3( )
S5(
)
F9( )
U
NV
F4
R*GCAT =
A*CONC**B
R8
Z8
Z
D5
3*#CONC.
%/HR*HR
O-STD 1-SAMP
O-STD GEN 1-FIELD
ML/MIN
MIN
PPBML
PPBML
%
149
Table 8
Main Program
Line #
Comments
500-533
INITIALIZATION, INPUT PARAMETERS
TURN OFF PRINTER
COUNTER,
500
INTIALIZE CONC.
501
ZERO STATISTICS REGISTERS
505,510
INPUT GC PARAMETERS
515-525
SELECT STD. OR SAMPLE,
TRAPPING SUB-R
531
INPUT TLAB,
532,533
INPUT PRESSURES + CORRECT FOR H2 0 VAPOR
535,536
SELECT KINTEK OR FF, H 2 S OR COS. SET PROPER MWT.
545-560
IF SAMPLE (L FD)
CONVERT TO K
PERMEATION TUBE OPTION
545
IF KINTEK GO TO KINTEK CALC SUB-R(595)
555
CORRECT "F2"
560
INPUT FLOW METER VOLTAGES.
595-630
TRANSFER TO
H2 0 VAPOR
P,
FLOW FOR T,
RETURN POINT FOR NEW CONC.
KINTEK CALCULATIONS
TUBE.
IF TUBE GO TO PT CALC (605)
595
SELECT CELL OR PERM.
601
INPUT RAW GAS PRESSURE (PSI).
605
INPUT FLOW. IF PERM. TUBE THEN GO TO PT CALC (620).
RETURN POINT FOR KINT. NEW CONC.
610
CORRECT FLOW FOR P, T, H 2 0 VAPOR. CALCULATE FLOWING CONC.
615
CALCULATE INJECTED CONC.
620
KINTEK PT CALC. IF NEW CONC, CALCULATE AT 630 ELSE INPUT
PARAMETERS.
625
INTERMEDIATE RESULT IN CONC.
630
CALCULATE FLOWING CONC,
CONVERT TO TORR.
GO TO 635 TO PRINT CONCS.
CALC.
INJECTED CONC.
150
Line #
Comments
635
PRINT FLOWING CONC. IF TRAPPING TEST GO TO TRAPPING SUB-R
(780)
645
INPUT # OF TRIALS. RESET INDEX.
646
RESET STATISTICS REGISTERS.
650-655
STABILITY CHECK
654
TURN PRINTER ON
655
PRINT COMMENTS ON FLAME, GAS FLOWS, OTHER.
660
SELECT FILE. IF SAMPLE, FILE 2. IF STANDARD FILE 1.
665
INJECT
GET INJECT TIME VALUES. TRANSFER PROGRAM CONTROL TO ROM
PROGRAM AT LINE 2600. END EXECUTION OF "MAIN PROGRAM"
ON 2ND "INJECT/STANDBY" OR "ERO" CONTROL IS TRANSFERRED
FROM LINE 4841 OF ROM PROGRAM TO LINE 870 OF "MAIN
PROGRAM" MORE INFO ON TRANSFER IN "ROM PATCHES"
670-725
REPORT
670
DELAY LOOP TO AVOID OVER PRINTING CHROMATOGRAM. IF NOT
FIRST RUN AT THIS CONC, PRINT ABBEREVIATED REPORT AT LINE
715.
680
GET VALUE OF DAY FROM MEMORY
685-710
PRINT PARAMETERS
715
ASSIGN # OF PEAKS IN CHROMATOGRAM TO USER VARIABLE
720,725
ABBREVIATED REPORT, PM#,
726
IF SAMPLE RUN GO TO TRAPPING CALCS AT 815. IF ONE OF LAST
THREE RUNS USE DATA FOR STATICS ELSE 728.
727- 732
RT, AREA, HEIGHT, BC CODE
STATISTICS CALCULATIONS
727
ADD DATA TO ZAREA + Z(AREA) 2 REGISTERS
728
INCREMENT INDEX, IF INDEX * # OF TRIALS INJECT AT 665
ELSE CALCULATE MEAN.
729
CALCULATE STD. DEV. AND %RSD
730,731
PRINT HEADER FOR STATISTICS REPORT
151
Line #
732
734-757
734-735
Comments
PRINT STATISTICS DATA
CALIBRATION CURVE
CHECK FOR GOOD DATA. IF YES STORE DATA (740) IF NO GO TO
# OF TRIALS AT SAME CONC (645).
740
STORE RxGCAT
741, 742
743
ASK FOR NEW CONC IF YES* INCREMENT CONC. COUNTER INPUT
VFPT ETC (560) OR FLOW (605). IF NO CONTINUE WITH
CALIBRATION CURVE CALCULATIONS.
744,745
PRINT CALIBRATION CURVE HEADER
746-748
LOOP TO PRINT CONC, RxrCAT, LOG C, LOG R
749-751
STORE DATA AS E LOG CONC, E(LOG CONC) 2 , ELOG(RxGCAT),
E(LOG RxGCAT) 2 , E(LOGCxLOGRxGCAT)
752
CALCULATE SLOPE
753
CALCULATE INTERCEPT,
754
PRINT CURVE PARAMETERS
755-757
CALCULATE AND PRINT CORR. COEFFICIENT
779
IF
780-845
NO SAMPLE,
1 0 INTERCEPT.
END
TRAPPING CALCULATIONS
780-785
INPUT CURVE PARAMETERS
790
SET FILE 2 FOR ANALYSIS.
(MANUAL
IF FIELD SAMPLE, END.
INJECT)
795
INPUT "F2",
800-805
CALCULATE THEORETICAL CONC.,
CORRECT FOR T,
P, H2 0.
SET TIME FUNCTION TIMES
BASED ON TRAPPING TIME.
810
END "MAIN PROGRAM"
815-830
CALCULATE CONC.
835
NEW CONC.
(MANUAL INJECT).
AND % EFF.
IF YES GO TO 795.
IF NO END (MANUAL INJECT).
152
Line #
Comments
870
LINK FROM ROM PROGRAM 4841 TO REPORT AT 670.
871
END
2690-8781
ROM PATCHES
2690
BEGIN ROM PATCH (ALLOWS STATEMENTS TO BE PLACED IN ROM
FOR CALLS BY "MAIN PROGRAM")
2711
ON 2nd "INJECT STANDBY"
REPORT"
2712
PREVENT FURTHER EXECUTION OF ROM PROGRAM.
4450
TRANSFERS TO "END OF REPORT"
8780
TRANSFERS CONTROL TO "MAIN PROGRAM" AT LINE 870..
8781
PREVENTS FURTHER EXECUTION OF ROM PROGRAM.
OR "ER0" TRANSFERS TO "END OF
153
Table 9
Plotting Subprogram
Line #
Comments
758-759
PRINT LABEL + SCALE FOR Y-AXIS
760
DRAW Y-AXIS
761-762
DRAW HASH MARKS AT 0.1 UNIT INTERVAL
763
DRAW X-AXIS
764-765
DRAW HASH MARKS AT 0.1 UNIT INTERVAL
766
CALCULATE X + Y POSITION IN PLOTTER UNITS
767-768
PLOT POINTS WITH "+"
769
CALCULATE END POINTS OF LINEAR REGRESSION CURVE
770
DRAW LINE BETWEEN END POINTS:
MOVE PRINT HEAD TO ORIGIN:
PRINT SCALE OF X-AXIS
771-772
CONTINUE PRINTING X-AXIS SCALE + LABEL
777
ASK IF TRAPPING TESTS WILL BE RUN:
778
IF YES, SET SAMPLE FLAG TO 1:
IF NO END
TRANSFER TO LINE 520 TO
ASK FOR FIELD OR STANDARD GENERATED SAMPLE
154
Table 10
Tracor Rotameter Calibrations
P(psi)
Reading
Flow Rate (mX min-1)
Carrier Control #1
60
1.0
-1.8,1.9
3.1
4.0
5.0
6.0
1.0
50
Carrier Control #2
0.9
50
1.0
60
1.0
80
2.0
4.0
6.0
18.0
29.0
41.9
54.2
67.1
80.1
15.3
24.8
29.8
37.0
47.4
72.2
106.7
Air
*~60
100
150
200
250
100
150
200
250
-30
60
100
140
200
* will not go below 50 easily
will not go below 100 easily
55.4
90.9
152.0
206.7
263.45
94.6
151.4
200.1
247.8
26.5
57.2
94.1
128.3
203.3
155
Table 11
Chromel-Alumel Thermocouple Calibration
my Reading
#1
#2
#3
#4
42.7
1.69
1.69
1.69
1.69
34.2
1.34
1.34
1.34
1.34
26.85
1.05
1.05
1.05
1.05
21.9
0.86
0.86
0.86
0.86
12.7
0.49
0.49
0.49
0.49
47.05
1.87
1.87
1.87
1.87
Temperature ("C)
Linear regression: T*C = 24.94 (voltage) + 0.55
0.5503681 ±0.1770746
Intercept
=
Slope
= 24.94490 ±0.1356055
R2
=
0.9998818
Sy.x
=
0.1575087
156
Fig.
8
I
I I
Rotameter calibrations
53
I
1
.
I
I
I I
I
A
F= 13.066(f) 1.3517
R2 i 0.9980
7
x/
I/
6
r-4
I-w
/
//
.- j
LL
Q-
OL
-
4
00
_J
3
F= 41.758 (f) 1.07121
R2 z 0.9978
2
I
O1
I
I
i
I
I
i
I
I
I
10 20 30 40 50 60 70 80 90 100 110
LEVEL
I
120
157
APPENDIX V
Empty Teflon Sample Loop Efficiencies
158
Table 12
Empty Teflon Sample Loop Trapping* Efficiency Tests
% Efficiency ±Standard Deviation (# Trials)
Loop #
1
1
2
3
4
5
5
6
7
8
9
10
11
11
11
12
12
13
14
14
14
15
16
17
18
19
20
20
21
21
22
22
22
23
24
25
26
27
28
28
29
30
31
32
OCS
71.79
69.95
70.90
69.98
73.60
74.74
75.94
76.10
72.03
74.15
73.57
72.26
69.38
71.73
68.33
73.34
69.42
74.21
72.395
74.71
66.34
73.52
75.36
70.95
74.51
76.48
70.05
67.33
65.93
65.39
71.28
65.24
68.67
71.36
72.97
78.66
73.78
74.12
73.40
69.21
72.97
73.94
74.64
71.37
±0.04
±2.31
±0.54
±1.07
±3.03
±0.09
±0.25
±0.075
±1.98
±0.30
±0.35
±0.90
±0.67
±0.51
±0.30
±0.73
±0.57
±0.51
±4.56
±0.57
±0.40
±0.27
±1.06
±0.37
±1.89
±0.14
±0.41
±0.55
±1.37
±0.77
±1.84
±0.84
±0.15
±0.24
±0.11
±0.52
±0.76
±0.45
±0.18
±0.74
±1.51
±0.42
±0.73
±1.16
H2S
(3)
(4)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(4)
(3)
(3)
(3)
(3)
(3)
(5)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
62.29 ±1.33 (6)
60.71
59.60
62.84
62.00
±0.49
±4.82
±2.10
±0.62
(3)
(3)
(3)
(3)
65.14 ±1.57 (3)
63.12 ±0.28 (3)
65.32 ±0.52 (3)
159
Loop #
% Efficiency ±Standard Deviation (# Trials)
OCS
HS
75.72
77.55
67.57
73.01
74.55
70.36
65.21
71.67
67.13
73.44
72.46
77.89
70.40
74.55
72.84
66.76
74.57
69.10
76.34
67.67
74.84
73.91
76.91
66.57
76.97
69.91
76.04
73.99
76.62
±0.20
±0.12
±0.94
±1.44
±0.55
(3)
(3)
(3)
(3)
(3)
±4.74
±0.44
±1.09
±2.74
(4)
±0.55
(3)
(3)
(3)
±0.20
±0.23
±0.60
±4.89
±0.61
±2.07
±0.38
(3)
(3)
(3)
(3)
(4)
±0.40
(3)
(4)
(3)
(3)
±0.23
±0.64
±0.36
±2.21
±0.59
±1.38
±0.33
±0.23
±0.52
±0.19
±1.17
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(4)
*Trapping E collection plus desorption
72.37 ±2.862% efficiency (3.95%
Average of 50 "1st tests" for OCS:
relative standard deviation). Total error = 53.88 or ±1.49%.
62.63 ±1.97% efficiency (3.45% relative
Average of 8/50 H2 S tests:
standard deviation). Total error = 12.33 or ±2.46%.
160
APPENDIX VI
Mechanical Fits to Plots of
Concentrations to Determine C(t i ) for
Wallops Island Flux Studies and Concentration and
Flux Results, Reported With Their Errors,
for HS and OCS
161
Fig. 54
Mechanical fits to OCS concentrations for August 5-6,
1982 field study
2 =
Y =-1072.992 + 0.859x; R
1.00
2
3 2
Y - -1.384 x 10- x + 5.741x - 5306.83; R
= 1.00
2
- 3.159x + 703.07; W= 1.00
2
- 3.696x + 763.06; R = 1.00
Y = 3.667 x 10-3x
Y = 4.557 x 10-3x
2
Y = 1.259 x 10-2x 2 + 17.501x - 5.638 x 103; R2 = 1.00
2
Y = 1779.18 - 1.88x; R = 1.00
Cocs
ppt
500
400
300
200
100
0
12
14
16
18
20
22
00
2
4
6
8
10
12
TIME
Fig. 55
Mechanical fits to H2 S concentrations for August 5-6,
1982 field study
-1100.36 + 0.857x; R2 = 1.00
-1.158 x 10-3x 2 + 5.171x - 5.520 x 103; R2 = 1.00
-1.133 x 10"2x2 + 15.6 4 8x - 5.066 x 103; R2
I
I
I
I
i
I
I
I
CH2 S
ppt
1.00
I
I
I
I
400
300
200
3:
100
b Eyeball
12
1
14
I
16
I
18
I
I
I
20
22
0
I
2
I
4
I
6
I
8
I
10
I
12
162
Fig.
16
Mechanical fits to OCS concentrations for
August 13-14, 1982 field study
-3.165 x 10-4x
2
2
2.891 x 10- x
1 818 x 10 3x
COC,,,
= 1.00
- 2.423x + 2.477 x 103; R
2
-6.704 x 10-4x
1.00
2
5.970 x 104 x
4
2 =
+ 0.948x - 623.23; R
2
- 0.297x + 91.262; R
2
1=
.00
2
+ 1.380x - 625.229; R = 1.00
2
- 3.960x + 2.227 x 103; R = 1.00
ppt
240
200
160
120
80
40
14
16
IS
20
22
00
2
4
6
8
10
12
14
TIME
Mechanical fits to H 2 S concentrations for
August 13-14, 1982 field study
Fig. 57
1.
2.
Y
3.
Y
4.
Y
5.
CH S
Y
6.
2 =
=
4 2
-5.893 x 10- x + 1.872x - 1.411 x 103; R
=
1.620 x 10- x
2
=
3 2
-1.710 x 10- x + 7.337x - 7.800 x 103; R = 1.00
=
9.826 x 10-4x
3 2
2
Y
2 =
2
Y = -1.448 x 10-3x
=
1.00
- 6.280x + 6.086 x 103; R . 1.00
- 4.776x + 5.794 x 103; R
2
2 =
+ 2.954x - 1.398 x 103; R
1.00
1.00
2
3 2
2.103 x 10- x - 4.666x + 2.671 x 103; R . 1.00
ppt
300
200
6
.
100
0
-5
13
15
17
19
21
23
3
I
TIME
-
5
7
9
II
13
163
Fig. 58
Mechanical fits to OCS concentrations for
August 18-19, 1982 field studies
2 =
2
10 4
Y = 6.119 x 10 - x - 2.392x + 2.471 x 103; R
1.
=
2 =
3 2
1.00
1.00
1.180 x 10- x - 4.929x - 5.203 x 103; R
2.
Y
3.
2
2
Y - -5.339 x 10-3x + 25.649x - 3.053 x 104; R = 1.00
4.
2
3 2
Y = -2.251 x 10- x + 1.852x - 2.564 x 102; R = 1.00
5.
Y
Y
6.
=
=
1.162 x 10-4x
2 =
- 0.656x + 9.570 x 102; R
1.00
2 =
5 2
-8.039 x 10- x + 0.413x - 1.904 x 102; R
Y = 6.720
COC S 7.
2
1.00
2
2
104x - 1.291x + 7.692 x 102; R = 1.00
x
ppt
300
I
2
200 -
3
s.,--i
100 ......
k
TIME
Mechanical fits to H 2S concentrations for
August 18-19, 1982 field studies
Fig. 59
I.
Y - 2.150 x 10-3
2
- 7.535x
2
6.722 x 103; R
*
2
2
1.00
2.
Y * 1.508A 10-5x - 0.2001 + 4.452 x 102; R
3.
Y . -3 339 x 10-2x + 1.636 x 102 - 1.959x 105; R
• 1.00
2
2
4.
Y a 2.225 x 10'2,2 - 11 683x + 1.611x 103;
5.
Y - -1.129 x 10-2,
2
2
2
9.248x - 1 319 x 103; R
1.00
2
2
• 1.00
1.00
6.
Y - 5.458 x 10-3x - 7.905x + 2.905 x 103, R
7.
Y - -1.705 x 103x
R.
Y = 6.810 x 10-4,2 - 1 410x + 9.711 x 102; R * 1.00
2
+ 3.895x - 1.954 x 103; R . 1.00
2
I
ppt
2
1 00
]
I
I
]
I
I
I
i
10
12
1400
1200
1000
-9
800
4
600
_5'
400
3:
:
200
I
SI
14
16
18
20
22
2
4
TIME
I
I
I II
6
8
I
164
Fig. 60
Mechanical fits to OCS concentrations for
August 26-27, 1982 field study
-3
1.035 x 10
1.153 x 10-
3
-3
3.766 x 10
2
2
2
2 =
x - 5.033x + 6.151 x 103; R = 1.00
x - 1.294x + 3.778 x 102; R
2
- 5.560x + 2.115 x 103; R
-9.417 x 10-4x
2
=
1.00
2
+ 2.294x - 9.350 x 102; R = 1.00
2
4 2
1.00
7.728 x 10" x - 2.329x + 2.164 x 103; R
Cocs
1.00
ppt
600
500
400
300
200
100
0
0
16
18
20
22
10
8
6
4
2
00
14
12
16
TIME
Fig.
61
Mechanical fits to H2 S concentrations for
August 26-27, 1982 field study
*
4.385 x 10-3x
2
* -2 637 x 10-4x
CH2S
ppt
2
- 18.429x + 1.936 x 104; R = 1.00
2
2
+ 0.670x - 3.!55 x 102; R = 1.00
700
600
500
400
300
200
100
0
16
18
20
22
0
2
4
TIME
6
8
10
12
14
16
165
Fig. 62
Mechanical fits to OCS concentrations for
September 3-4, 1982 field study
2 =
3 2
1.00
1.569 x 10- x - 6.083x + 6.295 x 103; R
2
3
2
-3-16x1
2
2
1.00
-1.386 x 103x + 5.018x - 4.122 x 103; R
-6.889 x 10-3x
2
2 =
+ 3.485 x 10x - 4.373 x 104;
1.00
2
1
4 2
2.633 x 10- x - 2.487 x 10- x + 8.693 x 10; R = 1.00
2 =
4 2
2.453 x 10" x - 3.843 x 10-1x + 1.964 x 102; R
Cocs
1.00
ppt
600
500
400
300
200
100
0
v
15
17
19
3
I
23
21
II
9
7
5
13
15
TIME
Mechanical fits to H2 S concentrations for
September 3-4, 1982 field study
Fig. 63
1.
2.
CHzs
4
Y = 5.908 x 10- x
2
2
- 2.461x + 2.655 x 103; R
= 1.00
2 =
3 2
1.00
Y = -3.415 x 10- x + 17.298x - 2.176 x 104; R
PPt
300
200
100
I
0
\
I
15
17
19
21
23
I
I
3
TIME
7
l0
i
9
II
0
13
15
166
Mechanical fits to OCS concentrations for
September 9-10, 1982 field study
Fig. 64
2
3 2
-1.280 x 10- x + 3.441x - 1.912 x 103; R = 1.00
2
2.068 x 10-3x 2 - 8.391x + 8.534 x 103; R = 1.00
2
4 2
2.221 x 10- x - 1.072x + 1.324 x 103; R = 1.00
3.008 x 10-4x
2
2
- 0.474x + 2.082 x 102; R = 1.00
2
2
-6.714 x 10-4x + 1.528x - 8.121 x 102; R2 = 1.0
Cocs
ppt
400
300
200
100
17
15
13
21
19
23
3
I
7
5
9
13
II
TIME
Mechanical fits to H 2 S concentrations for
September 9-10, 1982 field study
Fig. 65
Y z 6.011 x 10-4x
Y = -3 797 x 10-3x
CH2 S
I
I
I
2
2
- 1.684x + 1.368 x 103; R = 1.00
2
+
1
6
2
2. 13x - 1.021 x 104; R
I
I
I
I
I
1.00
I
I
I
ppt
300
200
,
100
62
\
o o
-
0
I
12
14
I
16
I
I
I
18
20
22
o o o o o o-
0
TIME
0-
0000
0
0
0
-
I
I
I
2
4
6
I1
8
10
12
167
Fig. 66
Mechanical fits to OCS concentrations for
September 14-15, 1982 field study
2
1.
Y = -5.232 x 10-3,2 + 14.803x - 9.510 x 103; P2 . 1. 0
2
1.00
2.
Y = 1.387 x 10-3x2 - 5.580x + 6.119 x 103; R
3
4 2
Y = -5.023 x 10- x + 0.982x + 4.382x 102;R
4.
Y * 3.682x 10-3x2 - 16.912x + 1.952x 104.R * 1 00
*
Z
1.00
2
5.
linear
Eyeball,
6.
Y * -3 764 x 10-3x
2
2
+ 5.7M64 - 1.754 a 103; R * 1.00
Eyeball,linear
Cocs
2
Y 1 -4.254 x 103x
2
1.00o
+ 10.660x - 5.594 x 103; R
ppt
1000
900
800
700
600
500
400
300
200
100
12
14
16
20
18
22
00
6
4
2
8
10
12
TIME
Mechanical fits to H2 S concentrations for
September 14-15, 1982 field study
Fig. 67
2
+ 2.878x - 1.584 x 103,
R2 , 1.00
1.
Y * -1.072 x 10-3
2.
Y = 2.012 x 10-3x2 . 7 686x + 7 447 x 10 , R = 1 00
3.
Y - -1 577 x 10-3x
3
4
Y * 1.841 x 10 3
5.
Y * -8 076 x 10-3x
6. .Y * -1.261 x 10-3x
7
8.
2
2
2
+ 6.253x - 6.052 x 103, R . 1.00
- 8.394
2
2
+ 9.604 x 103,
Y = 4.091 A 10-3x
2
R
1.00
2
+ 3.798x - 7.353 x 10; R . 1.00
2
+ 1.906x - 5 024 A 102. R = 1.00
Y * 2 151 x 10-3x2 - 3.267x + 1.324 x 103
2
2
2
R
= 1.00
- 6 939x + 3.046 x 103; R2 . 1.00
pp700
.- I
700 600
500
400
300
200
100
0
12
14
16
18
20
22
0
2
TIME
4
6
8
10
12
168
Fig. 68
Mechanical fits to OCS concentrations for
September 23-24, 1982 field study
R2 *
RZ
R2*
R2 RZ
-4
2 -1.5251 + 2004.527
y * 4.544xi0
y a 2.792x1O-xZ -13.75z +17461.813
y a Z.20xIO-3xZ-I.31 +702.15
- 7
y * 4.80z10-x2z .6Iz+ 3370.89
z
y
COCS
ppt
7.97x10-Gx 23
0.983
0.99
0.99
0.93
0.99
I
I
I
I
I
I
I
I
I I1
900
800 1-
I
700
600
Ii
500
A
I/
400
3oo
200
12
I
I
I
14
16
18
I
20
22
00
1 I
!
4
6
2
I
8
I
10
12
TIME
Fig. 69
Mechanical fits to H2 S concentrations for
September 23-24, 1982 field study
3 2
4
2
1.
Y = 1.087 x 10- x
2.
Y - -2.860 x 10-4x 2 + 0.560x + 1.483 x 102; R2 - 1.00
3.
Y = 3.786 x 10-3x2 - 14.426x + 1.389 x 104; R2 = 1.00
4.
Y
5.
Y
6.
7.
Cn2 S
ppt
Y
-5.295 x 10-3x
= 9.544
=
4
x 10- x
- 3.9
2
2
3 2
-6.584 x 10- x
2
Y = 7 767 x 10-4x
5x + 3.831 x 103; R = 1.00
2
+ 23.644x - 2.384 x 104; R = 1.00
-
4 662
.
2
x + 5.822 x 103; R = 1.00
2
+ 6.905x - 1.401 x 103; R
1.00
2
- 0.998x + 3.951 x 102; R = 1.00
500
400
300
200
100
0
13
15
17
19
21
23
I
TIME
3
5
7
9
II
13
169
Fig. 70
Mechanical fits to OCS concentrations for
September 28-29, 1982 field study
Y = -134.096 + 1.108 x 106 /x; R2 = 0.96
1/Y = -0.124 + 6.3 x 10-5 x; R2 = 0.85
OCS
ppt
1/Y = 0.774 - 7.649 x 10-5x; R2
0.99
1000
800
600
400
200
0
12
14
16
18
20
22
00
2
4
6
8
10
12
TIME
Mechanical fits to H2 S concentrations for
September 28-29, 1982 field study
Fig. 71
1.
2.
3.
CH2
ppt
400
Y : -3.710 x 10-4x
2
2 =
+ 0.641x + 1.864 x 102; R
2
Y = 3.574 x 10-4x2 - 1.617x + 1.929 x 103; R
Y
1 462 x 10-3x
2
=
2
- 5.483x + 5.301 x 103; R
1.00
1.00
1.00
I
300 -
2
EyeballI
200100-
12
14
16
18
20
22
0
TIME
O
0
0
0
0-
2
4
6
8
10
12
170
The
refers
numerical
results
to the average
period,
Cg refers
are
presented next.
output chamber concentration
during
C
a sampling
to the average input chamber concentration during a
and E
sampling period,
H2S
OCS and
for
refers
to
the
flux
average
calculated
for
a
particular sampling period.
In these tables A refers to standard deviation, El = (-C-0)(u)/A,
E2 = (C(t
2
)-C(tl))(H)/(t
2
-tl),
The C values presented
for
the
September
studies were
14-15,
corrected
for
and E = El + E2.
graphically
September
for OCS and H2 S in
23-24, and
Chapter
September 28-29
4
field
loss on the NAFION drier (33.9%) whereas
the values presented here have not been adjusted.
Individual
deviations
E2
values,
of
C
and
-20%.
however,
have
relative
typically
reliable
C0
values
typically
El
values
were
have
much
greater
uncertainty
represent most of the uncertainty reported in E.
and
standard
to
~30%.
therefore
171
Table 13
Concentration and Flux Results for
Wallops Island Flux Studies of OCS and H 2 S
AUGUST 5 - 6 ,
1982 FIELD STUDY
OCS
LINEAR REGRESSION
LOG(R*GCAT)=M + B LOG(C)
M=3.84308
B=1.61964
± 6.40219E-82
+ 2.30337E-82
LP#
SET#
PPT
CO + ACO
PPT
C + AC
138.229
21.1738
326.331
50.8969
548.113
87.9713
363.734
57.0619
64.2894
9.27987
52.3643
7.43238
449.011
67.2341
210.29
32.2788
NGS/M2-HR
El + AEl
58.6967
195.523
149.642
98.6757
3.9191
.970555
116.343
43.5784
24.6881
48.1364
41.0192
27.0469
5.47874
4.56174
32.6987
16.3067
NGS/M -HR
E2 + AE2
44.3325
47.9342
-39.2464
-70.6339
-24.7451
52.9025
-11.1534
-96.9622
22.3378
63.3902
90.693
72.3121
13.2291
11.9822
220.824
33.8453
60.3282
8.7958
50.183
7.17806
68.8621
8.88451
47.7897
6.808851
51.7379
7.36272
49.256
6.95344
76.4043
10.6287
70.7485
9.89637
NGS/M2 -HR
E + AE
103.029
243.458
110.395
28.0418
-28.826
53.873
105.19
-53.3918
47.0259
111.527
131.712
99.359
18.7078
16.5439
252.715
50.152
172
AUGUST 5 - 6 ,
H2S
1982 FIELD STUDY
LINEAR REGRESSION
LOG(R*GCAT)=M + B LOG(C)
M=2.29866
B=2.02649
± .146314
+ 5.25758E-02
101.763
276.678
259.579
176.181
332.944
116.803
49
48
38
7
12
20
SET#
PPT
CO + ACO
PPT
C +AC
LP*
NGS/M2 -HR
El ± AEl
76.6765
195.899
81.0511
55.0109
103.959
36.4707
22.0404
59.0096
27.5083
18.1231
33.7089
11.8902
25.5992
73.4127
69.4052
45.354
83.9802
29.6683
NGS/M 2 -HR
E2 + AE2
44.244
47.8385
-13.1484
-20.7836
-13.3683
-77.2881
26.9504
91.3049
71.4456
57.263
274.822
31.0372
NGS/M 2 -HR
E + AE
120.921
243.737
67.9027
34.2273
90.5904
-40.8174
48.9908
150.315
98.9539
75.3861
308.531
42.9274
173
AUGUST 13 - 14 ,
1982 FIELD STUDY
OCS
LINERR REGRESSION
LOG(R*GCAT)=M + B LOG(C)
M=3.71789
3=1.65467
+ .206782
+ 7.55778E-82
PPT
LP#
C+
C+fC
PPT
CO ± ACO
c
89.3415
35.5574
69.9447
27.3581
24.7162
9.81465
28.5636
18,.5248
23.4278
8.52251
23.4888
8.52324
24.6504
8.99364
32.4986
12.0663
87.5727
34.7413
78.7677
31.88801
194.164
81.4288
37
34,
SET*
NGS/M 2 - HR
El + AE1
37.488
23.252
.844078
1.74862
1.68256
-. 795548
5.37506
29.8942
25.1566
10.8349
12.3757
9.93789
1088005
6.14889
12.7266
22.5767
17.9398
36.2943
33.8554
21.9422
61.1785
9.25106
NGS/M2-HR
.E2 + AE2
-.694841
-8.87932
-4.87647
0
0
8
0
7.55984
3.37817
14.3087
52.2823
37.1869
28.6493
9.49278
8
8
0
8
12.6716
37.2062
32.3884
86.4327
28.8712
18.5966
32.3577
11.9588
23.3517
8.45186
25.7369
9.3791
28.788
7.44452
24.7668
8.98202
15.9616
5.64892
22.56802
8.1496
28.661
7.41289
24.9252
9.06361
22.4202
8.89046
NGS/M2-HR
E + AE
36.7132
14.3727
-3.23239
1.74862
1.68256
-.795548
5.37506
13.7879
36.4256
36.2509
113.381
67.0011
53.866
20.3277
12.3757
9.93789
10.800885
9.25186
25.3982
59.7829
58.3202
122.727
174
AUGUST 13 - 14 ,
1982 FIELD STUDY
H2S
LINEAR REGRESSION
LOG(R*GCAT)=M + B LOG(C)
M=1.52889
3=2.21755
+ .273382
+ 9.71528E-02
PPT
C ± AC
LP#
49
9
21
46
25
34
39
SET#
73.5039
63.5948
69.1474
88.3009
108.453
86.6279
199.954
NGS/M 2 -HR
El t AEl
45.4708
39.3409
42.7759
54.6246
53.5772
35.3031
71.2274
19.3478
16.5943
18.1443
23.5031
24.2225
16.4502
34.7892
PPT
CO + aCO
28.6379
24.5424
26.8489
34.8239
43.2839
34.1273
83.2622
NGS/M 2 -HR
E2 + AE2
1.37118
-10.9349
-3.53806
34.2645
5.99304
12.2051
56.0124
29.8907
25.7185
27.7912
36.4956
46.3656
35.534
88.3945
NGS/M 2 -HR
S+
46.842
28.4061
39.2378
88.8891
59.5702
47.5082
127.24
A
49.2385
42.3128
45.9356
59.9987
70.5881
51.9842
123.184
175
AUGUST 18 - 19 ,
1982 FIELD STUDY
OCS
LINEAR REGRESSION
LOG(R*GCRT)=M + B LOG(C)
M=3.7846 + 5.87733E-02
B1u.64079 + 2.19216E-02
PPT
CO t a-C
PPT
C + AC
LP#
46
25
19
15
43
37
40
1
9
7
39
12
26
5
41
313.87
46.2573
205.597
29.5041
146.276
20.5406
61.7074
8.4845
73.712
10.2294
269.972
39.3914
35.0147
4.66114
124.459
17.2891
50
8
31
2
35
34
13
6
30
21
1
2
3
4
5
6
7
8
9
10
11
12
13
3.18676
24.2376
3.1618
23.0514
2.9994
18.3684
2.36561
18.8775
2.4331
24.4972
3.19535
23.4301
3.04951
-
-
SET#
24.429
33.7853
4.49233
94.1169
13.0601
150.548
21.1809
190.836
27.2612
287.392
41.9553
NGS/M 2 -HR
El + AEl
179.053
112.192
76.2292
26.8183
33.9216
151.856
7.16646
31.2194
5.15556
21.7812
41.7963
52.8492
82.5891
37.0129
24.2341
17.298
7.67425
9.05062
31.7948
5.02714
8.6436
2.4662
6.63872
10.2913
13.1922
19.9746
NGS/M 2 -HR
E2 + AE2
-35.9778
-23.002
-10.3222
-10.6399
12.4355
5.60334
-2.84729
4.56464
16.4925
8.87169
13.1732
11.4792
31.0748
48.5808
30.7459
21.4029
8.73145
10.6666
41.4284
4.91527
18.1738
4.75469
17.3443
22.0523
28.2654
46.7362
A
1b
"
'
17.2739
2.21695
24.3594
3.17768
16.6888
2.1383
21.5781
2.79932
22.8877
2.96742
NGS/M 2 -HR
E + AE
143.075
89.1901
65.9071
16.1704
46.3571
157.459
4.31917
35.784
21.648
30.6529
54.9695
64.3284
113.664
85.5937
54.98
38.7009
16.4057
19.7172
73.2232
9.94242
26.8174
7.22089
23.983
32.3436
41.4576
66.7188
176
AUGUST 18 - 19 ,
1982 FIELD STUDY
H2S
LINEAR REGRESSION
LOG(R*GCRT)=M + B LOG(C)
M=1.54224
3=2.16432
+ .380473
+ .135313
PPT
E + A-C
LP*#
46
19
43
40
9
39
26
41
31
35
13
30
SET#
368.996
162.493
127.699
185.518
74.4886
1472.32
133.87
573.758
109.262
251.607
261.864
338.85
NGS/M 2 -HR
El t AEl
228.268
180.521
78.9966
65.2756
46.88
910.807
82.8142
179.151
34.1161
78.5619
81.7646
185.803
145.781
60.8235
47.0392
38.4291
26.5039
639.058
49.4286
124.352
21.0281
51.7877
54.0468
78.7805
PPT
o +
6co
222.413
92.4899
71.4562
58.334
40.1705
980.202
75.0973
356.936
59.477
147.738
154.234
202.282
NGS/M 2 -HR
E2 + AE2
-81.805
-35.7647
-7.60512
-7.15738
-6.82296
75.439
-164.932
20.6873
38.4481
26.5673
10.7209
26.8752
233.033
96.1647
74.2864
59.6358
40.8294
1030.51
79.9062
374.758
78.976
153.425
159.59
224.59
NGS/M 2 -HR
E + AE
147.263
64.7566
71.3915
58.1182
39.2571
986.246
-82.1179
199.838
72.5642
185.129
92.4855
131.878
378.814
156.988
121.326
98.0649
67.3333
1669.56
129.335
499.11
100.004
205.212
213.637
295.37
177
AUGUST 26 - 27 ,
1982 FIELD STUDY
OCS
LINEAR REGRESSION
LOCC(RCCAT)=M
M=2.87547
B=1.70495
ItLOCCC
+ .103873
+ 3.82558E-82
PPT
C ± AC
LP#
40
35
32
17
14
7
48
25
20
5
41
2
45
43
34
15
31
26
58
19
37
21
9
SET#
1
2
3
4
5
6
7
8
9
10
11
12
PPT
CO + ACO
557.813
130.337
299.083
67.8441
188.961
23.3804
39.7139
7.98802
40.8521
8.27307
29.4506
5.83516
25.6579
5.0199
114.974
24.679
435.997
182.286
468.531
187.717
412.953
95.9037
422.152
97.9136
NGS/M 2 -HR
NGS/M 2 -HR
El + AEl
E2 + AE2
319.389
167.926
52.8961
9.8426
6.68674
-1.9154
-5.82023
54.1679
252.607
269.852
237.463
245.706
97.2649
51.3456
19.1849
8.15977
9.04287
7.54262
5.8059
20.5305
75.7123
79.2467
71.3894
72.3942
-88.4686
-32.6541
-69.7655
0
0
8
0
38.6979
13.8133
-5.27727
-3.36195
11.9838
172.675
73.7626
24.6374
0
0
8
0
27.0685
99.73
115.771
102.377
108.894
41.5189
8.36321
27.6293
5.41433
23.4546
4.56344
23.8033
4.63128
30.0429
5.95686
32.5468
6.46864
37.5809
7.50566
27.4115
5.36628
27.6561
5.44895
24.3126
4.73039
29.0935
5.72165
24.9675
4.8578
NGS/M 2 -HR
E
230.921
135.272
-16.8695
9.8426
6.68674
-1.9154
-5.82023
92.8658
266.42
264.575
234.101
257.689
AE
269.94
125.108
43.8223
8.15977
9.04287
7.54262
5.8059
47.5991
175.442
195.017
173.766
181.288
178
AUGUST 26 - 27 ,
1982 FIELD STUDY
H2S
LINEAR REGRESSION
LOG(R*GCAT)=M + B LOG(C)
M=2.79475
B=1.81485
+ .142667
+ 5.31033E-02
PPT
PPT
CO + ACO
LP*
639.633
120.3
98.7294
107.293
105.199
74.7764
SET#
NGS/M 2 -HR
El + AEl
395.688
74.42
61.0758
66.3732
65.078
46.2581
134.399
23.1953
18.9346
20.559
20.1424
14.0032
194.301
33.178
27.0646
29.3831
28.7848
19.9527
NGS/M 2 -HR
E2 + AE2
-206.659
-47.3003
5.27752
0
-5.43431
-10.8669
257.865
36.2603
26.3981
0
30.7543
22.2407
NGS/M 2 -HR
E ± AE
189.03
27.1196
66.3533
66.3732
59.6437
35.3912
392.263
59.4556
45.3326
20.559
50.8966
36.2439
179
SEPTEMBER 3 - 4 ,
1982 FIELD STUDY
OCS
LINEAR REGRESSION
LOG(R*GCAT)=M + B LOG(C)
M=3.26143
B=1.68545
+ 8.84584E-02
+ 3.42733E-02
PPT
LP#
SET#
C+
575.546
121.936
421.033
85.5918
449.417
93.206
277.351
56.4047
52.8501
9.68396
328.112
66.7306
33.0731
5.83123
29.216
5.13631
46.4915
8.4326
51.4404
9.35975
75.2568
14.0812
74.4436
13.9254
79.6325
15.
NGS/M 2 -HR
El + AEI
327.743
235.081
256.532
162.873
18.6081
188.516
8.00201
4.16216
14.6183
21.9071
27.1636
36.686
38.1967
PPT
CO + fCo
AC
92.3277
65.9659
70.6813
42.2123
9.10393
5075435
6.02478
5.73081
8.1926
8.25601
13.1102
11.5179
12.546
NGS/M 2 -HR
E2 + AE2
-61.3304
-10.9044
-23.6422
-48.9993
-4.57176
-20.0237
-3.42877
0
8.0442
0
5.31594
0
0
150.47
137.176
188.006
59.4893
10.7034
82.9227
7.43807
0
9.62547
0
16.1036
0
0
45.7472
8.29829
41.0234
7.40464
34.7318
6.16833
14.0662
2.38297
22.7699
3.95306
23.3745
4.03674
20.1378
3.44364
22.4878
3.88612
22.8608
3.96273
16.0274
2.71522
31.3467
5.53555
15.1405
2.56498
17.8874
3.0647
NGS/M 2 -HR
E + AE
266.413
224.177
232.89
113.873
14.8364
168.492
4.57325
4.16216
22.6625
21.9071
32.4795
36.686
38.1967
242.798
203.142
178.687
101.702
19.8073
133.466
13.4629
5.73081
17.8181
8.25601
29.2138
11.5179
12.546
180
SEPTEMBER 3 - 4 ,
1982 FIELD STUDY
H2S
LINEAR REGRESSION
LOG(R*GCAT)=M + B LOG(C)
M-2.31718
B1.9800885
+ .11118
4.09525E-82
PPT
LP*
c
38
11
26
32
58
SET#
237.452
139.667
127.957
183.377
141.489
NGS/M 2 -HR
El ± AE1
146.892
86.4005
79.1565
63.9511
87.4785
36.7863
20.8386
19.2175
15.5228
21.3975
PPT
otL
±
A"c
o
50.8143
28.6733
26.473
21.3826
29.5143
NGS/M 2 -HR
E2 + AE2
-32.5832
-9.46042
-7.379
-2.62369
-8.58145
62.7472
45.9891
38.6807
22.4563
36.6743
NGS/M 2 -HR
9- + A
114.309
76.9401
71.7775
61.3274
78.8971
99.4536
66.8277
49.8981
37.9791
58.8718
181
SEPTEMBER 9 - 10 ,
OCS
1982 FIELD STUDY
LINEAR REGRESSION
LOG(R*GCAT)=M + B LOG(C)
M=3.44279
B=1.63541
+ 9.28853E-82
+ 3.67508E-82
LP*
398.823
35
21
46
18
8
43
47'
41
45
34
36
SET#
PPT
-CO + An0
PPT
C ± AC
357.652
78.9925
211.173
44.7918
44.2589
8.53536
44.0217
8.49082
26.8509
5.05712
28.4919
5.32987
25.8325
4.63044
27.8414
5.056
22.8488
4.219
27.8448
5.21055
57.4393
11.3604
34.0252
6.42316
NGS/M 2 -HR
El + AEl
218.599
206.426
114.143
19.9833
15.6148
10.1709
7.67722
3.57599
5.02842
2.87396
4.23437
22.7374
5.7061
88.837
68.2052
59.0073
34.8631
7.30886
7.92862
4.63538
5.36402
5.15199
5.44063
4.75713
5.75567
10.2014
7.00716
NGS/M2 -HR
E2 + AE2
5.49981
-22.7058
-38.4202
-13.1495
-4.08311
0
107.191
95.8759
55.3817
10.0906
9.91018
0
0
2.61534
11.3743
-7.81841
0
6.10478
12.01
8.05058
45.4566
8.73535
23.9631
4.41761
26.661
4.9429
11.9558
2.12014
1Q.7?Aq
1.41Qq7
18.4096
1.84595
16.0816
2.89571
19.2519
3.49032
18.913
3.4471
18.203
3.30419
21.
3.84787
20.6842
3.8111
24.8012
4.57292
NGS/M 2 -HR
E + AE
224.099
183.72
75.7223
6.83381
11.5317
10.1709
7.67722
3.57599
5.02842
2.87396
6.84971
34.1117
-2.11231
175.396
154.883
90.2448
17.3994
17.8388
4.63538
5.36402
5.15199
5.44863
4.75713
11.8604
22.2114
15.8577
182
SEPTEMBER 9 - 10 ,
1982 FIELD STUDY
H2S
LINEAR REGRESSION
LOG(R*GCAT)=M + B LOG(C)
M=2.31718
B=1.98005
+ .11118
± 4.09525E-02
PPT
C + AC
LP#
44
28
15
SET#
191.454
197.13
251.965
NGS/M 2 -HR
El + AE1
118.437
121.948
155.87
29.5045
30.4193
39.0996
PPT
CO + aCO
40.8233
42.0983
54.1622
NGS/M 2 -HR
E2 ± AE2
2.41248
6.87531
-15.4078
49.2569
51.0647
66.7812
NGS/M 2 -HR
E + AE
120.849
128.823
140.462
78.7614
81.484
105.881
183
SEPTEMBER 14 - 15 ,
1982 FIELD STUDY
OCS
LINEAR REGRESSION
LOG(R*GCRT)=M + B LOG(C)
M=3.3276
+ 9.06593E-02
B=1.68052 ± 3.59518E-02
PPT
C + AC
LP#
50
SET#
1
2
3
4
5
6
7
8
9
10
11
12
13
538.48
117.624
647.232
143.759
464.267
100.351
353.845
75.2693
225.471
46.4449
70.9398
13.5584
465.171
100.869
373.44
79.99
48.2821
9.08981
268.391
56.0101
275.573
57.361
347.301
71.9356
690.528
136.8
NGS/M 2 -HR
El t AEl
302.997
383.563
269.527
210.54
127.132
33.1145
240.091
215.545
21.5366
152.076
156.13
206.546
419.765
PPT
CO + CO
89.2346
105.718
74.9271
55.5579
35.4735
11.4536
80.1815
59.9912
7.84859
42.588
43.634
53.3376
100.963
NGS/M 2 -HR
E2 ± AE2
89.4603
-26.3098
-38.3847
-48.7117
-58.7568
-13.7809
68.9349
145.76
114.165
35.4736
1.82482
58.1729
8.65264
145.847
170.263
123.542
89.9487
53.6264
16.8066
119.321
90.2933
10.2178
64.2955
69.7938
196.124
819.211
48.684
9.84645
27.2009
4.88289
28.5746
5.13296
13.5068
2.32615
19.9613
3.52291
17.4101
3.03531
77.0632
14.8163
25.0107
4.48163
13.468
2.33514
22.5591
4.01108
23.1886
4.11595
13.419
2.30244
11.9759
2.05484
NGS/M 2 -HR
9 + ATE
392.457
357.253
231.143
161.828
68.3755
19.3337
309.026
361.304
135.702
187.55
157.955
264.718
428.417
235.082
275.982
198.469
145.507
89.1
28.2602
199.582
150.285
18.0584
106.883
113.428
249.462
920.173
184
SEPTEMBER 14 - 15 ,
1982 FIELD STUDY
H2S
LINEAR REGRESSION
LOG(R*GCAT)=M + B LOG(C)
M=2.31718
B=1.98005
+ .11118
± 4.09525E-02
PPT
t ± AC
LP#
21
30
7
50
45
46
36
47
13
28
38
40
SET#
222.84
223.228
166.934
75.3208
92.5612
25.2663
215.162
245.773
70.8752
69.3358
98.642
441.762
NGS/M 2 -HR
El + AEl
137.853
138.893
103.268
46.5948
57.26
15.6302
133.103
152.84
43.3498
42.8924
61.0217
273.282
34.3396
34.485
25.5118
11.0633
13.7624
3.51723
33.1782
38.2927
18.2733
10.1281
14.4483
65.3812
PPT
0 + ACO
47.5129
47.734
35.249
15.1808
18.9252
4.77885
45.911
53.08
14.8919
13.8838
19.8156
89.835
NGS/M 2 -HR
E2 ± AE2
9.63894
-14.0046
-38.2156
-10.6826
-13.5675
-3.43919
37.8762
-29.4896
10.5484
13.7124
47.7437
90.8682
58.7545
56.5659
43.5433
18.1465
21.7893
5.91523
54.3484
59.5137
16.1862
16.9727
54.2155
538.478
NGS/M2 -HR
E ± A7E
147.492
124.088
65.0528
35.9123
43.6925
12.191
170.979
122.55
53.8982
56.6048
108.765
364.15
93.0941
91.051
69.0551
29.2098
35.5517
9.43245
87.5266
97.8064
26.4595
27.1008
68.6638
603.859
185
SEPTEMBER 23 - 24 ,
1982 FIELD STUDY
OCS
LINEAR REGRESSION
LOG(R*GCAT)=M + B LOG(C)
M=3.28776
B3=1.69961
+ 7.45567E-02
± 2.97118E-02
LP#
50
SET#
1
2
3
4
5
6
7
8
9
10
11
12
PPT
CO + ACO
PPT
C + AC
514.518
94.2835
480.348
87.6008
484.888
88.3937
497.728
90.8175
543.557
99.8704
378.397
68.5829
367.223
65.6227
340.604
61.4187
431.384
78.4086
193.493
33.0882
359.148
63.9825
570.305
98.7072
NGS/M 2 -HR
NGS/M 2 -HR
El + AEl
E2 t AE2
305.962
279.894
286.935
296.377
331.407
230.001
212.987
199.68
256.115
114.979
206.284
348.88
71.1038
66.8751
66.9296
68.537
74.3678
51.2643
50.3803
46.8159
59.3014
25.2695
49.3969
74.143
-16.0218
-5.82612
4.09737
14.3579
24.2853
28.277
14.2674
17.6558
65.5552
59.0751
88.1995
62.8635
115.267
105.702
107.978
112.885
123.012
71.2331
81.8776
61.5891
89.1533
39.8351
80.4956
293.623
19.9294
2.98627
27.8978
4.26547
28.9757
3.15229
18.633
2.77915
7.83569
1.11952
6.5995
.942904
22.9286
3.46122
17.8192
2.68334
17.373
2.59447
7.6277
1.08981
25.6889
3.90062
6.33894
.905676
NGS/M 2 -HR
E
289.94
274.068
291.033
310.735
355.692
258.278
227.254
217.336
321.67
174.055
294.484
411.743
AE
186.371
172.577
174.908
181.422
197.38
122.497
131.458
188.405
148.455
65.1046
129.892
367.766
186
SEPTEMBER 23 - 24 ,
H2S
1982 FIELD STUDY
LINEAR REGRESSION
LOG(R*GCRT)=M + B LOG(C)
Ma2.31718
B=1.98005
± .11118
+ 4.09525E-02
PPT
CO t &CO
PPT
C
LP#
327.745
219.836
179.51
104.668
241.034
91.1935
92.5484
147.393
267.168
54.9583
52849.3
179.723
47
38
33
36
43
26
58
38
37
12
16
21
SETS
NGS/M 2 -HR
El t AEl
282.749
135.994
185.481
64.7494
149.108
56.414
57.2472
91.1799
165.275
33.9982
123956.
111.18
51.6081
33.8794
26.0841
15.5911
37.2959
13.6144
13.7068
22.6101
41.7644
7.94016
30021.3
26.3199
±+AC
71.6626
46.8767
36.08457
21.4468
51.6387
18.7349
18.836
31.2597
57.9241
18.863
10903.
36.8963
NGS/M2 -HR
E2 ± AE2
-54.7847
-18.2756
-24.7965
23.698
-13.3415
-7.6725
13.7414
32.5242
-35.4845
10.6171
28.2656
23.4549
87.9417
56.6539
44.1707
26.7799
63.609
19.4586
23.33
31.4917
65.7842
13.8253
13627.
107.378
NGS/M 2 -HR
E± AE
147.964
117.719
80.6842
88.4474
135.766
48.7415
70.9886
123.704
129.79
44.6153
123985.
134.635
139.55
90.5333
70.2548
42.371
100.905
33.0729
37.0368
54.1018
107.549
208.9655
43648.3
133.698
187
SEPTEMBER 28 - 29 ,
1982 FIELD STUDY
OCS
LINEAR REGRESSION
LOG(R*GCAT)=M + B LOG(C)
Ma3.19766
B01.73277
t 3.87642E-2
+ 1.48893E-82
PPT'
PPT
To + A o
LP*
58
6
38
37
SET#
1
2
3
4
5
6
7
8
9
18
11
12
13
778.863
83.6428
408.497
42.7973
689.42
65.3731
587.799
53.869
584.848
53.4176
41.1256
4.83818
35.6687
3.4792
34.8083
3.4504
26.6865
2.58513
39.2568
3.84369
139.335
13.6931
811.195
87.5824
678,.453
72.3543
NGS/M 2 -HR
El t AE1l
452.689
238.877.
356,624
382.283
381.495
9.60432
5.55831
12.4174
7.49481
12.1662
75.9034
486.867
400.699
70.3854
36.4226
55.2287
45.3847
44.8489
4.36639
3.94214
3.44196
2.72049
3.96731
12.1679
73.1386
60.4868
NGS/M 2 -HR
E2 + AE2
-68.3877
-42.8184
-33.3717
-26.8677
-21.9744
-'14.3337
-5.14937
8
3.74595
18.463
76.7259
228.865
-119.77
122.689
52.7344
88.8363
67.2452
67.5928
5.88661
4.36359
8
2.87484
4.91481
17.726
111.427
88.8761
38.2884
3.74422
23.6438
2.26842
32.9362
3.28243
19.2853
1.83446
16.6885
1.5772
25.6882
2.46294
26.6886
2.5713
14.7357
1.39332
14.5711
1.37775
19.59
1.86368
16.6366
1.57385
25.4658
2.44814
22.7209
2.17697
NGS/M2-HR
384.382
195.259
323.252
275.336
279.52
-4.72937
.4088932
12.4174
11.2488
22.6293
152.629
714.132
288.929
192.915
89.157
136.857
112.55
112.434
9.45301
8.38573
3.44196
5.59533
8.88132
29.8939
184.565
149.363
188
SEPTEMBER 28 - 29 ,
H2S
1982 FIELD STUDY
LINEAR REGRESSION
LOG(R*GCAT)=M + B LOG(C)
M=2.31718
B=1.988005
± .11118
+ 4.09525E-82
269.562
161.807
154.474
186.022
134.982
33.4193
223.977
235.779
SET#
PPT
PPT
C± Ar
LP#
NGS/M 2 -HR
El + AEl
166.756
100.097
95.5607
65.5871
83.4529
20.6738
138.556
145.857
41.8649
24.6447
23.4623
15.7797
280.3175
4.69851
34.3865
36.6613
-CO
CO
58.0007
34.0313
32.3831
21.783
28.802
6.39581
47.5479
50.8014
NGS/M 2 -HR
E2 + AE2
-13.1086
-16.4178
-22.031
-. 574952
-19.611
13.1603
16.3361
12.7933
84.8156
41.8273
40.0759
27.0306
35.4813
8.14345
59.848
61.9739
NGS/M 2 -HR
f ± AE
153.647
83.6791
73.5297
65.0121
63.8419
33.8341
154.892
158.651
126.68
66.472
63.5382
42.8103
55.7988
12.842
94.2345
98.6351
189
APPENDIX VII
Reproducibility Studies
190
Table 14
Reproducibility Studies
July 20-21,
1982
Drier- 1
Loop #
Loop #
1
30
28
2
29
31
3
34
32
486.3
534.7
4
9
6
604.4
653.2
5
25
7
692.1
675.8
6
38
23
588.8
714.7
7
19
18
562.2
591.4
8
20
17
494.6
690.9
9
21
2
621.3
703.7
10
5
37
651.8
868.5
Test
Drier-
3
03
1
OCS (ppt)
OCS (ppt)
658.0
582.5
742.1
675.75 (±94.5) ppt
Average "3" OCS mixing ratio:
(14% relative standard deviative)
Average "drier-1" OCS mixing ratio: 595.5 (±71.1) ppt
(11.9% relative standard deviative)
June 15-16,
Test #
1
1982
OCS (Loop #)(ppt)
598.2(1)
OCS (Loop #)(ppt)
605.1(2)
2
1157.4(3)
1207.5(4)
3
580.3(5)
502.2(6)
191
APPENDIX VIII
Wallops Island Field Studies:
Light Intensities and Air and Soil Temperatures
192
13
12
II
I0
9
-s
430
13
Fig.
72
5I IT
19
21
23
I
TIME
3
5
7
9
II
August 5-6, 1982 field study:
intensities versus time
Light
42
403. -
s 34 -
Outside
Chamber
32 3018 24-
1412 13
15
17
19
21
23
I
3
5
7
9
II
13
TIME
Fig. 73
August 5-6, 1982 field study:
temperatures versus time
Air and soil
193
13 12
II
I0
10 -
13
1
1
19
21
23
3
9
TlMo
4320
13
5I 17
21
19
23
I
3
TIME
7
5
9
13
II
August 13-14, 1982 field study:
intensities versus time
Fig. 74
Light
4036 -
34 -
Outside
3t -
Chamber
IS-
13
IS
17
19
21
23
I
3
5
7
9
II
13
TIME
Fig. 75
August 13-14, 1982 field study:
temperatures versus time
Air and soil
194
13
12
II
It
10
9-S
5
4
3
I
Fig. 76
23
21
19
I
15
13
9
7
5
3
I
TIME
13
II
August 18-19, 1982 field study:
intensities versus time
Light
4030-
St
Outside
Chamber
1
30-
@o
260
14
12 13
IS
17
19
21
23
I
3
5
7
9
II
13
TIME
Fig. 77
August 18-19, 1982 field study:
temperatures versus time
Air and soil
II
is
I0
Fig. 78
A
*
S
August 26-27, 1982 field study:
intensities versus time
Light
4
3
2
0
17
19
21
23
I
3
5
TIME
7
9
II
13
IS
17
42
40
3.
34
40
S3
36
34
32
30
34
32
30
26
21
24
24
22
22
20
10
14
12
12
I0
17
19
21
23
I
3
5
7
9
II
13
15
17
t1 19
21
23
I
TIME
Fig. 79
3
5
TIME
August 26-27, 1982 field study:
temperatures versus time
Air and soil
7
9
II
IS
I1
17
It
10
9
Fig. 80
September 3-4, 1982 field study:
intensities versus time
.
Light
-j
4
-
3
2
1
O -
IS
.
19
17
21
23
3
I
5
9
7
II
13
15
TIME
42
40
38 3
36
34
32 .
T,
42
40"
I
36
34
Outside
32
Chamber
I
r
I
,
Inside
Td
1
Chamber
d
20 - 7*
T
r
1I
,
"
30
26
TC 24
I
22
o
IS
U
/
'To
"
I14
14
I0
IS
IT
19
21
23
I
3 5
TIME
7
Fig.
81
9
II
13
IS
15
17
19
21
23
I
3
TIME
September 3-4, 1982 field study:
temperatures versus time
Air and soil
5
7
II
13
15
IS
-
12
II
10
9IO
Fig. 82
e4
September 9-10, 1982 field study:
intensities versus time
Light
I
0-8
13
15
17
21
19
23
3
I
5
9
7
II
13
TIME
42
40
42
40
38
3'
34
34
30
C 24
at
Is
1.
14
12
10O
8
13
IS
17
19
21
23
I
3
5
7
9
11
13
a
13IS
TIME
Fig. 83
17
19
21
23
I
TIME
September 9-10, 1982 field study:
temperatures versus time
Air and soil
3
S
7
9
II
t
S1
12
II
10
II
I
I
I
i
I
I
20
22
24
2
4
I
I
I
I
6
8
Fig. 84
i
September 14-15, 1982 field study:
intensities versus time
x
N. S
4
3
I
0
i
i
It
14
i
I
16
I0
10
12
TIME
40
3. -
-
36
34
32
o-
aso
I2
24
-
Outside
Chamber
3
, , ,N
so
,
IS 14 -
12
0K)
a
12"
14
16
18
20
22
24
2
4
6
8
10
12
it
14
16
TIME
Fig.
IS 20
22
24
2
TIME
85
September 14-15, 1982 field study:
temperatures versus time
Air and soil
4
6
S
10
J2
Light
13
12
II
10
September 23-24, 1982 field study:
intensities versus time
Fig. 86
.
•
4
a
0
TIME
42
40
36
36
*U
42
4036 36 34
Inside
32
30
26
-'I,
T
aI2
as - 24
so -
Outside
Chamber
ITab
I
a
24 22
T
o
4
12
10M
10
Is
I
TIME
Fig. 87
17
I9 21
23
I
TIME
September 23-24, 1982 field study:
temperatures versus time
Air and soil
3
5
Light
10II
Fig.
x
88
I0 -
September 28-29, 1982 field study:
intensities versus time
Light
430TIME
4'
40
42.
40-
3.
3t
S0
Outside
Chamber
_0
a
pM
to
22
It
Is
14
12
M
It-
10
8
13
1S
17
19
21
23
I
3
5
7
9
II
13
i5
15
TIME
Fig.
17
0
21
23
I
TIME
89
September 28-29, 1982 field study:
temperatures versus time
Air and soil
3
5
1
•
II
15