Research Articles
Soil-Atmosphere Exchange of
Radiatively and Chemically Active Gases
M. Aslam K. Khalil 1, Reinhold A. Rasmussen 2
1Dept. of Physics, Portland State University, EO.Box 751, Portland, Oregon 97207, USA
2Dept. of Environmental Science & Engineering, Oregon Graduate Institute, P.O.Box 91000, Portland, Oregon 97291, USA
Corresponding author: Aslam Khalil; e-mail: aslam@global.phy.pdx.edu
DOh http:lldx.doi.oro]l 0.1065/espr2000.04.021
Abstract. Exchanges between the soils and the atmosphere may
control or significantly affect the global budgets of many envi-
ronmentally important trace gases, both natural and man-made.
Flux measurements, taken in several ecosystems, show that soils
are a substantial source of chloroform (8 _+4 pg/m2/d) and a sink
for methyl chloride (-10"_36pg/m2/d). The known sources and sinks
of these gases are insufficient to explain the observed concentra-
tions. Our findings will help to balance the global budget of chlo-
roform but may put the budget of methyl chloride further out of
balance. We also found, consistent with previous research, that
soils are a substantial source of nitrous oxide and carbon monox-
ide and take up hydrogen and methane. The uptake of man-made
chlorocarbons was observed, but the rates are small. Observed
fluxes of non-methane hydrocarbons showed few patterns except
that soils may be a source of ethane and butane.
Keywords:CH4;CO2;N20; atmosphere; biota; butane; chloro-
carbons; chloroform; ethane; gases; global warming potential;
greenhouse gases; hydrocarbons; methyl chloride; nitrous ox-
ide; ocean-air exchange; ozone depletion; soil-atmosphere ex-
change; soils; trace gases
Introduction
It is well k n o w n that human activities are causing increas-
ing levels of key atmospheric trace gases that can lead to
global warming and deplete the stratospheric ozone layer.
Gases with the greatest potential for global warming that
are directly emitted by natural and anthropogenic processes
are CO2, NzO and C H 4. For ozone depletion the most im-
portant gases are CC13F (F-11) and CClzF2 (F-12). M a n y
other gases play lesser roles but are nonetheless important
to the future of the atmospheric environment. During the
last three decades, much has been learned about the sources
and sinks of these radiatively important trace gases and
ozone-depleting compounds. Yet, there are many unknowns
and uncertainties. In some cases, such as for N20, even the
present atmospheric observations cannot be adequately ex-
plained by the available information on the sources and sinks.
For the problem of the ozone layer, the global mass balance
of gases that contribute natural chlorine to the atmosphere,
such as methyl chloride and chloroform, are not understood
ESPR - Environ. Sci. & Pollut. Res. 7 (2) 79 - 82 (2000)
9 ecomed publishers, D - 8 6 8 9 9 Landsberg, Germany and Ft. Worth/TX, USA 9 Tokyo, Japan 9 Mumbai, India 9 Seoul, Korea
Soil-Atmosphere Exchange
at present (for a review see GRAEDELand KEENE, 1995; KHALIL
et al., 1999). One of the key areas of uncertainty is in the
exchanges of trace gases across the different media that con-
stitute the environment such as ocean-air exchange, exchange
between soils and the atmosphere and between the biota
and the atmosphere.
Over the years we have taken m a n y measurements of the
exchanges across different media that contribute to atmo-
spheric composition. Although flux measurements for the
major trace gases such as CO2, CH4, N 2 0 and CO have
been taken, few, if any data on the chlorocarbons and hy-
drocarbons have been reported thus far. We have obtained a
few measurements of exchanges of trace gases between the
soils and the atmosphere. In this paper we report these data
from sites distributed among forests, high latitude grass fields,
and mid-latitude agricultural soils. While these data are not
extensive, they point to directions for research on the bud-
gets of environmentally important trace gases and the roles
of natural and anthropogenic processes in determining the
composition of the atmosphere.
1 The Experiments
We have five data sets representing several ecosystems, two
from the Ducke Forest Reserve in Brazil during 1985 and
1987 Amazon Boundary Layer Experiments (ABLE: 2~
50~ from Greenland, near Sonderstrom (68~ 50~
from the Boola Boola National Forest in Australia (38~
146~ and from the agricultural lands around Chendu in
China (30~ 104~ At Boola Boola our work concentrated
mostly on methane emissions from termite mounds, pub-
lished earlier. But we also took measurements away from
the mounds throughout the year. We believe these measure-
ments are representative of the forest undisturbed by the
termites, and so are included in this paper. This is evidenced
by the fact that these soils took up methane, whereas soils
affected by the mounds produced methane (KHAuL et al.,
1990a,b). In China our work dealt with methane emissions
from rice fields, but we also took samples from other agri-
cultural crops and soils that are quite different from the rice
fields when it comes to emissions to the atmosphere.
In these experiments, a static chamber was placed over the
soils and samples were drawn periodically into evacuated
79
Soil-Atmosphere Exchange
0.8L stainless steel containers and pressurized to a b o u t
2 atmospheres. The base of the chamber was pushed into
the soil to make a seal against the outside air. In some cases
the seal was strengthened with mud. There is an inlet at-
tached to the chamber that allows outside air to replace the
air that is drawn out from the chamber. This is to prevent
sucking the air out of the soils rather than letting it accumu-
late at it natural rate (flux). The addition of outside air is
taken into account when calculating the flux (KHALILet al.,
1990b). The sampling times were of the order of 20 minutes
during which time two or three samples were drawn. Ex-
cept in China, we used a 17L stainless steel chamber with a
basal area of 0.73m 2. In China a 19L polypropylene cham-
ber with a basal area of 0.82 m 2 was used. The samples
were brought back to the laboratory for the analysis. Con-
centrations of gases were measured by several gas chromato-
graphs with FID, ECD, and H g O detectors. Standard meth-
ods described in our earlier papers were used for sampling
and analysis (tLCSM~JSSENand KrtAUL, 1980; RASMUSSENand
Lov-eLoc~, 1983; K~LIL et al., 1990a,b).
2 Results
The average emissions from these experiments are given in
Table 1. The table also shows the number of replicates in each
of the 5 experiments reported here. These replicates represent
measurements taken at different locations within the same area.
The category of "several crops" in the China experiments in-
cludes a dry field of Canola plants, a field of potatoes, and
one of peas. These were combined since only one measure-
ment was taken in each of these cases, and the emissions were
found to be similar. A recently plowed field, without any crop,
was also sampled and serves as a control that shows the effect
of the crop on emissions of gases.
Greenhouse and Related Gases: Hydrogen and methane are
taken up by most soils that we studied, except the moist
Canola field. All three replicates in this case showed emis-
sions of methane. The origin of this methane may be the
residual effect from a previous crop of rice or potentially
anaerobic conditions below the soil due to wetness.
The results for carbon monoxide are mixed. There is a ten-
dency for uptake by soils, but in some cases there is either
no exchange or the soils appear as a small source. We found
emissions of nitrous oxide in almost all the cases we stud-
ied, except the grassy high latitude field where a small sink
was observed. This pattern is consistent with previous stud-
ies (ScHMIDTet al., 1988; M ~ v a , 1987; DtsxstmY et al., 1982;
BREMNER and BLACKMER,1978). The emission of NzO from
the agricultural fields in China may be the effect of fertilizer
applications. Large fluxes of carbon dioxide were also ob-
served. These could occur because our chambers are dark,
and when plants are covered, CO 2 is produced by respira-
tion. Some of the carbon dioxide could also come from mi-
crobial respiration in the soils.
Chlorine-Containing Gases: Our studies show that most soils
are a source of chloroform and a sink of methyl chloride
(except for the high latitude grassy field). These patterns of
uptake of methyl chloride and emissions of chloroform are
seen in almost all the replicates. The production of chloro-
80
Research Articles
form in soils has been reported earlier, but there are no
records of flux measurements (FR~,,~ and FRANK, 1990). For
the chlorocarbons, there is some indication of uptake by
soils, but the fluxes observed are at the limits of detection
making it difficult to draw firm conclusions.
Non methane hydrocarbons: The results on the fluxes of
C2-C4 hydrocarbons are inconclusive. Both emissions and
uptake were observed, but no clear patterns were seen. Emis-
sions are small at around 5 micrograms/m2/d, and uptakes
are generally smaller, except for some of the crop fields where
C2H2 and C2H 4 were taken up by the soils at rates up to
25 mg/m2/d. On average, there is an indication that ethane
and butane are released from the soils.
Analysis of Composite Data: To look at the dominant pat-
terns we pooled the experiments, as shown in Table 1, and
estimated the expected fluxes and their uncertainties based
on the observed variability. We chose the Hodges-Lehman
non-parametric statistical estimator for the middle value of
the flux based on all the data (HOLLANDERand WOLFE, 1973).
This estimator is less sensitive to outliers than the usual sta-
tistical measures such as the average value. A confidence
limit can also be calculated from this analysis that can sup-
port a conclusion on whether the present data indicate that
the soils are a net sink or a source (here calculated as ap-
proximate 90% confidence limits). The results are included
in the last four columns of Table 1. The estimated middle
values are our suggested average fluxes to or from the soils,
based on the data presented here.
3 Discussion and Conclusions
The global exchange rate of trace gases between the soils and
the atmosphere are complicated by the heterogeneous nature
of the production and destruction processes involved. Even
the same soils may be a source at one time and sink at another
time of the year. Yet there are many consistencies in the mag-
nitude and sign of the net flux across the disparate locations
where we took measurements that provide strong evidence
that soils are sources and sinks for the gases studied.
At present the budgets of many of the gases we have reported
here are unbalanced. Although we recognize that these data
are insufficient to make accurate estimates of global exchange
rates, it is nonetheless necessary to see whether these fluxes
have the potential for being significant contributors to the
budgets of these environmentally important trace gases. If the
median values of the composite observations reported in
Table 1 are e x t r a p o l a t e d to the land area of the world
(1.49 x 10 TM m2), it shows that the uptake of hydrogen is of
the order of 20 Tg/yr and methane around 30 Tg/yr, CO is of
the order of 60 Tg/yr and CH3CI is of the order of 0.5 Tg/yr.
There is substantial source of NzO of the order of 10 Tg/yr
(not including the agricultural soils), and the emission of chlo-
roform would be of the order of 400 gigagrams/yr if the present
data are representative of global conditions. For the man-made
chlorocarbons, there are losses into the soils, which, when
extrapolated, are a few tens of gigagrams per year.
Previous estimates of uptake by soils are 70 Tg/yr for Hy-
drogen, 20-40 Tg/yr for methane, 200-400 Tg/yr for Car-
ESPR - Environ. Sci. & Pollut. Res. 7 (2) 2000)
Research Articles Soil-Atmosphere Exchange

T a b l e 1: E m i s s i o n s a n d u p t a k e o f t r a c e g a s e s by s o i l s o f s e v e r a l e c o s y s t e m s

G r e e n h o u s e a n d Related G a s e s (mg/m=/d)

COs 28 19 9 4 0 19 23 1 13 11 14 +
(g/mS/d)

Hs -0,5 -0,3 -0,4 0.0 -0.1 -0.2 -0.6 0.1 -0.3 -0.4 -0.2

CH 4 -1.1 -0.8 -1.0 -- -0.0 7.5 -0.3 -0.6 -0.5 -0.6 -0.3

CO 0.2 0.0 0.6 0.2 -0.1 -1.8 2.3 -0.1 -1.0 -1.5 -0,4

NsO 1.3 0.6 0.0 0.6 -0.3 1.0 0.9 3.9 0.8 0.6 1.1 +

ChlorineContainingGases(p~m~)

CH3CI -11 -15 -- -8 -4 -- -- -- -10 -13 -4

CHCI 3 - - ~'~ 3 52 35 -0 4 6 0 8 4 13 4-

F-11 0.1 -0,5 -- -0.1 0.0 -1.3 -0.5 -0.6 -0.5 -0.6 -0.3

F-12 -- -3.1 -- 0.9 0.3 -- -- -- -0.2 -3.1 0.9 O

F-113 -- -0.6 -- 0.0 -0.1 -1.2 -0.7 -0.2 -0.5 -0.7 -0.3

CHsCCI13 -0.6 0.3 -- -0.7 -12.2 -0.2 0.6 0.4 -1.3 -2.7 0.3 O

CCt~, -- -0.4 -- -0.0 0.0 -0.5 0.2 -0.1 -0.1 -0.2 0.1 O

N o n - M e t h a n e H y d r o c a r b o n s (iJg/m2/d)

C2Hs -- 4.0 1.2 4.9 -0.1 0.3 17.4 3.9 8.1 3.9 11.3 4-

02H , 8.0 4.2 3.8 -1.8 2.1 -20.6 6.0 -7.1 -16 3.8 O

CsH 2 7.5 -0.5 6.8 0.4 -5.9 -25.8 -2.9 -10.3 -17.2 -2.7

C3H 8 -8.0 4.3 -3.2 -1.1 . . . . 2.1 -5.6 4.3 0

C3H 8 2.2 5.9 4.7 -3.1 -2.1 9.4 -0.8 3.6 -1.0 5.9 0

i-C,H,0 0.8 2.6 3.7 0.1 0.8 10.2 -1.8 3.7 1.6 6.3 +

n- C,H~o 1.1 2.2 0.8 0.6 0.3 8.4 -0.3 1.3 0.6 5.2 4-

Replicate ~ 8 6 56 2 2 3 3 1 -- -- --

Dates ~ 7/85 5/87 4/85-11~ ~86 7/86 4/88 4~8 ~88 -- --

Notes:
1) Blanks ( - - ) indicate that the gas was not measured in the experiment.
2) Replicates indicates the number of independent experiments at each site.
3) Dates shows the time when the experiments were done.
4) The composite is the estimate of the middle value when all the experiments are pooled together. It is calculated using a non-parametric statistical estimator
described in the text. The upper and lower ranges quoted are 90% confidence limits. The last column shows a qualitative evaluation of whether the soils are
a source (+), a sink (-) or if no evaluation can be made using the present data (o).

bon monoxide and a source of NzO of 10-12 Tg/yr (com- restrial sources. The soil sink as implicit in the data reported
piled in WAKNECK, 1999). Our limited data are compatible here, would make this discrepancy even larger, requiring
with these estimates. CO and H 2 fluxes are below the global more sources and emissions to balance the sinks. Yet all soils
average from previous studies and CH 4 and N20 are close. are not likely to be sinks for methyl chloride since there is
This comparison provides perspective for our results. It sug- evidence that it is emitted by wood rotting fungi (WAXLINC
gests that collectively the soils we sampled were not widely and Hmd'ER, 1998). Results from field studies of this process
different from the global average conditions. have not been reported yet.
The cases of chloroform and methyl chloride are particu- For chloroform, the soil source discussed here would bring
larly noteworthy. At present, the current estimates of identi- qualitative agreement between sources and sinks, and would
fied sources are not sufficient to balance the estimated an- also provide the correct pattern for the latitudinal distribu-
nual losses of these gases by their reaction with tropospheric tion of chloroform which shows a northern hemisphere to
hydroxyl radicals. This discrepancy is particularly large for southern hemisphere ratio of around two with highest con-
methyl chloride, for which only about half of the estimated centrations in middle northern latitudes (KHALILet al., 1999
3.7 Tg/yr total emissions, based on reaction with OH, can and references therein). Readers may also be interested in
be explained by measured fluxes from the oceans and ter- our data on emissions of these gases from rice fields (KHALIL

ESPR - Environ. Sci. & Pollut. Res. 7 (2) 2 0 0 0 81

Soil-Atmosphere Exchange
et al., 1998). These studies show sizable emissions CH4, N 2 0 ,
and H z as was expected. In addition emissions of chloro-
form (CHC13) and CO, and mild uptake of F-11 and F-12
were observed (methyl chloride was not measured). These
results are consistent with the data reported here.
Acknowledgments. We thank Bob Dalluge, Don Stearns, Bob Watkins,
and Martha Shearer for their contributpons to this work. Portions of this
work were supported by grants from the National Science Foundation
(ATM-8308038), Department of Energy (DE-FG06-85ER6031), National
Aeronautics and Space Administrabon (NAG-1-589). Support for analy-
sis of the data was provided by the Chemical Manufacturers Associa-
tion (Chlorine Chemistry Council) and the European Chemical Industry
Council (Euro Chlor) for the Global Emissions Inventory Activity (GEIA).
Additional support was provided by the resources of the Biospherics
Research Corporation and the Andarz Co.
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Book Reviews
ii~lrl
Heavy Metals in the Environment: An Integrated Approach
Conference Presentations from the 1st International Conference "Metals in the Environment"
Editor: D.A. Lovejoy (Institute of Geology and Lithuanian Society of Metaloecologists), Vilna, Lithuama, 1999
Publisher: Institute of Geology, Vilna, Lithuania, 1999; 350 pp; 10 US $; ISBN: 9986-615-17-8
Different from organic pollutants, which can be degraded physically,
chemically or biologically in the environment, heavy metals are eternal
substances. They can only change their forms in chemical compounds
which may be more or less toxic. Most dangerous in the environment
are the mobile forms of heavy metals. A number of scientists in the
fields of biology, biochemistry, geology, chemistry, geography, metrol-
ogy, epidemiology, etc. have investigated the behavior of heavy metals
in the environment. The complexity of the problems requires the inte-
grated approach of interdisciplinary teams of scientists.
The 1st International Conference "Metals in the Environment" orga-
nized by the Lithuanian Society of Metaloecologists took place in V,lna.
During the conference, the following problems were discussed prima-
rily: Metals in the biosphere, hydrosphere and lithosphere, Pollunon by
metals, Metalotox]cology, Bioindication and biotesting of metals. Over
60 scientific articles from 10 countries and based on conference presen-
tations are available in this book.
Investigations revealed the steady increase of heavy metal concentration
in soil and groundwater. Anomalies related to metal processing, motor
transport or thermal electric power stations can be clearly distinguished
in the topsoxl of urbanized territorxes. Topsoil is often contaminated to
dangerous or extremely dangerous levels in these areas demonstrating
anomalies. Ra&onuclides are accumulated in the coohng basins of Nuclear
Power Plants (D. ~eburnis, D. Mare(~iufionien& K. dok~,as)
Many factors of soil and synthetic organic matter stimulate the forma-
tion of mobile forms of heavy metals (D. Btazauskiene, L. Lubyte).
82
Research Articles
KHALIL, M.A.K; RASMUSSEN,R.A.; FRENCH,J.R.J; HOLT, J.A. (1990a):
The influence of termites on atmosperic trace gases. J. Geophys. Res.
95, 3619-3634
KHAUL,M.A.K; RASMUSSEN,R.A.; WANG,M.-X.; REN, L. (1990b): Emis-
sions of trace gases from Chinese rice fields and biogas generators.
Chemosphere 20, 207-226
KHALIL,M.A.K; RASMUSSEN,R.A.; SH~RZR, M.J.; CHEW,Z.-L.; YAO,H.;
YANG,J. (1998): Emission of methane, nitrous oxide and other trace
gases from rice fields in China. J. Geophys. Res. 103 (D19) 25,241-
25,250
KHALIL,M.A.K.; MOORE, R.M.; HARPER,D.B.; LOBERT,J.M.; ERICKSON,
D.J.; KOROPALOV,V.; STURGES,W.T.; KEENE, W.C. (1999): Natural
emissions of chlorine containing gases: Reactive chlorine emissions
inventory. J. Geophys. Res. 104, 8333-8346
MINAMI, K. (1987): Emission of nitrous oxide from Agro-Ecosystem.
JARQ 21, 22-27, 1987
RASMUSSEN,R.A:; KHAUL, M.A.K. (1988): Atmospheric halocarbons:
Measurements and analyses of selected trace gases. In: Proceedings
of the NATO Advanced Study Institute on Atmospheric Ozone.
Edited by A.C.Aikin, 209-231 (U.S.Department of Transportation,
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RASMUSSEN,R.A.; LOWLOCK,J.E. (1983): The atmospheric lifetime ex-
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Academic Press, N.Y.
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rotting fungi and an estimate of global flux to the atmosphere. Mycol.
Res. 102, 769-787
Received: September 8th, 1999
Accepted: March 21 st, 2000
Online-First: April 4th, 2000
Large amounts of heavy metals are accumulated in the sewage sludge
from wastewater treatment plants. The toxic effect of metals reduces
the possibilities of using the sludge as a fertilizer. Different methods are
discussed for reducing the toxic effect of heavy metals: The use of peat
(O. Dilifinas) as a natural sorbent, reducing the solubility of heavy met-
als (V. Paulauskas), using macrophytes for the biological removal of
heavy metals (V. Katinas), etc.
To better understand the effects of heavy metals on the environment,
investigations were carried out on living organisms using micro and
macrophytes, soil fungi and ammals (J. Rubikas, J. Bar~ien6, A. Burba,
D. Stankevi~iene, E. Krolak). Fish hemostasis is even disturbed by heavy
metals at low concentrations similar to the concentrations of these met-
als found in clean fresh water. Meanwhile, considerable concentrations
of metals are not seen to cause physiological changes in mollusks. All of
the microorganisms and higher organisms investigated have evolved
different mechanisms of tolerance in environments polluted with heavy
metals. Blood parameters show the harmful effect of heavy metals on
human health in polluted sites (J. Imbrasiene).
Multipurpose, geochemical mapping allows one to solve the tasks aimed
at via investigations on ecological states and the rational use of nature
(K. Jok.{as, L. Ginzburg, R. Tarag~kevi~ius).
Dr. Ona Gyliene
Institute of Chemistry,
A. Go.~tauto 9, 2600 Vilna, Lithuania
E-mail: gyliene@kU.mii.lt
ESPR - Environ. Sci. & Pollut. Res. 7 (2) 2000)