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Chinese Science Bulletin
© 2007
Science in China Press
Springer-Verlag
The first determination of atmospheric phosphine in
Antarctica
†
ZHU RenBin1 , KONG DeMing1, SUN LiGuang1, GENG JinJu2 & WANG XiaoRong2
1
2
Institute of Polar Environment, University of Science and Technology of China, Hefei 230026, China;
State Key Laboratory of Pollution Control and Resource Reuse, Nanjing University, Nanjing 210093, China
phosphine, Antarctica, Millor Peninsula, atmosphere
Phosphine (PH3) is a highly toxic gas and also a reductive atmospheric trace gas, which competes with methane and other greenhouse gases for hydroxyl radicals
and thus enhances an indirect greenhouse effect[1,2]. For
more than one hundred years, the sources and mechanisms of biological PH3 formation in natural environ―
ments have been investigated and discussed[3 10]. Natural and anthropogenic sources could produce enough
PH3 to be a trace component throughout the Earth’s atmosphere influencing the biogeochemical cycles and the
atmospheric chemistry of phosphorus[11,12]. Therefore,
measurements of PH3 in the Earth’s atmosphere and
studying its sources and sinks are very important for the
understanding of phosphorus geochemical cycles. The
limited observations indicated that high PH3 concentrations generally exist in the atmosphere in the populated
areas[13] while the remote offshore atmosphere the PH3
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concentration is low (at the ng/m3 level during the night
and at the pg/m3 level during daylight)[11,12]. However,
PH3 in Antarctic atmosphere and its affecting factors
have not been reported until now. Furthermore, it is especially important to study PH3 concentration and its
atmospheric chemistry under the strong UV-radiation
due to the occurrence of Ozone Hole in Antarctica. During the 22th Chinese National Antarctic Research Expedition (CHINARE-22), the authors collected the air
samples on Millor Peninsula, where Zhongshan Station
(69°22′24″S, 76°22′40″E) is located, and preliminarily
studied the summertime variation of PH3 concentration
Received June 2, 2006; accepted August 3, 2006
doi: 10.1007/s11434-007-0010-x
†
Corresponding author (email: [email protected])
Supported by the National Natural Science Foundation of China (Grant Nos.
40676005 and 40406001), AAD Science Project 2873 and the Opening Foundation
of State Key Laboratory of Soil and Sustainable Agriculture
Chinese Science Bulletin | January 2007 | vol. 52 | no. 1 | 131-135
ATMOSPHERIC SCIENCE
It is generally thought that phosphine (PH3) concentrations exist at the low ng/m3 level during the night
and at the pg/m3 level during daylight in the remote atmosphere of the lower troposphere. The first determination of gaseous PH3 on the Antarctic Millor Peninsula is reported in this paper. No PH3 was detected in the air samples around 10:00 when it was sunny. However, PH3 was found in all the 10:00 air
samples when it was cloudy or light snow with the average of 75.3±28.8 ng/m3 (n=5). It was also found
in nearly all the samples around 22:00 with the average of 87.2±70.9 ng/m3 (n=11). Atmospheric PH3
concentrations around 22:00 were generally higher than those around 10:00 in January and they were
almost the same in February. In addition, PH3 concentrations around 22:00 showed a downtrend with
the decreasing air temperature, suggesting that light intensity and air temperature had an important
effect on atmospheric PH3 concentration. It is very surprising to have found that high concentrations of
PH3 exist in the Antarctic atmosphere under the influence of strong UV-radiation and light intensity. The
tentative analyses show that dry, cold and very clean atmosphere may be very suitable for the PH3 survival and cause the concentration to increase and accumulate in the local atmosphere. New approaches for the PH3 formation and the process of atmospheric chemistry may exist under such an
extreme environment. Atmospheric PH3 may also be from the emissions of local sources.
and its possible affecting factors.
As illustrated in Figure 1, the sampling site was selected on Millor Peninsula. This peninsula is located
within the Antarctic Circle, one of the several main icefree areas along the coast of Antarctica in the summer. It
has the cold and dry characteristics of typical polar continental climate due to the effects of circular cyclone and
high pressure from Antarctic continent. The vegetation is
very sparse, biological and chemical weathering processes are very weak and no true soil develops in this area
due to severe climatic conditions and exposure to the
bedrock[14].
The observation site for atmospheric PH3 was set up
on a hilltop (about 30 m asl) approximately 300 m to the
south of Zhongshan Station (Figure 1). The air samples
were sucked from the outside through the tread pump
and were stored in 0.5 L Tedlar sampling bags with
polypropylene valves[12]. The sampling frequency was
once every four to six days. On each sampling day, the
sampling time was respectively set at around 10:00 (local time, the same below) in the daytime and 22:00 in
the nighttime, so that the difference between the atmospheric PH3 concentration in the daytime and that in the
nighttime can be compared. The Tedlar bags were
washed with the local air for five times before sampling.
The 22 air samples were collected during December 23,
2005―February 17, 2006. All the air bags were stored
and shipped in a big barrel filled with N2 that produced a
PH3-free storage space. The barrels with the sample
Figure 1
Tedlar bags were all frozen and preserved under −20℃
and dark conditions for lab analysis. To test the stability
of these air samples and the property of Tedlar bags, the
authors stored two kinds of PH3 standards (15180 ng/m3
and 151.8 ng/m3, respectively) in two Tedlar gas bags
(TPV/L-005) and two aluminium foil compound membrane gas bags (ordinary gas bag, LMCL-005), respectively, to detect whether the concentrations of PH3 standards changed over the transport period (Table 1). PH3
concentrations in all the gas samples were determined
by NPD-GC (Agilent 4890D) in State Key Laboratory of
Pollution Control and Resource Reuse, Nanjing University. The method has also been described in ref. [7], [15].
The detection limit of PH3 was about 0.1 ng /m3.
As listed in Table 1, the concentration of the PH3
standard gas declined from 151.8 ng/m3 to 77.7 ng/m3
(decreasing by 48.8%) in one ordinary gas bag. The
concentration declined from 15180 ng/m3 to 1423.2
ng/m3 (decreasing by 90.6%) in another ordinary gas
bag. Although one Tedlar bag was damaged during the
transport period, the concentration for the PH3 standard
gas was almost stable in another Tedlar bag with the
decrease of only 1.4%, indicating that the properties of
Tedlar bag are much better than aluminium foil compound membrane gas bag. Tedlar bag almost does not
absorb PH3. In addition, Tedlar bag can screen light due
to aluminium foil compound membrane outside Tedlar
membrane. Therefore it is thought that the air samples
The atmospheric PH3 observation site on Millor Peninsula, east Antarctica.
Table 1 Comparisons between Tedlar bag and ordinary gas bags over the transport perioda)
Type
PH3 standard concentration (ng/m3)
Final concentration (ng/m3) (n=3)
Changing rate (%)
Ordinary gas bag
151.8
77.7±6.0
−48.8
Ordinary gas bag
15180
1423.2±120.5
−90.6
Tedlar gas bagb)
15180
14953.8±289.5
−1.4
a) The transport period of all the three types were December 11, 2005―April 13, 2006. b) Another Tedlar bag was destroyed during the transport.
132
ZHU RenBin et al. Chinese Science Bulletin | January 2007 | vol. 52 | no. 1 | 131-135
demann and Bergmann[16] determined PH3 (0 ― 295
ng/m3) in the biogases from animal slurry. Glindemann
et al.[11] determined atmospheric PH3 (0―157 ng/m3) in
the different regions of Germany, Argentina, Tunisia,
Seychelles, Israel and Namibia. Liu et al.[13] measured
atmospheric PH3 in Beijing City (14.9 ng/m3) and paddy
fields nearby (137.3 ng/m3). The work presented in this
paper shows that atmospheric PH3 concentrations on
Millor Peninsula are consistent with the reported values
above. However, Gassmann et al.[17] determined PH3 in
the offshore clean atmosphere in the different regions
with the range of 0.041―0.885 ng/m3. Therefore it is
generally thought that PH3 concentrations are below 1
ng/m3 in the remote air of lower troposphere. It is very
surprising that Antarctic atmospheric PH3 concentrations
in the nighttime and under the weather of overcast or
light snow were 1―2 order of magnitude higher than
those earlier reported data for the remote regions far
away from industry, although PH3 in some Antarctic air
samples was not detectable on sunny morning. What
causes a relatively high buildup of atmospheric PH3 on
Antarctic Millor Peninsula? We tentatively discuss such
scientific riddle in the following two aspects:
Firstly, the high buildup of atmospheric PH3 may be
linked with the extreme Antarctic environment conditions. Recently, Glindemann et al.[12] have determined
gaseous PH3 in remote air samples (0.39―2.45 ng/m3,
16 locations) in the upper troposphere (10 km high apart
from the oceanic surface) over the North-Atlantic during
daylight around noontime. PH3 concentrations were
above 1 ng/m3 in the remote atmosphere under strong
Figure 2 The linearly corresponding relationships between PH3 concentrations in the standard gases and peak areas of GC. (a) and (b) show the relationships at the low level (0―1000 ng/m3) and high level (1000―13000 ng/m3) of PH3 concentration, respectively.
ZHU RenBin et al. Chinese Science Bulletin | January 2007 | vol. 52 | no. 1 | 131-135
133
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concentration.
In recent years, some researchers have determined
―
atmospheric PH3 in other global regions[3,11 13,16]. Glin-
ATMOSPHERIC SCIENCE
stored in Tedlar bags are almost stable. On the other
hand, a good linearly responding relationship exists between PH3 concentrations in the standard gases and
chromatographic peak areas (Figure 2), suggesting the
GC was in a good state. Every sample was measured in
parallel at least three times, the results were close to
each other and the average was the final result.
Summertime PH3 concentrations in the atmosphere on
Millor Peninsula are displayed in Figure 3. Gaseous PH3
was found in nearly all the Antarctic air samples (except
the samples on January 3, 2006) around 22:00. The air
samples taken around 22:00 between December 23,
2005 and February 17, 2006 contained 10.4 to 229.0
ng/m3 PH3 with the average of 87.2±70.9 ng/m3 (n=11).
The concentrations around 22:00 showed a downtrend
during the period from January to February 2006 in correspondence with the air temperature variations. The
peak value occurred during the period from January 12
to January 20 with the highest concentration of
229.0±6.8 ng/m3. No PH3 was detected in almost half of
the air samples around 10:00 since they might be collected on sunny days. However, PH3 was found in all the
10:00 air samples when it was cloudy or light snow with
the range of 48.1―121.7 ng/m3 and the average of
75.3±28.8 ng/m3 (n=5). In addition, the changes of atmospheric PH3 concentrations around 10:00 were consistently correlated with those around 22:00. However,
average PH3 concentrations around 22:00 were generally
higher than those around 10:00 in January, suggesting
that sunlight intensity had an important effect on atmospheric PH3 concentration. They were almost equal in
February since it was mainly cloudy or lightly snowy
and light intensity showed an insignificant difference
(Figure 3). Therefore light intensity and air temperature
are the main factors affecting Antarctic atmospheric PH3
Figure 3 Summertime PH3 concentration in the atmosphere (a) and air
temperature (b) on Millor Peninsula, east Antarctica. Error bar indicates
the standard deviation of three repetitive measurements for every sample.
sunlight and UV-radiation. The related experiment
shows that atmospheric PH3 could possibly survive the
daylight much longer at high altitudes because of a lack
of UV-induced oxidants in the clean and dry air, and PH3
can more easily sustain its mobile gaseous state in the
atmosphere compared to gases like H2S and NH3[12].
Millor Peninsula is located within the Antarctic Circle.
This area has a very dry, cold climate and a very clean
1
Cao Y, Song Y, Sun G Y, et al. Review of toxicology on phosphine. J
atmosphere. Here, it is concluded that the climatic and
environmental conditions on Millor Peninsula may even
be more suitable for the survival of atmospheric PH3
than those in the upper troposphere. Therefore, PH3
could sustain a longer lifetime and thus accumulated in
the Antarctic atmosphere. In addition, it is possible that
new approaches for the PH3 formation and the process
of atmospheric chemistry also exist in local atmosphere.
Secondly, atmospheric PH3 may be from the emissions of local sources. The prevailing wind directions
were around northeast and east over Millor Peninisula
during the atmospheric sample collection periods.
Northeast of the sampling site is also the direction where
two large penguin colonies and a small salt marsh
named Wolong Beach are located (Figure 1). Marine
phosphorus is enriched in Antarctic penguin guano
(2.0%―6.2%), ornithogenic soil or sediment (2.0%―
6.6%)[18]. High N2O and CH4 emissions from the ornithogenic soils have also been observed in the summertime of the coastal Antarctica[19,20]. Recently, matrix-bound PH3 (MBP) has also been analyzed in emperor penguin guano (2.54±1.28 ng/kg), Gentoo penguin
guano (6.21±2.15 ng/kg), and ornithogenic soils or
sediments in the maritime Antarctic[15]. Therefore, the
emissions from the guanos and ornithogenic soils or
sediments in penguin colonies might be the predominant
sources of atmospheric PH3 at the Antarctic locations.
Wolong Beach located between Zhongshan Station and
Russian Progress Station has an influx of the sewage
from two scientific stations. The sewage and waste are
important sources of atmospheric PH3[3,16]. Therefore,
atmospheric PH3 may be from the emission of salt marsh.
The two tentative analyses need to be further confirmed
by in situ observation and laboratory simulation in the
future.
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