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Atmospheric Environment 41 (2007) 1567–1573
www.elsevier.com/locate/atmosenv
Short communication
Phosphine in the marine atmosphere along a hemispheric
course from China to Antarctica
Renbin Zhua,, Dietmar Glindemannb, Deming Konga, Liguang Suna,
Jinju Gengc, Xiaorong Wangc
a
Institute of Polar Environment, University of Science and Technology of China, Hefei City, Anhui Province 230026, PR China
b
Glindemann Environmental Services, Goettinger Bogen 15, 06126 Halle, Germany
c
State Key Laboratory of Pollution Control and Resource Reuse, Nanjing University, Nanjing 210093, PR China
Received 25 July 2006; received in revised form 19 October 2006; accepted 19 October 2006
Abstract
The gas phosphine (PH3) is a part of an atmospheric link of the phosphorus cycle on earth. Previous research reported
the terrestrial lower tropospheric PH3 at night in the 1 ng m3 range in remote areas, with the peak of 100 ng m3 in
populated areas, and at daytime even lower concentrations in the pg m3 range. The data of the global marine atmospheric
PH3 are still very sparse.
This study presents surprisingly high concentrations of PH3 in the order of 0.1–1 mg m3 in many of 32 samples of the
marine atmosphere in the latitudinal range from 301N to 651S (the cruise of research ship Xuelong from Shanghai Harbor,
China, to Antarctica). The highest concentrations were measured near coastal areas of Eastern Asia and Western
Australia. A significant correlation exists between marine atmospheric PH3 concentration and air temperature at 22:00
(local time). PH3 concentrations at different latitudes strongly decline with daylight intensity according to a logarithmic
relationship. These surprisingly high concentrations of the readily oxidizable PH3 in the air indicate hitherto unknown but
important PH3 emission sources in marine environment. More work is necessary to evaluate the sources of atmospheric
PH3 from marine biosphere.
r 2006 Elsevier Ltd. All rights reserved.
Keywords: Phosphine; Marine atmosphere; Southern ocean; Antarctica
1. Introduction
Phosphine (PH3) is a gaseous carrier of phosphorus in its geochemical cycles, and it might be of
importance to the phosphorus balance of natural
ecosystem. In nature, it exists in two different forms:
free gaseous PH3 and matrix-bound PH3 (MBP)
Corresponding author. Tel./fax: +86 551 3601415.
E-mail address: [email protected] (R. Zhu).
1352-2310/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2006.10.035
(Gassmann and Glindemann, 1993; Glindemann
et al., 1996a). PH3 was detected in many terrestrial
media such as river and lake sediments (Dévai et al.,
1988), marsh soils (Dévai and Delaune, 1995),
landfills and communal waste (Jenkins et al., 2000;
Roels and Verstraete, 2004), animal slurry or
human feces (Glindemann and Bergmann, 1995;
Glindemann et al., 1996a; Ding et al., 2005; Zhu
et al., 2006b), paddy fields (Eismann et al., 1997;
Han et al., 2000) and natural rocks rich in
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phosphorus (Glindemann et al., 2005a). The discovery of PH3 in the natural environment brought
up many questions on the traditional viewpoint of
the phosphorus cycle because PH3 can easily
transfer into air from the solid or water-phase.
Reviews on the subject have been made by Roels
and Verstraete (2001) and Glindemann et al.
(2005b).
The studies of PH3 in marine environment are
rare compared with those in the terrestrial and fresh
water environment. MBP has been found in the
marine sediments of Hamburg Harbor (0.2–55.6
ng kg1) in Germany and Jiaozhou Bay (maximum
685 ng kg1) in China, suggesting that marine biospheres are significant sources for atmospheric PH3
(Gassmann and Schorn, 1993; Gassmann, 1994; Yu
and Song, 2003).
PH3 was even shown to be ubiquitously present in
the low terrestrial troposphere (Glindemann et al.,
1996b; Liu et al., 1999). Atmospheric PH3 in marine
surface air of the Northern Sea and Wadden Sea
(Gassmann et al., 1996) and in the high troposphere
above the North-Atlantic (Glindemann et al., 2003)
has also been observed. Marine atmospheric PH3 is
a good indicator of possibly important coastal or
marine emission sources. However, it is a problem
that PH3 data in the global marine atmosphere are
still very sparse. Therefore, it is necessary that
atmospheric PH3 concentration be measured in the
marine boundary layer over a larger portion of the
world’s oceans.
At present, only a few laboratories are able to be
sufficiently sensitive to detect PH3 in atmospheric
air. This work took the rare opportunity to collect a
large number of marine air samples during the 22th
Chinese Antarctic Research Expedition (CHINARE-22) and analyze atmospheric PH3 concentrations. These air samples taken in the marine
boundary layer covered the latitudes ranging from
301N to 651S. The purposes of this study were (1) to
determine the spatial variations of atmospheric PH3
in the marine boundary layer, and (2) to discuss the
main environmental factors affecting atmospheric
PH3 concentrations and the distribution of the
source strength from the marine biosphere.
2. Expeditionary areas and methods
Marine atmospheric air samples were taken on
the research ship Xuelong that set out from
Shanghai harbor, China, on 15 November 2005,
on the way south. The sampling sites are shown in
60°E
90°E
120°E
CHINA
30°N
INDIA
0°
Equator
PHILIPPINES
MALAYSIA
INDONESIA
INDIAN
OCEAN
30°S
AUSTRALIA
60°S
ANTARCTICA
Fig. 1. Track of research ship Xuelong from Shanghai harbor to
Zhongshan Station during CHINARE-22. Bold line indicates the
track of research ship. Bold black dots indicate air sampling sites.
Fig. 1. Main research and sampling areas included
China Yellow Sea, South China Sea, Philippine Sea,
Eastern Indian Ocean and Southern Ocean around
Antarctic continent. The ship Xuelong reached
Australian Fremantle harbor on 7 December 2005
and left this harbor on 12 December 2004. The ship
headed south along the 122 1E and reached Chinese
Zhongshan Station, Eastern Antarctica on 15
December 2005 (Fig. 1).
Total 32 air samples in the marine boundary layer
were collected at 32 sampling sites (one sample was
taken per site), respectively, on the track. To avoid
the impacts of anthropogenic factors and research
ship self, we collected air samples upwind on the
fore (Zhu et al., 2003). The sampling height was
about 2 m from the deck of the fore (about 25 m
apart from the oceanic surface). The sampling time
was 10:00 and 22:00 (local time) every day to
compare the differences of atmospheric PH3 between the daytime and nighttime, although the
sampling locations of day and night were different
due to the ongoing movement of the ship. The air
temperature and daylight intensity were simultaneously recorded above the oceanic surface.
The air samples were sucked from the outside through stainless-steel tube installed to the
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Table 1
Comparisons between Tedlar gas bag and aluminum foil compound membrane gas bag (ordinary gas bag) over the transport period
Type
Phosphine standards (ng m3)
Initial time
Determination time
Result (ng m3) n ¼ 3
CV (%)
Ordinary gas bag
Ordinary gas bag
Tedlar gas bag
151.8
15180
15180
2005.11.12
2005.11.12
2005.11.12
2006.4.13
2006.4.13
2006.4.13
77.776.0
1423.27120.5
14953.87289.5
48.8
90.6
1.4
Note: Another Tedlar bag was destroyed during the transport (Zhu et al., 2006a).
sampler and stored in 0.5 l Tedlar gas bags with
polypropylene valves (Glindemann et al., 2003). All
the air bags were stored and shipped in two big
barrels filled with N2 which produced a PH3-free
storage space. Three control sample bags, which
were filled with PH3-free air before the expedition
and shipped in the barrel, did not contain PH3 after
the expedition in the laboratory. The barrels with
the sample Tedlar bags were preserved under
20 1C and dark conditions until laboratory analysis. To test the stability of PH3 in these air samples,
we stored two kinds of PH3 standards (15180 and
151.8 ng m3 in air, respectively) in two Tedlar gas
bags (TPV/L-005) and, for comparison purposes, in
two aluminum foil compound membrane gas bags
(ordinary gas bag, LMCL-005), respectively. These
gas bags with PH3 standards were preserved under
the same conditions as the sample Tedlar bags. It
was found that the use of Tedlar bags for the
expedition is justified because the PH3 concentration of the standard was almost stable in Tedlar air
bags over the transport period. The PH3 standard
concentration in aluminum foil compound member
air bags showed a rapid decrease (Table 1), and
therefore these bags were not used for air sampling
(Zhu et al., 2006a).
PH3 was analyzed by an HP4890 GC equipped
with an NPD (nitrogen-phosphorus detector) in
State Key Laboratory of Pollution Control and
Resource Reuse, Nanjing University. Gas samples
in syringes were directly injected through a drying
tube (NaOH as drying agent, Merck, Germany, No.
101567 to remove H2O, CO2 and H2S) into a 6-port
valve on the GC. The PH3 in the N2 was then
enriched in two successive capillary cryo-traps
(cooled down with liquid nitrogen) and desorbed
into the GC column. The column temperature was
40 1C, and the detector temperature was 220 1C. The
flow rates of the detector gases were 2 ml min1 for
H2, 120 ml min1 for air and 30 ml min1 for N2, as
the make-up gas. PH3 (10 ppmv in N2, certified)
used as authentic reference, was purchased in
pressure cylinders from Nanjing Special Gas Plant.
Every sample was measured at least three times.
About 50 ml gas samples were cryo-trapped to reach
a detection limit of 0.1 ng m3 of PH3. The
determination of PH3 concentration was also
described by Ding et al. (2005) and Zhu et al.
(2006b).
The correlations between atmospheric PH3 concentrations and environmental variables were analyzed using the standard statistical methods given in
SPSS software. The correlation is significant at the
po0.05 level.
3. Results
Latitudinal trends of PH3 in the lower troposphere in the range between 301N and 651S are
shown in Fig. 2. The latitudinal trends of PH3 at
10:00 and 22:00 (local time) are closely correlated
except the initial three sampling sites, and no
evident differences at most of the sampling sites
were found between atmospheric PH3 concentrations at 10:00 and 22:00 (local time). In contrast to
other marine areas of this study, atmospheric PH3
above the surface of Southern Ocean (in the range
from 401S to 651S) is very sparse (below 1 ng m3)
and almost no PH3 was detected in some air
samples; that is generally at the same level as the
remote air samples taken by Glindemann et al.
(1996b, 2003).
Three evident PH3 peaks were observed in the
ranges of 301N–201N, 51N–201S and 251S–401S,
respectively. As illustrated in Fig. 2a, the highest
PH3 concentration (5753.2 ng m3) was observed in
the ambient marine air adjacent to Shanghai harbor
around 10:00, greatly exceeding the PH3 content in
other marine atmosphere. The concentration
abruptly declined to below the detection limit at
151N latitude. Atmospheric PH3 concentrations
slowly increased with the latitude and reached the
second peak value (293.0 ng m3) close to 61S. Then
the concentration slowly decreased to 47.2 ng m3 at
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7000
6000
PH3 (ng m-3)
5000
1200
1000
800
600
400
10:00
200
0
30
20
10
0
-10
-20
-30
-40
-50
-60
-70
Latitude (°)
PH3 (ng m-3)
800
600
400
200
22:00
0
30
20
10
0
-10
-20
-30
-40
-50
-60
-70
Latitude (°)
Fig. 2. Latitudinal distributions of marine atmospheric phosphine at 10:00 (a) and 22:00 (b). The positive and negative values indicate
northern and southern latitudes, respectively. Every sample was measured at least three times. The error bar indicates standard deviation.
about 271S and a relatively little peak value
(126.2 ng m3) occurred at 321S. PH3 concentrations
in the marine atmosphere around 22:00 are also
shown in Fig. 2b. High PH3 of 515.4 ng m3 was
observed at about 81S. A peak value (147.2 ng m3)
was also observed between 301S and 401S. Then,
PH3 concentrations at 10:00 and 22:00 (local time)
were near or below 1 ng m3 in the range from 401S
to 651S, suggesting that PH3 emission from the
Southern Ocean was low.
As can be seen in Fig. 3a, no significant
correlation is obtained between marine atmospheric
PH3 concentration and air temperature at 10:00
since PH3 concentration may be predominantly
impacted by light intensity, and a temperature effect
is not evident. However, a significant correlation
exists between PH3 concentration at 22:00 and air
temperature (Fig. 3b), indicating that atmospheric
PH3 levels could be related to local temperature,
which mediates the production and emission of PH3
in the biosphere. Earlier research also showed that
atmospheric PH3 concentration was higher during
the warm period, with more microbial or chemical
activity (Glindemann et al., 1996b; Liu et al., 1999).
Therefore, temperature may be one of the main
factors affecting marine atmospheric PH3 concentrations when light oxidation is inhibited or
weakened.
Marine atmospheric PH3 concentrations at different latitudes decline with daylight intensity
according to a logarithmic relationship (Fig. 4).
That is clearly indicating PH3 oxidation mediated
by the solar UV-radiation, which transforms PH3
back to phosphate (Glindemann et al., 1996b; Liu
et al., 1999). High PH3 concentrations preferably
occur at the sampling sites in the northern hemisphere (winter), where daylight intensity and PH3
oxidation was relatively weaker, compared to the
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8000
700
10:00
22:00
600
500
PH3 (ng m-3)
6000
PH3 (ng m-3)
1571
4000
y = 4.86x + 73.73
r= 0.18; p=0.51
2000
400
y = 7.94x - 22.82
r = 0.60; p=0.019
300
200
100
0
-100
0
-5
5
15
35
25
0
Air temperature (°C)
5
10
15
20
25
30
35
Air temperature (°C)
Fig. 3. Correlations between marine atmospheric PH3 concentration and air temperature at daytime 10:00 (a) and nighttime 22:00 (b). In
(a), the correlation was analyzed without the maximum outlier.
accounts for the differences of PH3 concentrations
between the air samples taken from the northern
and southern hemispheres.
7000
6000
4. Discussion
PH3 (ng / m3)
5000
y = -304.27Ln(x) + 2147.9
1200
r = 0.79; p=0.02
800
400
0
0
400
800
1200
Light intensity (w/h)
Fig. 4. Correlation between marine atmospheric PH3 concentration and sunlight intensity at 10:00 (local time). The data for
atmospheric phosphine in this analysis originate from the air
sampling latitudinal range of 301N–401S.
southern hemisphere, which had an opposite season
(summer). In addition, the results above also
indicate that daylight intensity overrides the influence of temperature on atmospheric PH3 concentrations on the global scale, suggesting that the
daylight effect is one of the main factors that
These surprisingly high concentrations of PH3 (in
the order of 0.1–1 mg m3) need an explanation in
many marine atmospheric samples in the latitudinal
range from 301N to 401S. Previous research
reported the remote lower tropospheric PH3 at
night in the 1 ng m3 range, with the peak of
100 ng m3 in populated areas, and at daytime even
lower concentrations in the pg m3 range (Glindemann et al., 1996b; Liu et al., 1999). It would be
interesting to know and to quantify the source
processes that would cause the marine atmosphere
to accumulate much PH3. Potential PH3 sources
include the biosphere, geochemistry, industries
(including inadvertent phosphide and PH3 generation by a combination of high temperature and
chemical reduction of phosphate, for example in
metallurgy), use of PH3 as a fumigant, cosmic
phosphide-containing fallout, and atmospheric
lightning chemistry (Glindemann et al., 2003).
Firstly, it could be possible that the marine
biosphere in China Yellow Sea (from 301N to
201N) and tropical ocean (101N–201S) is a significant emission source of PH3. That would explain
the PH3 concentration as high as 5753.2 ng m3 in
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the ambient air adjacent to Shanghai harbor around
10:00, which may be also correlated with overcast
sky on this sampling day (20 November 2005). MBP
was recently investigated in the marine sediments of
Jiaozhou Bay in adjacent East China Sea, and the
highest PH3 concentration reached 685.0 ng kg1
(dry, Yu and Song, 2003), which is much higher
than earlier literature data from terrestrial paddy
soils, marshes and landfills. The coast of the
investigation area has also a lot of biologically
active mariculture areas, with a large amount of
organic mariculture sewage input, as a possible
condition of PH3 production and emission. The
emission of PH3 could be driven by other gases—
Zhu et al. (2003) observed high nitrous oxide
concentration
above
the
tropical
ocean
(101N–101S), suggesting high gas emissions from
tropical marine biosphere via the effects of microorganisms. Other biologically active coastal seas
could as well provide conditions of gas emission
including PH3 to explain the high PH3 concentration in other marine atmospheric air samples.
Secondly, PH3 from various anthropogenic
sources may be transported into the inshore atmosphere since the track for research ship Xuelong was
very close to Euro-Asian continent, Philippines,
Malaysia, Indonesia and Australian continent in the
range of 301N–401S. These coastal areas are densely
populated and highly industrialized, and might
provide the conditions for anthropogenic high PH3
emissions from industries and waste sites. The
unexpectedly high marine atmospheric PH3 concentrations in the latitudinal range from 301N to 201N
might well be caused by migration of atmospheric
PH3 from land. These observation sites are very
close to land where the predominant winds were
northwest, and the sampled air mass was significantly influenced by Asian continental sources.
Another more fanciful possibility to explain that
marine atmospheric PH3 could be predominantly
from coal fires. In South China and Southwest
China, heavy acid rain occurred in the precipitation
due to the combustion of local coal (Wang and
Wang, 1996). Acid rain from coal power plants may
liberate MBP from soils, rocks, or rusting ironphosphide of harbor machinery and natural coal fire
underground may reduce phosphate to PH3, which
could provide this PH3 forming mechanism (Glindemann et al., 2003) and explain why inshore
atmospheric PH3 is high in China.
Another possibility is the formation of PH3 by
atmospheric lightning chemistry near our sampling
area from 201N to 201S that belongs to the tropical
ocean with strong lightning activity. Glindemanna
et al. (2004) made spark discharge experiments in
the laboratory to simulate lightning and revealed
the reduction of phosphate to PH3 in presence of
organic matter as reductive chemical. The necessary
organic matter and phosphate could originate from
the flourishing tropical rain forest along the coast,
that makes organic dust, pollen etc very abundant in
the tropical atmosphere.
PH3 could be a very mobile gaseous phosphorus
species which can rise up very high in the atmosphere without major ‘‘wash out’’ compared to
other more water soluble and ‘‘sticky’’ gases like
reduced sulfur gases which could be adsorbed by
water droplets and organic aerosol (Glindemann et
al., 2003). The oxidation of tropospheric PH3 is
delayed under the rainy and overcast weather
conditions. Therefore, it is very possible that PH3
formed by the discussed mechanisms above is
accumulated to explain the high concentrations in
our air samples.
The final fate of all atmospheric PH3 will be
oxidation into water-soluble phosphate, which
enters the marine or coastal biosphere via rain.
We do not know whether PH3 formation and
atmospheric PH3 have significant positive distributing effects on the even dissemination of phosphorus
at the global scale. The redistribution of phosphorus
via PH3 from rich phosphorus sources could
additionally fertilize areas that are poor in phosphorus. The investigations of PH3 production and
emission deserve more scientific attention. The local
and global impact of PH3 on the biogeochemical
phosphorus cycle remains a task that should be
accomplished in the near future.
Acknowledgments
This work was funded by the National Natural
Science Foundation of China (Grant Nos.
40676005, 40406001), AAD Science Project 2873
and The Opening Foundation (PCRRF06006) of
State Key Laboratory of Pollution Control and
Resource Reuse Nanjing University.
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