ARTICLE IN PRESS

Atmospheric Environment ] (]]]]) ]]]–]]]

www.elsevier.com/locate/atmosenv

Nitrogen isotopic signature of soil-released nitric oxide (NO)

after fertilizer application
Dejun Li, Xinming Wang
State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, P.O. Box 1131,
Wushan, Guangzhou 510640, China
Received 9 September 2007; received in revised form 21 January 2008; accepted 23 January 2008

Abstract

Nitrogen isotopic signatures are very useful for identifying sources of atmospheric NOx or NO 3 . Although soil is a
major source of atmospheric nitric oxide (NO), yet nitrogen isotopic composition of soil-released NO has not been directly
measured. Since a large portion of soil NO emission is induced by fertilizer application in food production, in the present
study we determined N isotopic signatures of NO from cropland soils fertilized with urea and ammonium bicarbonate
(ABC). NO was oxidized to NO2 and then converted to nitrite for nitrogen isotope analysis; tests with NO standard gas
revealed no significant nitrogen isotopic fractioning during the trapping and processing procedures. While the applied urea
and ABC had d15N values of +1.3% and +7.2%, respectively, soil-released NO had d15N values increasing from 48.9%
(day 2) to 28.0% (day 13) after urea fertilization and from 48.6% (day 2) to 19.9% (day 13) after ABC fertilization.
This much 15N depleted isotopic composition of soil-released NO makes it possible to distinguish soil emission from fuel
+
combustion for the contribution of atmospheric NOx or NO 3 . Nitrogen isotopic compositions of soil substrate NH4 and

NO3 were also determined, and the instantaneous nitrogen isotopic enrichment factor of NO relative to those of substrate
NH+ 
4 and NO3 indicated both nitrification and denitrification occurred for NO production, although only NH4 -based
+

fertilizers were applied.

r 2008 Elsevier Ltd. All rights reserved.

Keywords: Nitrogen isotope; Nitric oxide; Soil emission; Fertilization

1. Introduction predominant sources may differ from remote

Nitrogen (N) oxides (NOx ¼ NO+NO2) are
among the most important molecules in atmo-
spheric chemistry (Seinfeld and Pandis, 1998). On
the global scale, major sources of NOx include fossil
fuel combustion, soil release, biomass burning and
lightning (IPCC, 2001), but atmospheric distribu-
tion of NOx is highly non-uniform, and their
Corresponding author. Tel./fax: +86 20 85290180.
E-mail address: wangxm@gig.ac.cn (X. Wang).
regions to urban areas. Source identification and
apportionment of the atmospheric NOx and their
atmospheric transformed products are of critical
importance for the understanding of N cycling, for
the study of chemical processes in the atmosphere,
and for the control of NOx-related environmental
problems, like photochemical smog.
The use of stable isotopic composition as a
potential source tracer for atmospheric gases and
aerosol species is reasonably well documented
(McArdle et al., 1998; Norman et al., 1999; Yeatman

1352-2310/$ - see front matter r 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2008.01.042

Please cite this article as: Li, D., Wang, X., Nitrogen isotopic signature of soil-released nitric oxide (NO) after fertilizer application.
Atmospheric Environment (2008), doi:10.1016/j.atmosenv.2008.01.042
 ARTICLE IN PRESS
2 D. Li, X. Wang / Atmospheric Environment ] (]]]]) ]]]–]]]
et al., 2001). Just as stable isotopes of sulfur in source
apportioning of aerosol SO2 4 (McArdle et al., 1998),
N isotopic compositions can provide important
information regarding the sources and processing
of aerosol ammonium and nitrate (Yeatman et al.,
2001; Gao, 2002; Widory, 2007). N isotopic signature
was also used to identify the main sources of
ammonium and nitrate in rain waters (Russell et
al., 1998; Gao, 2002; Xiao and Liu, 2002).
A powerful tool as it is, N isotopic signature can
only be successfully applied with accumulating data
of N isotopic fingerprints of emission sources and
major environmental processes. However, to date N
isotopic signatures of NOx from some major
sources, like soil release, has not been directly
measured and well characterized, although soils are
regarded as one of the most important contributors
to the atmospheric NOx, probably only next to
fossil fuel combustion in magnitude (Davidson and
Kingerlee, 1997). According to the global soil NO
emission estimates, the fertilized cropland soil was
responsible for 26–41% of the global total soil NO
emission, and most of the NO emission from
cropland soil was induced by N fertilizer application
(Yienger and Levy, 1995; Davidson and Kingerlee,
1997; Bouwman et al., 2002; Yan et al., 2005).
Although not directly measured, N isotope of
soil-derived NO was proposed to be more depleted
in the heavier N isotope with a d15N value up to
about 20%, and differed from the anthropogeni-
cally derived ones (Freyer, 1978; Freyer et al., 1993).
But the proof must await actual isotopic measure-
ments (Heaton, 1987; Freyer et al., 1993). In this
study, we measured N isotopic composition of NO
emitted from cropland soil following application of
urea (NH4HCO3) and ammonium bicarbonate
(ABC) with the aim to get the N isotopic informa-
tion for soil-derived NO.
2. Materials and methods
2.1. Chemicals
Methanol was of HPLC grade and water was
double-distilled. Both NO standard gas and N2 had
a purity of 99.999%. All other chemicals were of
AR grade.
2.2. Experimental design
The soil used in this experiment was collected
directly from a vegetable field (top layer of 0–20 cm)
Please cite this article as: Li, D., Wang, X., Nitrogen isotopic signature of soil-released nitric oxide (NO) after fertilizer application.
Atmospheric Environment (2008), doi:10.1016/j.atmosenv.2008.01.042
in the suburban of Guangzhou. The soil type is
lateritic red earth, which is typical in subtropical
China. Some soil properties were analyzed after the
soil was mixed well (National Standard Bureau
of China, 1987). Soil pH averaged 6.9970.02
(extracted with KCl solution), with an initial total
C content of 1.6970.07% and a total N content of
0.1470.01%. Soil texture was sandy clay loam with
a bulk density of 1.1870.18 g cm3.
The well-mixed soil was put into six stainless-steel
frames (30 cm  30 cm  10 cm) with water-filled
channel on the top. The experiment was conducted
under laboratory conditions (2572 1C). Before the
experiment, the six frames with soils were left for a
week except that deionized water was sprayed to the
soil to maintain the gravimetric soil moisture within
a range (16–24%) similar to that of the vegetable
field in this region (Li and Wang, 2007).
Two types of N fertilizer, urea and ABC, were
dissolved in 100 ml water and applied to the soil
surface with a hand-held sprayer at a rate of
20 g N m2. Each N fertilizer treatment had three
replicates.
2.3. Flux measurement
NO fluxes were measured by a dynamic flow-
through chamber technique, which was similar to
that used by Pilegaard et al. (1999). The chambers
were made of stainless steel with inner walls covered
by Teflon films. Each chamber had an area of
30 cm  30 cm with a total volume of 9 l. It has one
inlet port, one exhaust port and one outlet port for
sampling. Inside each chamber, a thermo-sensor
was fixed to measure air temperature, and a fan
attached to ensure sufficient mixing of air within the
chamber. Upon measurement, the sampling cham-
bers were put onto the frames. An additional
reference chamber, closed at the bottom with Teflon
sheet, was adopted for in situ quantification of
chemical reactions and chamber wall deposition
effects (Kirkman et al., 2002). Ambient air was
pumped into the chambers at a rate of 4 l min1
through Teflon tubes. The residence time of air
in the chambers was about 2.25 min. After approx-
imate 15 min (over five cycles of residence time),
when a steady state was reached inside the
chambers, NO were analyzed by a model 42C
chemiluminescence NO–NO2–NOx analyzer
(Thermo Environmental Instruments Inc., USA).
By the contrast of sampling chambers and the
 ARTICLE IN PRESS
D. Li, X. Wang / Atmospheric Environment ] (]]]]) ]]]–]]]
reference chamber, net fluxes from the soils could be
obtained (Pilegaard et al., 1999).
2.4. Trapping of NO for N isotopic analysis
The principle of selectively trapping atmospheric
NO for N isotope analysis was similar to that used
by Ammann et al. (1999). A solid oxidizer (CrO3/
H3PO4) was used to convert NO into NO2 (Levaggi
et al., 1972). The tubular deluder was a sand-blasted
Pyrex tube (3 mm  5 mm  75 mm) with N-free
coating of KOH/guaiacol (Williams and Grosjean,
1990). The coating was prepared by wetting the tube
with a methanol (HPLC grade) solution of KOH/
guaiacol and drying in pure N2 gas (99.999%).
The NO trapping system was shown in Fig. 1.
The chambers were the same as those for flux
measurement. After the chamber was put onto the
frame, using a portable pump air was circulated
within a loop consisting of the chamber and the
trapping system. The flow rate was controlled to be
1.0 l min1 by a mass flow controller. Under the
same conditions, a breakthrough test with two
trapping tubes connected in series indicated that
nitrite (the preferential product of NO2 and
guaiacol) in the second denuder was undetectable
with an Ion Chromatography (761 compact IC,
Metrohm, Switzerland).
After sampling, the tubes were eluted with 0.5 ml
methanol and 0.5 ml water. The elute was collected
in a 1 ml vial and dried in a vacuum desiccator.
After drying, the residual was carefully collected in
tin (Sn) boats and stored air-tightly until isotope
analysis.
(1) Chamber
(3) CrO3/H3PO4 oxidiser
(3) (3) Absorbent tube
(3) Airflow controller
(5) Pump
(1) (2) (5)
(4)
Fig. 1. Schematic diagram of the NO trapping system.
Please cite this article as: Li, D., Wang, X., Nitrogen isotopic signature of soil-released nitric oxide (NO) after fertilizer application.
Atmospheric Environment (2008), doi:10.1016/j.atmosenv.2008.01.042
3
2.5. Measurements of inorganic N concentrations
Soil samples before fertilization and in each NO
sampling day were collected with a 1-cm-diameter
corer to a depth of 5 cm. The soil samples from the
same treatment were thoroughly mixed, and the
coarse stones and roots were removed by hand.
About 10 g fresh sample (50 g for soil sample before
fertilization) was extracted with 100 ml 2 M KCl
solution and filtered through 0.45 mm membrane
filter after shaking 1 h on an orbital shaker. The
extracts were stored in the refrigerator at 18 1C for
later analysis. NH+4 was determined by indophenol
blue method, and NO 
3 (plus NO2 ) was analyzed by
copper–cadmium reduction method (National Stan-
dard Bureau of China, 1987). Final values of N
pools were reported as mg N g1 dry soil, where dry
soils referred to constant weight after drying at
105 1C.
2.6. Isolating soil NH+4 and NO3 by ammonia
diffusion method for N isotopic analysis
Based on the procedure of Downs et al. (1999),
sequential diffusion method was used for isolating
the soil NH+ 
4 and NO3 fractions. Aliquot of soil
extract containing 60–150 mg N of each sample was
transferred to 100 ml wide-mouth polyethylene
bottle, followed by adding 0.2 g magnesium oxide
(MgO) powder to increase the solution pH.
Ammonia diffusing out of solution was captured
on PTFE band enclosed, acid-soaked glass-fibre
filter (GF/F; Whatman, Maidstone, UK). The NH+ 4
fraction was left to diffuse from the sample for 7
days, whereupon the filter trap was removed and a
fresh one was put into the bottle, followed by
adding 0.4 g Davarda’s alloy to reduce NO 3 to
NH+ +
4 , and collected the transformed NH4 in an
identical manner. The removed filter packs were
opened and the filter strips were dried in a
desiccator. The dried filter strips were packed in
tin boats for analysis and stored in individual air-
tight vials until they were analyzed. Different from
Downs et al. (1999), the filter pack was impregnated
with 30 ml of 2 M citric acid, which was proven to be
effective to replace H2SO4 for NH3 collection
(Schleppi et al., 2006).
2.7. N isotope analysis
N isotopic composition of tin-wrapped samples
and fertilizers was determined with an online system
 ARTICLE IN PRESS
4 D. Li, X. Wang / Atmospheric Environment ] (]]]]) ]]]–]]]

of ThermoQuest Deltaplus XL isotope ratio mass
spectrometer coupled to an EA 1112 automatic
elemental analyzer through a ConFlo II continuous
flow interface (EA-IRMS, Thermo Finnigan MAT,
Bremen, Germany). N isotopic data are reported as
d15N value following Mariotti (1983):
d15 N ¼ ½ðRsample =Rstandard Þ  1  1000,
15 14
where R is the ratio of N/ N, and the standard is
the atmospheric N2.
2.8. QC/QA
During the analysis of each batch of samples,
reagent blank and standard reagent of known d15N
value (0.4%) were also analyzed. Low background,
excellent reproducibility (70.2%) and accuracy
(70.2%) were achieved.
To evaluate whether isotopic fractionation oc-
curred during NO trapping and the following
processes, 5 ppmv NO gas (499.999% NO diluted
in 499.999% N2) was trapped and got isotopic
composition determined the same way as soil-
released NO.
N isotopic composition of pure NO gas was
analyzed using a HP 6890 gas chromatography
(GC) coupled with the DELTA plus XL isotope ratio
fertilized sites range from 1.19 to 44 ng N m2 s1
and are generally larger than those from corre-
sponding sites that were not recently fertilized
(0.01–3.5 ng N m2 s1) (McKenney and Drury,
1997, and references therein). So majority of NO
released was reasonably fertilizer-induced in the
present study. N isotopic composition for NO was
(1)
only measured from day 2 to day 13 after
fertilization, during which NO fluxes were also
measured (Fig. 2a). Urea and ABC fertilizers used
in the present study had d15N values of 1.3% and
7.2%, respectively. As indicated in Fig. 2b, soil-
released NO from both urea- and ABC-treated plots
was significantly depleted in 15N compared to the
d15N values of the fertilizers. NO released from both
urea- and ABC-fertilized plots had initial d15N
values of nearly 50%, but from day 2 to day 6 the
d15N values increased sharply to 430%, and
tended to level off from day 6 to day 13.
NO is produced as an intermediate during
nitrification from NH+ 
4 to NO3 and denitrification

from NO3 to N2 (Ludwig et al., 2001). Both
500
Urea
ABC
400
NO fluxes (ng N m-2 s-1)

mass spectrometer. The GC was equipped with two

300
HP-plot columns in series (60 m  0.32 mm 
0.25 mm) in a split injection mode (40:1). Oven
200
temperature was kept at 40 1C.
100
3. Results and discussion
0
3.1. Method evaluation
0 2 4 6 8 10 12 14
For the NO standard gas, d15N value was -15
50.270.3% (n ¼ 5) when it was directly analyzed
by GC-IRMS, and was 50.470.3% (n ¼ 5) when -20
δ15N in emitted NO (per mil)

analyzed by EA-IRMS after NO was trapped and -25

converted to NO 2 with the trapping system the -30
same way as the soil-released NO. No significant
difference existed between the two groups of data, -35
indicating no isotopic fractionation during the -40
trapping and the following processing procedures. -45
Urea
3.2. d15N values of soil-released NO -50
ABC
-55
From our previous study in vegetable fields, NO 0 2 4 6 8 10 12 14
emission drastically increased after N fertilizer Days after fertilization
application (Li and Wang, 2007); and other studies Fig. 2. Variation of (a) NO fluxes and (b) d15N of NO over the
also indicated that NO emission from recently sampling period.

Please cite this article as: Li, D., Wang, X., Nitrogen isotopic signature of soil-released nitric oxide (NO) after fertilizer application.
Atmospheric Environment (2008), doi:10.1016/j.atmosenv.2008.01.042
 ARTICLE IN PRESS
D. Li, X. Wang / Atmospheric Environment ] (]]]]) ]]]–]]] 5

processes kinetically favor utilizing the lighter N
isotope (14N), which leads to more depleted d15N
values in the products than in the reactants
(Högberg, 1997). Although no measurements have
been reported about N isotopic composition of soil-
derived NO, other gaseous N (N2 and N2O)
produced by nitrification and denitrification were
found to be highly depleted in 15N (e.g., Högberg,
1997; Pérez et al., 2001). In a study by Pérez et al.
(2001), N2O emitted from an agricultural field
fertilized with urea had highly depleted d15N values
(46%) during the first week when N2O emissions
were the highest, just as soil-released NO after
fertilization in the present study. They also observed
enriched d15N values (+5%) at the end of the
second week when emissions were low. Based on
calculated equilibrium N isotope effects for bacter-
ial denitrification from nitrite to NO, and measured
kinetic fractionation effects for denitrification reac-
tion, Freyer et al. (1993) estimated that natural NO
emissions would be 15N depleted with d15N value up
to about 20%. The relatively depleted d15N value
in soil-derived NO was also indirectly supported by
the few existing field measurements, for example,
Moore (1977) reported that d15N was 9.373.5%
for NO2 in clean air, where a larger portion of NO2
was converted from NO from natural soil emission.
From our study, after about 2 weeks of fertilization,
NO had d15N values of 28.0% and 19.8% for
the urea and ABC-treated plots, respectively, and
during the experiment period d15N values for
emitted NO averaged approximately 35.5% and
29.1% for the urea and ABC-treated plots,
respectively. These results well-confirmed previous
projections of the much depleted 15N for soil-
released NO.
Urea and ABC application would also induce
large amount of NH3 volatilization (Xing and Zhu,
2000). Since significant isotopic fractionation usual-
ly occur during NH3 volatilization, the volatilized
NH3 can be 15N depleted to a d15N value of about
40% relative to the substrate, and leave the
remaining N enriched in 15N when the substrate
supply is limited (Högberg, 1997). Additionally, as
shown in Fig. 2b and Fig. 3c and d, products of
15
nitrification like NO and NO 3 were also N
+
depleted. Therefore the remaining NH4 would
become heavier and relatively enriched in 15N
(Fig. 3), which in turn caused increasing d15N
values for nitrification products (like NO and NO 3)
and volatilized NH3 (Högberg, 1997).
3.3. d15N of soil-released NO in comparison with
those of substrate NH+4 and NO 3
In this study, as indicated by the changes of
soil NH+4 and NO 3 (Fig. 3), nitrification was
the process controlling NO production. Over the

350 300
300 250
μg N g-1 dry soil

μg N g-1 dry soil

250 200
200
150
150
100
100
50 50
0 0

0 2 4 6 8 10 12 0 2 4 6 8 10 12
40 40
30 30
δ15 N (per mil)

δ15 N (per mil)

20 20
10 10
0 0
-10 -10
-20 -20
-30 -30
0 2 4 6 8 10 12 0 2 4 6 8 10 12
Days after fertilization

Fig. 3. Variation of concentrations of NH+  15 +

4 (solid circles) and NO3 (open circles) in (a) urea- and (b) ABC-treated soil, and d N in NH4

(solid circles) and NO3 (open circles) in (c) urea- and (d) ABC-treated soil over the sampling period.

Please cite this article as: Li, D., Wang, X., Nitrogen isotopic signature of soil-released nitric oxide (NO) after fertilizer application.
Atmospheric Environment (2008), doi:10.1016/j.atmosenv.2008.01.042
 ARTICLE IN PRESS
6 D. Li, X. Wang / Atmospheric Environment ] (]]]]) ]]]–]]]

2-week sampling period, NO 3 pools increased with to 16.0% for NO emitted from the urea- and
the decline of NH+ 4 pools in both urea- and ABC- ABC-fertilized soil, respectively, and most of
treated plots. This increase of soil NO 3 pools after eoveralldenit were within the range of reported
application of NH+ 4 -based fertilizer implied the enrichment factors for denitrification (Pérez et al.,
existence of nitrification. In some studies, instanta- 2001, Fig. 4). These facts indicated that both
neous enrichment factor (e ¼ d15Nproduct nitrification and denitrification occurred for NO
15
d Nsubstrate) was used to differentiate between production during the sampling period.
nitrification and denitrification as the production
sources for N2O and N2 (Barford et al., 1999; Pérez
et al., 2001). In this study, we used measured d15N
values for NO +
3 and NH4 substrates (Fig. 3) and 3.4. d15N of soil-released NO in comparison with
emitted NO (Fig. 2) to calculate instantaneous other emission sources
enrichment factors for NO each day assuming that
the entire NO production was either via nitrifi- Since very little isotopic fractionation is envisaged
cation (eoverallnit ¼ d15N–NOemittedd15N–NH+ 4 ) at the high temperatures of combustion, the d15N
or denitrification (eoveralldenit ¼ d15N–NOemitted values of NOx emitted from combustion processes
d15N–NO 3 ). eoverallnit were 65.2% to 56.2% were expected to be similar to the N which was
and 58% to 45.4% for NO emitted from the oxidized (Heaton, 1986). But further measurements
urea- and ABC-fertilized soil, respectively, during found that d15N values of NOx from combustion
the sampling period, and well fell in the range of the processes exhibited a much large range probably
reported enrichment factors (Fig. 4). eoveralldenit due to different combustion mode (Widory, 2007).
ranged from 31% to 18.6% and from 30.4% In Table 1, we compiled reported data of N isotopic
signature in emitted NOx from different sources.
NOx emitted from coal-fired power station had a
-10 d15N range from 5% to 13%, and those emitted
from vehicle exhaust had a range from 14% to
-20
Denitrification 4%. Since our results revealed much depleted d15N
-30 values, it seems that the three major sources of NO
-40 could be distinguished by their N isotopic signa-
ε overall-nit and ε overall-denit (per mil)

tures.
-50
It should be emphasized that this study was just a
-60 Nitrification first attack on N isotope composition for soil-
-70
derived NO. As the kinetic isotope fractionation in
0 2 4 6 8 10 12 14 biological processes is very dependent on the
-10 particular environmental conditions (Heaton,
-20 1986), more measurements are needed in order to
DeniNitrification get a representative range for N isotopic composi-
-30
tions of soil-derived NO.
-40

-50

-60 Nitrification Table 1

N isotopic composition of NO emitted from different sources
-70
0 2 4 6 8 10 12 14
Sources d15N (%) References
Days after fertilization
Vehicle exhaust 3.4 to 3.9 Moore (1977)
Fig. 4. Calculated overall instantaneous enrichment factors (e)
Vehicle exhaust (gasoline) 11 to 2 Heaton (1990)
for each day assuming that the emitted NO was produced by
Vehicle exhaust (diesel) 13 to 2 Heaton (1990)
either nitrification (eovernit ¼ d15N–NOemittedd15N–NH+ 4 , solid
Vehicle exhaust 14 to 7 Heaton (1987)
circles) or denitrification (eoverdenit ¼ d15N–NOemitted
Coal-fired power station 6 to 13 Heaton (1990)
d15N–NO 3 , open circles) from (a) urea- and (b) ABC-fertilized
Coal-fired power station 5.2 Heaton (1987)
soil. Shaded areas indicate the range of enrichment factors for
Urea-fertilized soil 48.9 to 28 This study
nitrification and denitrification available in the literature (Pérez et
ABC-fertilized soil 48.6 to 19.8 This study
al., 2001, and references therein).

Please cite this article as: Li, D., Wang, X., Nitrogen isotopic signature of soil-released nitric oxide (NO) after fertilizer application.
Atmospheric Environment (2008), doi:10.1016/j.atmosenv.2008.01.042
 ARTICLE IN PRESS
D. Li, X. Wang / Atmospheric Environment ] (]]]]) ]]]–]]]
4. Conclusions
In the present study, N isotopic signatures were
first determined for NO emitted from cropland soil
fertilized with urea and ABC. The results indicated
that NO emitted from fertilized soil was signifi-
cantly depleted in 15N. As d15N values of NOx from
fertilized cropland is quite distinctive compared to
those from coal-fired power plants and vehicle
exhaust, N isotope tracer may be a useful tool to
distinguish atmospheric NOx sources, especially
between biogenic soil emission and fossil fuel
combustion.
Acknowledgment
This work was supported by the National
Basic Research Program of China (Project no.
2002CB410803) and an innovative project of
Guangzhou Institute of Geochemistry (54O7342101).
References
Ammann, M., Siegwolf, R., Pichlmayer, F., Suter, M., Saurer,
M., Brunold, C., 1999. Estimating the uptake of traffic NO2
from 15N abundance in Norway spruce needles. Oecologia
118, 124–131.
Barford, C.C., Montoya, J.P., Altabet, M.A., Mitchell, R., 1999.
Steady-state nitrogen isotope effect of N2 and N2O produc-
tion in Paracocus denitrificans. Applied and Environmental
Microbiology 65, 989–994.
Bouwman, A.F., Boumans, L.J.M., Batjes, N.H., 2002. Modeling
global annual N2O and NO emissions from fertilized fields.
Global Biogeochemical Cycles 16, 1080, doi:10.1029/
2001GB001812.
Davidson, E.A., Kingerlee, W., 1997. A global inventory of nitric
oxide emissions of from soils. Nutrient Cycling in Agroeco-
systems 48, 37–50.
Downs, M., Michener, B., Fry, B., Nadelhoffer, K., 1999.
Routine measurement of dissolved inorganic 15N in precipita-
tion and streamwater. Environmental Monitoring and As-
sessment 55, 211–220.
Freyer, H.D., 1978. Seasonal trends of NH+ 
4 and NO3 nitrogen
isotope composition in rain collected at Jülich, Germany.
Tellus 30, 83–92.
Freyer, H.D., Kley, D., Volz-Thomas, A., Kobel, K., 1993. On
the interaction of isotopic exchange processes with photo-
chemical reactions in atmospheric oxides of nitrogen. Journal
of Geophysical Research 98, 14791–14796.
Gao, Y., 2002. Atmospheric nitrogen deposition to barnegat Bay.
Atmospheric Environment 36, 578–5794.
Heaton, T.H.E., 1986. Isotopic studies of nitrogen pollution in
the hydrosphere and atmosphere: a review. Chemical Geology
(Isotope Geoscience Section) 59, 87–102.
Heaton, T.H.E., 1987. 15N/14N ratios of nitrate and ammonium
at Pretoria, South Africa. Atmospheric Environment 21,
843–852.
Please cite this article as: Li, D., Wang, X., Nitrogen isotopic signature of soil-released nitric oxide (NO) after fertilizer application.
Atmospheric Environment (2008), doi:10.1016/j.atmosenv.2008.01.042
7
Heaton, T.H.E., 1990. 15N/14N ratios of NOx from vehi-
cle engines and coal-fired power stations. Tellus 42B,
304–307.
Högberg, P., 1997. Tansley review no. 95: 15N natural abundance
in soil–plant systems. New Phytologist 137, 179–203.
IPCC, 2001. Climate Change 2001: The Scientific Basis-Con-
tribution of Working Group I to the Third Assessment
Report of the Intergovernmental Panel on Climate Change.
Cambridge University Press, New York.
Kirkman, G.A., Gut, A., Ammann, C., Gatti, L.V., Cordova,
A.M., Moura, M.A.L., Andreae, M.O., Meixner, F.X., 2002.
Surface exchange of nitric oxide, nitrogen dioxide, and ozone
at a cattle pasture in Rondônia, Brazil. Journal of Geophy-
sical Research 107, 8083.
Levaggi, D.A., Siu, W., Feldstein, M., Kothny, E.L., 1972.
Quantitative separation of nitric oxide from nitrogen dioxide
at atmospheric concentration range. Environmental Science
and Technology 6, 250–252.
Li, D.J., Wang, X.M., 2007. Nitric oxide emission from a typical
vegetable field in the Pearl River Delta, China. Atmospheric
Environment 41, 9498–9505.
Ludwig, J., Meixner, F.X., Vogel, B., Förstner, J., 2001. Soil–air
exchange of nitric oxide: an overview of processes, environ-
mental factors, and modeling studies. Biogeochemistry 52,
225–257.
Mariotti, A., 1983. Atmospheric nitrogen is a reliable standard
for natural 15N abundance measurements. Nature 303,
685–687.
McArdle, N., Liss, P., Dennis, P., 1998. An isotopic study
of atmospheric sulphur at three sites in wales and at mace
head, eire. Journal of Geophysical Research 103,
31079–31094.
McKenney, D.J., Drury, C.F., 1997. Nitric oxide produc-
tion in agricultural soils. Global Change Biology 3,
317–326.
Moore, H., 1977. The isotopic composition of ammonia, nitrogen
dioxide and nitrate in the atmosphere. Atmospheric Environ-
ment 11, 1239–1243.
National Standard Bureau of China, 1987. Analytical Methods
for Forest Soils (3rd Fascicule). National Standard Bureau
Press, Beijing (in Chinese).
Norman, A.L., Barrie, L.A., Toom-Sauntry, D., Sirois, A.,
Krouse, H.R., Li, S.M., Sharma, S., 1999. Sources of aerosol
sulphate at Alert: apportionment using stable isotopes.
Journal of Geophysical Research 104, 11619–11631.
Pérez, T., Trumbore, S.E., Tyler, S.C., Matson, P.A., Ortiz-
Monasterio, I., Rahn, T., Griffith, D.W.T., 2001. Identi-
fying the agricultural imprint on the global N2O budget using
stable isotopes. Journal of Geophysical research 106,
9869–9878.
Pilegaard, K., Hummelshøj, P., Jensen, N.O., 1999. Nitric oxide
emission from a Norway spruce forest floor. Journal of
Geophysical Research 104, 3433–3445.
Russel, K.M., Galloway, J.N., Macko, S., Moody, J.L.,
Scudlark, J.R., 1998. Sources of nitrogen in wet deposition
to the Chesapeake bay region. Atmospheric Environment 32,
2453–2465.
Schleppi, P., Bucher-Wallin, I., Saurer, M., Jäggi, M., Landolt,
W., 2006. Citric acid traps to replace sulphuric acid in
the ammonia diffusion of dilute water samples for 15N
analysis. Rapid Communications in Mass Spectrometry 20,
629–634.
 ARTICLE IN PRESS
8 D. Li, X. Wang / Atmospheric Environment ] (]]]]) ]]]–]]]

Seinfeld, J.H., Pandis, S.N., 1998. Atmospheric Chemistry and
Physics: From Air Pollution to Climate Change. Wiley, New
York.
Widory, D., 2007. Nitrogen isotopes: tracers of origin and
processes affecting PM10 in the atmosphere of Paris. Atmo-
spheric Environment 41, 2382–2390.
Williams, E.J., Grosjean, D., 1990. Removal of atmospheric
oxidants with annular denuders. Environmental Science and
Technology 24, 811–814.
Xiao, H.Y., Liu, C.Q., 2002. Sources of nitrogen and sulfur in
wet deposition at Guiyang southwest China. Atmospheric
Environment 36, 5121–5130.
Xing, G.X., Zhu, Z.L., 2000. An assessment of N loss from
agricultural fields to the environment in China. Nutrient
Cycling in Agroecosystems 57, 67–73.
Yan, X.Y., Ohara, T., Akimoto, H., 2005. Statistical modeling of
global soil NOx emissions. Global Biogeochemical Cycles 19,
GB3019, doi:10.1029/2004GB002276.
Yeatman, S.G., Spokes, L.J., Dennis, P.F., Jickells, T.D., 2001.
Compositions of aerosol nitrogen isotopic composition at two
polluted coastal sites. Atmospheric Environment 35, 1307–1320.
Yienger, J.J., Levy II, H., 1995. Empirical model of global soil
biogenic NOx emissions. Journal of Geophysical Research
100, 11447–11464.

Please cite this article as: Li, D., Wang, X., Nitrogen isotopic signature of soil-released nitric oxide (NO) after fertilizer application.
Atmospheric Environment (2008), doi:10.1016/j.atmosenv.2008.01.042