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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
+
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 in the suburban of Guangzhou. The soil type is
apportioning of aerosol SO2 4 (McArdle et al., 1998), lateritic red earth, which is typical in subtropical
N isotopic compositions can provide important China. Some soil properties were analyzed after the
information regarding the sources and processing soil was mixed well (National Standard Bureau
of aerosol ammonium and nitrate (Yeatman et al., of China, 1987). Soil pH averaged 6.9970.02
2001; Gao, 2002; Widory, 2007). N isotopic signature (extracted with KCl solution), with an initial total
was also used to identify the main sources of C content of 1.6970.07% and a total N content of
ammonium and nitrate in rain waters (Russell et 0.1470.01%. Soil texture was sandy clay loam with
al., 1998; Gao, 2002; Xiao and Liu, 2002). a bulk density of 1.1870.18 g cm3.
A powerful tool as it is, N isotopic signature can The well-mixed soil was put into six stainless-steel
only be successfully applied with accumulating data frames (30 cm 30 cm 10 cm) with water-filled
of N isotopic fingerprints of emission sources and channel on the top. The experiment was conducted
major environmental processes. However, to date N under laboratory conditions (2572 1C). Before the
isotopic signatures of NOx from some major experiment, the six frames with soils were left for a
sources, like soil release, has not been directly week except that deionized water was sprayed to the
measured and well characterized, although soils are soil to maintain the gravimetric soil moisture within
regarded as one of the most important contributors a range (16–24%) similar to that of the vegetable
to the atmospheric NOx, probably only next to field in this region (Li and Wang, 2007).
fossil fuel combustion in magnitude (Davidson and Two types of N fertilizer, urea and ABC, were
Kingerlee, 1997). According to the global soil NO dissolved in 100 ml water and applied to the soil
emission estimates, the fertilized cropland soil was surface with a hand-held sprayer at a rate of
responsible for 26–41% of the global total soil NO 20 g N m2. Each N fertilizer treatment had three
emission, and most of the NO emission from replicates.
cropland soil was induced by N fertilizer application
(Yienger and Levy, 1995; Davidson and Kingerlee,
1997; Bouwman et al., 2002; Yan et al., 2005). 2.3. Flux measurement
Although not directly measured, N isotope of
soil-derived NO was proposed to be more depleted NO fluxes were measured by a dynamic flow-
in the heavier N isotope with a d15N value up to through chamber technique, which was similar to
about 20%, and differed from the anthropogeni- that used by Pilegaard et al. (1999). The chambers
cally derived ones (Freyer, 1978; Freyer et al., 1993). were made of stainless steel with inner walls covered
But the proof must await actual isotopic measure- by Teflon films. Each chamber had an area of
ments (Heaton, 1987; Freyer et al., 1993). In this 30 cm 30 cm with a total volume of 9 l. It has one
study, we measured N isotopic composition of NO inlet port, one exhaust port and one outlet port for
emitted from cropland soil following application of sampling. Inside each chamber, a thermo-sensor
urea (NH4HCO3) and ammonium bicarbonate was fixed to measure air temperature, and a fan
(ABC) with the aim to get the N isotopic informa- attached to ensure sufficient mixing of air within the
tion for soil-derived NO. chamber. Upon measurement, the sampling cham-
bers were put onto the frames. An additional
2. Materials and methods reference chamber, closed at the bottom with Teflon
sheet, was adopted for in situ quantification of
2.1. Chemicals chemical reactions and chamber wall deposition
effects (Kirkman et al., 2002). Ambient air was
Methanol was of HPLC grade and water was pumped into the chambers at a rate of 4 l min1
double-distilled. Both NO standard gas and N2 had through Teflon tubes. The residence time of air
a purity of 99.999%. All other chemicals were of in the chambers was about 2.25 min. After approx-
AR grade. imate 15 min (over five cycles of residence time),
when a steady state was reached inside the
2.2. Experimental design chambers, NO were analyzed by a model 42C
chemiluminescence NO–NO2–NOx analyzer
The soil used in this experiment was collected (Thermo Environmental Instruments Inc., USA).
directly from a vegetable field (top layer of 0–20 cm) By the contrast of sampling chambers and the
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 ] (]]]]) ]]]–]]] 3
reference chamber, net fluxes from the soils could be 2.5. Measurements of inorganic N concentrations
obtained (Pilegaard et al., 1999).
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
2.4. Trapping of NO for N isotopic analysis same treatment were thoroughly mixed, and the
coarse stones and roots were removed by hand.
The principle of selectively trapping atmospheric About 10 g fresh sample (50 g for soil sample before
NO for N isotope analysis was similar to that used fertilization) was extracted with 100 ml 2 M KCl
by Ammann et al. (1999). A solid oxidizer (CrO3/ solution and filtered through 0.45 mm membrane
H3PO4) was used to convert NO into NO2 (Levaggi filter after shaking 1 h on an orbital shaker. The
et al., 1972). The tubular deluder was a sand-blasted extracts were stored in the refrigerator at 18 1C for
Pyrex tube (3 mm 5 mm 75 mm) with N-free later analysis. NH+4 was determined by indophenol
coating of KOH/guaiacol (Williams and Grosjean, blue method, and NO
3 (plus NO2 ) was analyzed by
1990). The coating was prepared by wetting the tube copper–cadmium reduction method (National Stan-
with a methanol (HPLC grade) solution of KOH/ dard Bureau of China, 1987). Final values of N
guaiacol and drying in pure N2 gas (99.999%). pools were reported as mg N g1 dry soil, where dry
The NO trapping system was shown in Fig. 1. soils referred to constant weight after drying at
The chambers were the same as those for flux 105 1C.
measurement. After the chamber was put onto the
frame, using a portable pump air was circulated 2.6. Isolating soil NH+4 and NO3 by ammonia
within a loop consisting of the chamber and the diffusion method for N isotopic analysis
trapping system. The flow rate was controlled to be
1.0 l min1 by a mass flow controller. Under the Based on the procedure of Downs et al. (1999),
same conditions, a breakthrough test with two sequential diffusion method was used for isolating
trapping tubes connected in series indicated that the soil NH+
4 and NO3 fractions. Aliquot of soil
nitrite (the preferential product of NO2 and extract containing 60–150 mg N of each sample was
guaiacol) in the second denuder was undetectable transferred to 100 ml wide-mouth polyethylene
with an Ion Chromatography (761 compact IC, bottle, followed by adding 0.2 g magnesium oxide
Metrohm, Switzerland). (MgO) powder to increase the solution pH.
After sampling, the tubes were eluted with 0.5 ml Ammonia diffusing out of solution was captured
methanol and 0.5 ml water. The elute was collected on PTFE band enclosed, acid-soaked glass-fibre
in a 1 ml vial and dried in a vacuum desiccator. filter (GF/F; Whatman, Maidstone, UK). The NH+ 4
After drying, the residual was carefully collected in fraction was left to diffuse from the sample for 7
tin (Sn) boats and stored air-tightly until isotope days, whereupon the filter trap was removed and a
analysis. 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
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
4 D. Li, X. Wang / Atmospheric Environment ] (]]]]) ]]]–]]]
of ThermoQuest Deltaplus XL isotope ratio mass fertilized sites range from 1.19 to 44 ng N m2 s1
spectrometer coupled to an EA 1112 automatic and are generally larger than those from corre-
elemental analyzer through a ConFlo II continuous sponding sites that were not recently fertilized
flow interface (EA-IRMS, Thermo Finnigan MAT, (0.01–3.5 ng N m2 s1) (McKenney and Drury,
Bremen, Germany). N isotopic data are reported as 1997, and references therein). So majority of NO
d15N value following Mariotti (1983): released was reasonably fertilizer-induced in the
present study. N isotopic composition for NO was
d15 N ¼ ½ðRsample =Rstandard Þ 1 1000, (1)
only measured from day 2 to day 13 after
15 14
where R is the ratio of N/ N, and the standard is fertilization, during which NO fluxes were also
the atmospheric N2. measured (Fig. 2a). Urea and ABC fertilizers used
in the present study had d15N values of 1.3% and
2.8. QC/QA 7.2%, respectively. As indicated in Fig. 2b, soil-
released NO from both urea- and ABC-treated plots
During the analysis of each batch of samples, was significantly depleted in 15N compared to the
reagent blank and standard reagent of known d15N d15N values of the fertilizers. NO released from both
value (0.4%) were also analyzed. Low background, urea- and ABC-fertilized plots had initial d15N
excellent reproducibility (70.2%) and accuracy values of nearly 50%, but from day 2 to day 6 the
(70.2%) were achieved. d15N values increased sharply to 430%, and
To evaluate whether isotopic fractionation oc- tended to level off from day 6 to day 13.
curred during NO trapping and the following NO is produced as an intermediate during
processes, 5 ppmv NO gas (499.999% NO diluted nitrification from NH+
4 to NO3 and denitrification
in 499.999% N2) was trapped and got isotopic from NO3 to N2 (Ludwig et al., 2001). Both
composition determined the same way as soil-
released NO.
N isotopic composition of pure NO gas was 500
analyzed using a HP 6890 gas chromatography Urea
ABC
(GC) coupled with the DELTA plus XL isotope ratio 400
NO fluxes (ng N m-2 s-1)
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
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D. Li, X. Wang / Atmospheric Environment ] (]]]]) ]]]–]]] 5
processes kinetically favor utilizing the lighter N the urea and ABC-treated plots, respectively, and
isotope (14N), which leads to more depleted d15N during the experiment period d15N values for
values in the products than in the reactants emitted NO averaged approximately 35.5% and
(Högberg, 1997). Although no measurements have 29.1% for the urea and ABC-treated plots,
been reported about N isotopic composition of soil- respectively. These results well-confirmed previous
derived NO, other gaseous N (N2 and N2O) projections of the much depleted 15N for soil-
produced by nitrification and denitrification were released NO.
found to be highly depleted in 15N (e.g., Högberg, Urea and ABC application would also induce
1997; Pérez et al., 2001). In a study by Pérez et al. large amount of NH3 volatilization (Xing and Zhu,
(2001), N2O emitted from an agricultural field 2000). Since significant isotopic fractionation usual-
fertilized with urea had highly depleted d15N values ly occur during NH3 volatilization, the volatilized
(46%) during the first week when N2O emissions NH3 can be 15N depleted to a d15N value of about
were the highest, just as soil-released NO after 40% relative to the substrate, and leave the
fertilization in the present study. They also observed remaining N enriched in 15N when the substrate
enriched d15N values (+5%) at the end of the supply is limited (Högberg, 1997). Additionally, as
second week when emissions were low. Based on shown in Fig. 2b and Fig. 3c and d, products of
15
calculated equilibrium N isotope effects for bacter- nitrification like NO and NO 3 were also N
+
ial denitrification from nitrite to NO, and measured depleted. Therefore the remaining NH4 would
kinetic fractionation effects for denitrification reac- become heavier and relatively enriched in 15N
tion, Freyer et al. (1993) estimated that natural NO (Fig. 3), which in turn caused increasing d15N
emissions would be 15N depleted with d15N value up values for nitrification products (like NO and NO 3)
to about 20%. The relatively depleted d15N value and volatilized NH3 (Högberg, 1997).
in soil-derived NO was also indirectly supported by
the few existing field measurements, for example, 3.3. d15N of soil-released NO in comparison with
Moore (1977) reported that d15N was 9.373.5% those of substrate NH+4 and NO 3
for NO2 in clean air, where a larger portion of NO2
was converted from NO from natural soil emission. In this study, as indicated by the changes of
From our study, after about 2 weeks of fertilization, soil NH+4 and NO 3 (Fig. 3), nitrification was
NO had d15N values of 28.0% and 19.8% for the process controlling NO production. Over the
350 300
300 250
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)
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
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
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 ] (]]]]) ]]]–]]] 7
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
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8 D. Li, X. Wang / Atmospheric Environment ] (]]]]) ]]]–]]]
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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