Seasonal variation of &lt;sup&gt;15&lt;/sup&gt;N/&lt;sup&gt;14&lt;/sup&gt;N ratios in atmospheric nitrate species

Freyer, H. D.

doi:10.3402/tellusb.v43i1.15244

Cited by 134 publications

(101 citation statements)

References 24 publications

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“…Nitrate in RF had typical δ 15 N values for areas with low N deposition from anthropogenic sources (Heaton 1987;Freyer 1991;Garten Jr. 1992, Fig. 3).…”

Section: Shifts Of δ 15 N Values As Indicator Of N Transformationsmentioning

confidence: 99%

Stable N isotope composition of nitrate reflects N transformations during the passage of water through a montane rain forest in Ecuador

2010

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“…Nitrate in RF had typical δ 15 N values for areas with low N deposition from anthropogenic sources (Heaton 1987;Freyer 1991;Garten Jr. 1992, Fig. 3).…”

Section: Shifts Of δ 15 N Values As Indicator Of N Transformationsmentioning

confidence: 99%

Stable N isotope composition of nitrate reflects N transformations during the passage of water through a montane rain forest in Ecuador

2010

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“…Variations in O 3 concentration have also been suggested to impact δ 15 N by altering the ratio of atmospheric NO and NO 2 (10,11). Using a box model (10), we estimate that the ∼40% increase in tropospheric O 3 concentration from the preindustrial period to the (Table S1), is likely the result of postdepositional processing.…”

mentioning

confidence: 99%

“…We hypothesize that the link between δ 15 N and H + is the effect of acidity on the thermodynamic equilibrium partitioning of atmospheric nitrate between HNO 3(g) and p-NO − 3 . In the atmosphere, the equilibrium partitioning of nitrate is achieved quickly (minutes to several hours) between the gas phase and the fine-mode aerosol phase (< 1 μm) (23 (11,12). Eq.…”

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confidence: 99%

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Nitrogen isotopes in ice core nitrate linked to anthropogenic atmospheric acidity change

Geng

Alexander²,

Cole‐Dai

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

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Nitrogen stable isotope ratio (δ 15 N) in Greenland snow nitrate and in North American remote lake sediments has decreased gradually beginning as early as ∼1850 Christian Era. This decrease was attributed to increasing atmospheric deposition of anthropogenic nitrate, reflecting an anthropogenic impact on the global nitrogen cycle, and the impact was thought to be amplified ∼1970. However, our subannually resolved ice core records of δ 15 N and major ions (e.g., NO − 3 , SO 2− 4 ) over the last ∼200 y show that the decrease in δ 15 N is not always associated with increasing NO − 3 concentrations, and the decreasing trend actually leveled off ∼1970. Correlation of δ 15 N with H + , NO − 3 , and HNO 3 concentrations, combined with nitrogen isotope fractionation models, suggests that the δ 15 N decrease from ∼1850-1970 was mainly caused by an anthropogenic-driven increase in atmospheric acidity through alteration of the gas−particle partitioning of atmospheric nitrate. The concentrations of NO − 3 and SO 2− 4 also leveled off ∼1970, reflecting the effect of air pollution mitigation strategies in North America on anthropogenic NO x and SO 2 emissions. The consequent atmospheric acidity change, as reflected in the ice core record of H + concentrations, is likely responsible for the leveling off of δ 15 N ∼1970, which, together with the leveling off of NO − 3 concentrations, suggests a regional mitigation of anthropogenic impact on the nitrogen cycle. Our results highlight the importance of atmospheric processes in controlling δ 15 N of nitrate and should be considered when using δ 15 N as a source indicator to study atmospheric flux of nitrate to land surface/ecosystems.fossil fuel emissions | proxy | industrial | acid deposition | clean air act

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“…Indeed, isotopic measurements have proven to be instrumental in identifying and quantifying sources, processes affecting the formation of atmospheric nitrate [particulate NO 3 − plus gas-phase nitric acid (HNO 3 ); hereafter defined as NO 3 − ], and the role of its precursors (i.e., the complex chemical interactions between NO x , halogens, and ozone) (8)(9)(10) (21), with interpretation depending on regional atmospheric contexts.…”

mentioning

confidence: 99%

Isotopic composition of atmospheric nitrate in a tropical marine boundary layer

Savarino

Morin

Erbland

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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Long-term observations of the reactive chemical composition of the tropical marine boundary layer (MBL) are rare, despite its crucial role for the chemical stability of the atmosphere. Recent observations of reactive bromine species in the tropical MBL showed unexpectedly high levels that could potentially have an impact on the ozone budget. Uncertainties in the ozone budget are amplified by our poor understanding of the fate of NO x (= NO + NO 2 ), particularly the importance of nighttime chemical NO x sinks. Here, we present year-round observations of the multiisotopic composition of atmospheric nitrate in the tropical MBL at the Cape Verde Atmospheric Observatory. We show that the observed oxygen isotope ratios of nitrate are compatible with nitrate formation chemistry, which includes the BrNO 3 sink at a level of ca. 20 ± 10% of nitrate formation pathways. The results also suggest that the N 2 O 5 pathway is a negligible NO x sink in this environment. Observations further indicate a possible link between the NO 2 /NO x ratio and the nitrogen isotopic content of nitrate in this low NO x environment, possibly reflecting the seasonal change in the photochemical equilibrium among NO x species. This study demonstrates the relevance of using the stable isotopes of oxygen and nitrogen of atmospheric nitrate in association with concentration measurements to identify and constrain chemical processes occurring in the MBL.monitoring | oxidation | tropic | bromine chemistry | aerosols T he tropical marine lower troposphere is one of the most photochemically active compartments of the global atmosphere. The year-round high solar radiation, temperature, and humidity render this region the second largest contributor to methane removal via the OH sink (1). A large proportion of tropospheric ozone loss also occurs in the tropical marine boundary layer (MBL), where the concentrations of precursors, such as NO x (= NO + NO 2 ) and volatile organic carbons (VOCs) (2), are generally too low to keep the ozone production rate above its destruction rate. The destruction of ozone is further highlighted by the recently discovered role of halogen chemistry at low latitudes (3), which is known to destroy ozone catalytically (4). The subtle oxidation chemistry coupling NO x , halogens, and VOCs with ozone production and destruction in the MBL is still not fully understood, as demonstrated by the historically overlooked bromine chemistry (3) or the role of heterogeneous N 2 O 5 hydrolysis as a NO x sink (5, 6).Being the end product of the NO x /O 3 /VOC interaction, atmospheric nitrate is particularly well suited to probe such chemistry, especially through its stable isotope composition (7). Indeed, isotopic measurements have proven to be instrumental in identifying and quantifying sources, processes affecting the formation of atmospheric nitrate [particulate NO 3 − plus gas-phase nitric acid (HNO 3 ); hereafter defined as NO 3 − ], and the role of its precursors (i.e., the complex chemical interactions between NO x , halogens, and ozone...

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Seasonal variation of <sup>15</sup>N/<sup>14</sup>N ratios in atmospheric nitrate species

Cited by 134 publications

References 24 publications

Stable N isotope composition of nitrate reflects N transformations during the passage of water through a montane rain forest in Ecuador

Stable N isotope composition of nitrate reflects N transformations during the passage of water through a montane rain forest in Ecuador

Nitrogen isotopes in ice core nitrate linked to anthropogenic atmospheric acidity change

Isotopic composition of atmospheric nitrate in a tropical marine boundary layer

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