Seasonal variations of triple oxygen isotopic compositions of atmospheric sulfate, nitrate, and ozone at Dumont d'Urville,  coastal Antarctica

Ishino, Sakiko; Hattori, Shohei; Savarino, Joël; Jourdain, Bruno; Preunkert, Susanne; Legrand, Michel; Caillon, Nicolas; Barbero, Albane; Kuribayashi, Kiyoshi; Yoshida, Naohiro

doi:10.5194/acp-17-3713-2017

Cited by 51 publications

(99 citation statements)

References 67 publications

(129 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Previous isotopic studies have reported the Δ 17 O(NO 3 − ) at the coast of Antarctica (Ishino et al, ; Savarino et al, ) and in the interior of Antarctica (Erbland et al, ; Frey et al, ; McCabe et al, ; Savarino et al, ), generally finding a distinctive Δ 17 O seasonal cycle that reflects the higher relative contribution of O 3 oxidation and/or stratospheric input during the austral winter and increased HO x + RO x oxidation during the austral summer. Previous Antarctica δ 15 N(NO 3 − ) measurements indicate a distinctive seasonal cycle driven by localized snowpack emissions during periods of sunlight (Erbland et al, ; Frey et al, ; Savarino et al, ).…”

Section: Introductionmentioning

confidence: 96%

“…In contrast, the oxygen (O) isotopic composition (δ 18 O & Δ 17 O) is associated with the incorporation of oxygen atoms from various atmospheric oxidants, as gaseous precursors (i.e., NO x and SO 2 ) are oxidized to NO 3 − or SO 4 2− (Alexander et al, ; Michalski et al, ). The number of isotopic studies of NO 3 − or SO 4 2− in polar regions are relatively meager but have received increased attention in recent years, and interpretations of the isotopic signals continue to evolve (Erbland et al, ; Frey et al, ; Hill‐Falkenthal et al, ; Ishino et al, ; McCabe et al, ; Savarino et al, , ). However, to utilize stable isotopes in NO 3 − and SO 4 2− in a paleoclimate context (i.e., ice core studies) in the interior of Antarctica, we must have a better understanding of the isotopic signatures of these molecules in the polar atmosphere.…”

Section: Introductionmentioning

confidence: 99%

“…The Δ 17 O of NO 2 should reflect NO x photochemical cycling between NO‐O 3 ‐RO 2 (or HO 2 ), resulting in expected values near 28‰ to 39‰ (Morin et al, ), representing a NO + O 3 branching ratio of 0.72 to 1.0. Post‐NO 2 reaction pathways have been assumed to reflect O isotopic mass balance with the associated oxidants, which has been derived in previous works (Alexander et al, ; Ishino et al, ; Michalski et al, ; Morin et al, ). Based on this framework, the NO 2 + OH pathway is expected to produce the lowest Δ 17 O(NO 3 − ) values (17.3‰ to 25.1‰), while volatile organic compound (VOC) hydrogen abstraction by the nitrate radical (NO 3 + VOC) and XONO 2 hydrolysis are expected to produce the highest Δ 17 O(NO 3 − ) values (38.0‰ to 42.3‰) (Table ; Morin et al, ).…”

Section: Introductionmentioning

confidence: 99%

“…Previous Antarctica δ 15 N(NO 3 − ) measurements indicate a distinctive seasonal cycle driven by localized snowpack emissions during periods of sunlight (Erbland et al, ; Frey et al, ; Savarino et al, ). Studies of Δ 17 O(SO 4 2− ) at Dumont d'Urville (DDU; Ishino et al, ) and Dome C (Hill‐Falkenthal et al, ) also indicate seasonal cycles reflecting shifts in gas‐phase to aqueous‐phase oxidation (Hill‐Falkenthal et al, ). However, the oxidation dynamics involving NO 3 − and SO 4 2− over Antarctica, particularly in the interior, are far from solved (Hill‐Falkenthal et al, ; Savarino et al, ).…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Assessing the Seasonal Dynamics of Nitrate and Sulfate Aerosols at the South Pole Utilizing Stable Isotopes

et al. 2019

Self Cite

View full text Add to dashboard Cite

Atmospheric nitrate (NO3− = particulate NO3− + gas‐phase nitric acid [HNO3]) and sulfate (SO42−) are key molecules that play important roles in numerous atmospheric processes. Here, the seasonal cycles of NO3− and total suspended particulate sulfate (SO42−(TSP)) were evaluated at the South Pole from aerosol samples collected weekly for approximately 10 months (26 January to 25 October) in 2002 and analyzed for their concentration and isotopic compositions. Aerosol NO3− was largely affected by snowpack emissions in which [NO3−] and δ15N(NO3−) were highest (49.3 ± 21.4 ng/m3, n = 8) and lowest (−47.0 ± 11.7‰, n = 5), respectively, during periods of sunlight in the interior of Antarctica. The seasonal cycle of Δ17O(NO3−) reflected tropospheric chemistry year‐round with lower values observed during sunlight periods and higher values observed during dark periods, reflecting shifts from HOx‐ to O3‐dominated oxidation chemistry. SO42−(TSP) concentrations were highest during austral summer and fall (86.7 ± 73.7 ng/m3, n = 18) and are indicated to be derived from dimethyl sulfide (DMS) emissions, as δ34S(SO42−)(TSP) values (18.5 ± 1.0‰, n = 10) were similar to literature δ34S(DMS) values. The seasonal cycle of Δ17O(SO42−)(TSP) exhibited minima during austral summer (0.9 ± 0.1‰, n = 5) and maxima during austral fall (1.3 ± 0.3‰, n = 6) and austral spring (1.6 ± 0.1‰, n = 5), indicating a shift from HOx‐ to O3‐dominated chemistry in the atmospheric derived SO42− component. Overall, the budgets of NO3− and SO42−(TSP) at the South Pole were complex functions of transport, localized chemistry, biological activity, and meteorological conditions, and these results will be important for interpretations of oxyanions in ice core records in the interior of Antarctica.

show abstract

Section: Introductionmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Assessing the Seasonal Dynamics of Nitrate and Sulfate Aerosols at the South Pole Utilizing Stable Isotopes

et al. 2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…SO 2 has 17 O = 0 ‰ due to the rapid isotopic exchange with abundant vapor water whose 17 O is near 0 ‰ (Holt et al, 1981). S(IV) oxidation by H 2 O 2 and O 3 leads to 17 O(SO 2− 4 ) = 0.7 and 6.5 ‰, respectively, on the basis of 17 O(H 2 O 2 ) = 1.4 ‰ (Savarino and Thiemens, 1999) and assuming 17 O(O 3 ) = 26 ‰ (Vicars and Savarino, 2014;Ishino et al, 2017 (Dubey et al, 1997;Luz and Barkan, 2005;Lee et al, 2002;Bao et al, 2000). Sulfate produced by NO 2 oxidation is suggested to occur either via a radical chain mechanism (Shen and Rochelle, 1998), via oxygen-atom transfer from OH − (Clifton et al, 1988), or from O 2 based on experimental results of He et al (2014) (Fu, 2014).…”

Section: Introductionmentioning

confidence: 99%

Isotopic constraints on heterogeneous sulfate production in Beijing haze

et al. 2018

View full text Add to dashboard Cite

Abstract. Discerning mechanisms of sulfate formation during fine-particle pollution (referred to as haze hereafter) in Beijing is important for understanding the rapid evolution of haze and for developing cost-effective air pollution mitigation strategies. Here we present observations of the oxygen-17 excess of PM 2.5 sulfate ( 17 O(SO 2− 4 )) collected in Beijing haze from October 2014 to January 2015 to constrain possible sulfate formation pathways. Throughout the sampling campaign, the 12-hourly averaged PM 2.5 concentrations ranged from 16 to 323 µg m −3 with a mean of (141 ± 88 (1σ )) µg m −3 , with SO Our estimate suggested that in-cloud reactions dominated sulfate production on polluted days (PDs, PM 2.5 ≥ 75 µg m −3 ) of Case II in October 2014 due to the relatively high cloud liquid water content, with a fractional contribution of up to 68 %. During PDs of Cases I and III-V, heterogeneous sulfate production (P het ) was estimated to contribute 41-54 % to total sulfate formation with a mean of (48 ± 5) %. For the specific mechanisms of heterogeneous oxidation of SO 2 , chemical reaction kinetics calculations suggested S(IV) (= SO 2 q H 2 O + HSO − 3 + SO 2− 3 ) oxidation by H 2 O 2 in aerosol water accounted for 5-13 % of P het . The relative importance of heterogeneous sulfate production by other mechanisms was constrained by our observed 17 O(SO 2− 4 ). Heterogeneous sulfate production via S(IV) oxidation by O 3 was estimated to contribute 21-22 % of P het on average. Heterogeneous sulfate production pathways that result in zero-17 O(SO 2− 4 ), such as S(IV) oxidation by NO 2 in aerosol water and/or by O 2 via a radical chain mechanism, contributed the remaining 66-73 % of P het . The assumption about the thermodynamic state of aerosols (stable or metastable) was found to significantly influence the calculated aerosol pH (7.6 ± 0.1 or 4.7 ± 1.1, respectively), and thus influence the relative importance of heterogeneous sulfate production via S(IV) oxidation by NO 2 and by O 2 . Our local atmospheric conditions-based calculations suggest sulfate formation via NO 2 oxidation can be the dominant pathway in aerosols at high-pH conditions calculated assuming stable state while S(IV) oxidation by O 2 can be the dominant pathway providing that highly acidic aerosols (pH ≤ 3) exist. Our local atmospheric-conditions-based calculations illustrate the utility of 17 O(SO 2− 4 ) for quantifying sulfate forPublished by Copernicus Publications on behalf of the European Geosciences Union. 5516 P. He et al.: Isotopic constraints on heterogeneous sulfate production in Beijing haze mation pathways, but this estimate may be further improved with future regional modeling work.

show abstract

Vertically uniform formation pathways of tropospheric sulfate aerosols in East China detected from triple stable oxygen and radiogenic sulfur isotopes

Lin

Biglari

Zhang

et al. 2017

Geophysical Research Letters

View full text Add to dashboard Cite

Sulfate aerosols (SO42−) in the continental outflow from East China significantly alter the atmospheric sulfur budget across the Pacific Rim, but its formation pathways, especially in the free troposphere (FT), remain poorly understood. Here we analyze stable oxygen (δ17O and δ18O) and radiogenic sulfur (35S) isotopes in SO42− collected at a mountain site in East China to investigate SO42− formation pathways at varying altitudes. We find that Δ17O (=δ17O‐0.52 × δ18O) in SO42− is not correlated with 35S (a direct measure of high‐altitude air masses). This pattern notably differs from the currently known 35S‐Δ17O relation. The result implies that the formation pathway of tropospheric SO42− in East China is vertically uniform, likely due to large emissions and active convection in this region. Our measurements provide unambiguous isotopic constraints for reducing uncertainties in modeling SO42− in the FT over East China, which greatly affects regional climate but current models fail to accurately estimate.

show abstract

Seasonal variations of triple oxygen isotopic compositions of atmospheric sulfate, nitrate, and ozone at Dumont d'Urville, coastal Antarctica

Cited by 51 publications

References 67 publications

Assessing the Seasonal Dynamics of Nitrate and Sulfate Aerosols at the South Pole Utilizing Stable Isotopes

Assessing the Seasonal Dynamics of Nitrate and Sulfate Aerosols at the South Pole Utilizing Stable Isotopes

Isotopic constraints on heterogeneous sulfate production in Beijing haze

Vertically uniform formation pathways of tropospheric sulfate aerosols in East China detected from triple stable oxygen and radiogenic sulfur isotopes

Contact Info

Product

Resources

About