Heterogeneous sulfate production in the remote marine environment: Cloud processing and sea‐salt particle contributions

Gurciullo, Christopher S.; Lerner, B. M.; Sievering, H.; Pandis, Spyros N.

doi:10.1029/1999jd900082

Cited by 29 publications

(15 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Though essentially qualitative conclusions may be drawn from this study, the present observations provide an operational basis on which a physicochemical modeling of the air mass ageing processes may be carried out. Recent studies have pointed out the potential importance of in situ sulfate formation in the sea spray [ Gurciullo et al , 1999; Laskin et al , 2003; Sievering et al , 2004; Alexander et al , 2005]. This process has potential climatic implications, as it may mediate the rate of new particle formation in the marine boundary layer.…”

Section: Resultsmentioning

confidence: 99%

Isotopic analysis of aerosol sulfate and nitrate during ITCT‐2k2: Determination of different formation pathways as a function of particle size

Patris¹,

Cliff²,

Quinn³

et al. 2007

J. Geophys. Res.

View full text Add to dashboard Cite

[1] The triple isotopic composition of oxygen in sulfate and nitrate, and the sulfur isotopic composition of the sulfate fine fraction, have been measured on size-segregated aerosol samples collected at Trinidad Head, coastal California, alongside the ITCT-2k2 campaign in April-May 2002. The isotopic anomalyO has been determined in both sulfate and nitrate and was used as a specific tracer of the formation pathways of these species. Coarse mode sulfate in all samples exhibited a small but significant D 17O anomaly indicating either uptake or in situ formation of secondary sulfate on sea spray. Non-sea-salt sulfate D 17O in the coarse fraction is consistent with (1) either primarily coagulation of finer sulfate particles, when D 17O is low in all size fractions, or (2) ozone-driven oxidation of SO 2 within the sea spray, as observed in the relatively higher D 17O in coarse particles compared to fine. It is proposed that tripleisotope measurements of sulfate oxygen can be used to quantify the budget of in situ sea spray nss-SO 4 formation. The D 17O measured in size-resolved nitrate revealed, for the first time, differences in the nitrate formation budget as a function of particle size in a given air mass. The coarse particle nitrate possessed a higher D 17 O, suggesting a relatively larger N 2 O 5 hydrolysis contribution to the nitrate formation budget compared to fine particles where homogeneous formation is more important. We conclude that the complete isotope ratio analysis may provide a basis for future modeling of the formation and transformation processes of the soluble aerosol, based on direct observation of the mechanisms.

show abstract

Section: Resultsmentioning

confidence: 99%

Isotopic analysis of aerosol sulfate and nitrate during ITCT‐2k2: Determination of different formation pathways as a function of particle size

Patris¹,

Cliff²,

Quinn³

et al. 2007

J. Geophys. Res.

View full text Add to dashboard Cite

show abstract

“…However, if the pH ≈ 8 of surface seawater applies to sea‐salt aerosols, then the S(IV) loss rate constant for oxidation by O 3 in these aerosols would be 10 5 times faster than in‐cloud oxidation by H 2 O 2 , more than making up for their lower liquid water content [ Chameides and Stelson , 1992]. Because of the high CO 3 2− /HCO 3 − content of seawater, sea‐salt aerosols have a high acid‐buffering capacity or alkalinity, equal to 0.07 equivalents per kilogram (eq kg −1 ) of dry sea‐salt emitted [ Gurciullo et al , 1999]. The range of global estimates for the sea‐salt flux to the atmosphere, 5000–10,000 Tg yr −1 [ Chin et al , 2002; Gong et al , 2002; Grini et al , 2002], thus implies a source of alkalinity of 0.35–0.7 T eq yr −1 , enabling the fast oxidation of 6.1–12.2 Tg S yr −1 to sulfate under high‐pH conditions.…”

Section: Introductionmentioning

confidence: 99%

Sulfate formation in sea‐salt aerosols: Constraints from oxygen isotopes

Alexander¹

2005

J. Geophys. Res.

367

388

View full text Add to dashboard Cite

[1] We use observations of the mass-independent oxygen isotopic composition (D 17 O) of sulfate in the marine boundary layer (MBL) to quantify the sulfate source from aqueous SO 2 (S(IV)) oxidation by O 3 in alkaline sea-salt aerosols. O values are associated with high concentrations of sea-salt aerosols, providing evidence for the S(IV) + O 3 pathway. We use a global chemical transport model (GEOS-CHEM) to interpret quantitatively the INDOEX observations and to assess the global importance of sulfate production in sea-salt aerosols. The model accounts for titration of sea-salt alkalinity in the MBL by uptake of acid gases (SO 2 , H 2 SO 4 , and HNO 3 ), shutting down the S(IV) + O 3 pathway. We find that this titration occurs rapidly over much of the oceans except at high latitudes (strong sea-salt emission) and is due to both the S(IV) + O 3 reaction and HNO 3 (g) condensation; that is, sulfate formation in sea-salt aerosols is limited by the alkalinity flux from the ocean and by competition for this alkalinity supply from HNO 3 (g). The model is consistent with the D 17O magnitudes and patterns in the INDOEX data. Titration of alkalinity is critical for the success of the model simulation. Regeneration of sea-salt aerosol alkalinity by OH uptake is inconsistent with the D 17O observations in INDOEX. Model results indicate that sulfate production in sea-salt aerosols decreases MBL SO 2 concentrations and gas phase H 2 SO 4 production rates by typically 10-30% (up to >70%) and increases MBL sulfate concentrations by typically >10% (up to 30%). Globally, this mechanism contributes 9% of atmospheric sulfate production and 1% of the sulfate burden. The impact on H 2 SO 4 (g) formation and implications for the potential formation of new particles in the MBL warrants inclusion in models examining the radiative effects of sulfate aerosols.

show abstract

“…Over the oceans, gas‐phase H 2 SO 4 and HNO 3 react with sea salt to form sodium sulfate and sodium nitrate, respectively, affecting the partition of NH 3 and HNO 3 between gas and aerosol phases. Sea salt itself is responsible for a fraction of sulfate formation; SO 2 is oxidized by H 2 O 2 and O 3 in aerosol water associated with sea salt [ Sievering et al , 1991, 1992; Chameides and Stelson , 1993; Erickson et al , 1999; Gurciullo et al , 1999], at a rate that depends on sea salt alkalinity.…”

Section: Introductionmentioning

confidence: 99%

Global radiative forcing of coupled tropospheric ozone and aerosols in a unified general circulation model

et al. 2004

View full text Add to dashboard Cite

[1] Global simulations of sea salt and mineral dust aerosols are integrated into a previously developed unified general circulation model (GCM), the Goddard Institute for Space Studies (GISS) GCM II 0, that simulates coupled tropospheric ozone-NO xhydrocarbon chemistry and sulfate, nitrate, ammonium, black carbon, primary organic carbon, and secondary organic carbon aerosols. The fully coupled gas-aerosol unified GCM allows one to evaluate the extent to which global burdens, radiative forcing, and eventually climate feedbacks of ozone and aerosols are influenced by gas-aerosol chemical interactions. Estimated present-day global burdens of sea salt and mineral dust are 6.93 and 18.1 Tg with lifetimes of 0.4 and 3.9 days, respectively. The GCM is applied to estimate current top of atmosphere (TOA) and surface radiative forcing by tropospheric ozone and all natural and anthropogenic aerosol components. The global annual mean value of the radiative forcing by tropospheric ozone is estimated to be +0.53 W m À2 at TOA and +0.07 W m À2 at the Earth's surface. Global, annual average TOA and surface radiative forcing by all aerosols are estimated as À0.72 and À4.04 W m À2 , respectively. While the predicted highest aerosol cooling and heating at TOA are À10 and +12 W m À2 , respectively, surface forcing can reach values as high as À30 W m À2 , mainly caused by the absorption by black carbon, mineral dust, and OC. We also estimate the effects of chemistry-aerosol coupling on forcing estimates based on currently available understanding of heterogeneous reactions on aerosols. Through altering the burdens of sulfate, nitrate, and ozone, heterogeneous reactions are predicted to change the global mean TOA forcing of aerosols by 17% and influence global mean TOA forcing of tropospheric ozone by 15%.

show abstract

Heterogeneous sulfate production in the remote marine environment: Cloud processing and sea‐salt particle contributions

Cited by 29 publications

References 24 publications

Isotopic analysis of aerosol sulfate and nitrate during ITCT‐2k2: Determination of different formation pathways as a function of particle size

Isotopic analysis of aerosol sulfate and nitrate during ITCT‐2k2: Determination of different formation pathways as a function of particle size

Sulfate formation in sea‐salt aerosols: Constraints from oxygen isotopes

Global radiative forcing of coupled tropospheric ozone and aerosols in a unified general circulation model

Contact Info

Product

Resources

About