Can new particle formation occur in the clean marine boundary layer

An analysis of new particle formation probability in the marine boundary layer (MBL) is conducted using a detailed aerosol dynamics and gas-phase chemistry model, thermodynamically correct classical binary (H2O-H2SO4) nucleation theory, and recently developed ternary (H2O-H2SO4-NH3) nucleation theory. Additionally, the effect of boundary-layer meteorology (i.e., adiabatic cooling, small scale fluctuations, and entrainment) in enhancing nucleation is also examined. The results indicate that for typical marine conditions, binary nucleation does not occur for any realistic conditions regardless of adiabatic cooling, turbulent fluctuations, or entrainment. For polar marine conditions, binary nucleation does occur due to lower temperatures, and is enhanced due to turbulent fluctuations. An increase in detectable particle sizes (N3>3 nm), is only seen after multiple boundary layer circulations for conditions of high dimethyl sulphide (DMS) concentrations (400 ppt). Under extreme conditions of entrainment of free-troposphere layers containing very low aerosol condensation sinks and extraordinary high sulphuric acid concentrations (>108 molecules cm−3), increases in detectable particles up to 10,000 cm−3 are predicted only in polar marine air, but are viewed as unlikely to occur in reality. Comparison of model simulations with observed values of DMS and sulphuric acid in polar marine air masses suggest that binary nucleation may lead to an enhancement of ≈ 1000 cm−3 in N3 particle concentration, but not to enhancements of ≈ 10,000 cm−3. Ternary nucleation is predicted to occur under realistic sulphuric acid (1.2×107 molecules cm−3) and ammonia (>5 ppt) concentrations; however, significant growth to detectable sizes (N3) only occurs for DMS concentrations of the order of 400 ppt and very low aerosol condensation sinks, but these conditions are thought to be very infrequent in the MBL and are unlikely to make a significant contribution to the general MBL aerosol concentration. It is plausible that the background MBL aerosol concentration could be maintained by a slow, almost undetectable production rate, and not by noticeable nucleation events where large enhancements in N3 concentrations are observed. The former requires sustained DMS concentrations of the order of 100 ppt which seems unlikely. In summary, the occurrence of new particles in the unperturbed MBL would be difficult to explain by DMS emissions alone. DMS emissions can explain the occurrence of thermodynamically stable sulphate clusters, but under most conditions, to grow these clusters to detectable sizes before they are scavenged by coagulation, an additional condensable species other than DMS-derived sulphuric acid would be required. In the event, however, of significant removal of the preexisting aerosol due to precipitation, the MBL aerosol can be replenished through growth of new particle formed through ternary nucleation under moderately high DMS concentrations.

[1]  Y. Viisanen,et al.  Experiments on gas–liquid nucleation of sulfuric acid and water , 1997 .

[2]  Andrea Saltelli,et al.  Uncertainty and sensitivity analyses of OH-initiated dimethyl sulphide (DMS) oxidation kinetics , 1995 .

[3]  L. Pirjola,et al.  FORMATION OF SULPHURIC ACID AEROSOLS AND CLOUD CONDENSATION NUCLEI: AN EXPRESSION FOR SIGNIFICANT NUCLEATION AND MODEL COMPRARISON , 1999 .

[4]  S. Jennings,et al.  New particle formation: Nucleation rates and spatial scales in the clean marine coastal environment , 1998 .

[5]  H. Reiss,et al.  Hydrates in supersaturated binary sulfuric acid–water vapor: A reexamination , 1987 .

[6]  L. Pirjola,et al.  Parameterizations for sulfuric acid/water nucleation rates , 1998 .

[7]  L. Pirjola,et al.  Modelling the formation of H2SO4–H2O particles in rural, urban and marine conditions , 1998 .

[8]  Comment on ``The relationship between DMS flux and CCN concentration in remote marine regions'' by S. N. Pandis, L. M. Russell, and J. H. Seinfeld , 1995 .

[9]  C. O'Dowd,et al.  On the photochemical production of new particles in the coastal boundary layer , 1999 .

[10]  J. Richter,et al.  The Shape of Internal Waves of Finite Amplitude from High-Resolution Radar Sounding of the Lower Atmosphere , 1970 .

[11]  P. Mcmurry,et al.  New Particle Formation in the Remote Troposphere: A Comparison of Observations at Various Sites , 1999 .

[12]  K. Lehtinen,et al.  Interaction between SO2 and submicron atmospheric particles , 2000 .

[13]  A. Bandy,et al.  Low yields of SO2 from dimethyl sulfide oxidation in the marine boundary layer , 1992 .

[14]  J. Olivero,et al.  H2O in the atmosphere , 1996 .

[15]  C. N. Davies,et al.  The Mechanics of Aerosols , 1964 .

[16]  L. Pirjola,et al.  Stable sulphate clusters as a source of new atmospheric particles , 2000, Nature.

[17]  J. Gras,et al.  On the vapor pressure of sulfuric acid , 1980 .

[18]  T. Bates,et al.  Regional and seasonal variations in the flux of oceanic dimethylsulfide to the atmosphere , 1987 .

[19]  L. Pirjola,et al.  The effect of atmospheric waves on aerosol nucleation and size distribution , 2000 .

[20]  F. Raes.  Entrainment of free tropospheric aerosols as a regulating mechanism for cloud condensation nuclei in the remote marine boundary layer , 1995 .

[21]  Sonia M. Kreidenweis,et al.  A study of new particle formation and growth involving biogenic and trace gas species measured during ACE 1 , 1998 .

[22]  P. Kasibhatla,et al.  Is aerosol production within the remote marine boundary layer sufficient to maintain observed concentrations , 1999 .

[23]  Monte Carlo Algorithms for Solving Boundary Value Problems of the Potential Theory , 1991 .

[24]  S. Pandis,et al.  Removal of sulphur from the marine boundary layer by ozone oxidation in sea-salt aerosols , 1992, Nature.

[25]  L. Radke,et al.  Particle production associated with marine clouds , 1990 .

[26]  R. Reid,et al.  The Properties of Gases and Liquids , 1977 .

[27]  A. Jefferson,et al.  Sources and sinks of H2SO4 in the remote Antarctic marine boundary layer , 1998 .

[28]  M. H. Smith,et al.  Marine aerosol, sea-salt, and the marine sulphur cycle: a short review , 1997 .

[29]  R. P. Thorn,et al.  Measurements of dimethyl sulfide, dimethyl sulfoxide, dimethyl sulfone, and aerosol ions at Palmer Station, Antarctica , 1998 .

[30]  J. Seinfeld,et al.  Photooxidation of dimethyl sulfide and dimethyl disulfide. I: Mechanism development , 1990 .

[31]  A. Jaecker-Voirol,et al.  Heteromolecular nucleation in the sulfuric acid-water system , 1989 .

[32]  A. R. Ravishankara,et al.  Heterogeneous and Multiphase Chemistry in the Troposphere , 1997 .

[33]  C. N. Hewitt,et al.  Dimethyl sulfide, methane sulfonic acid and physicochemical aerosol properties in Atlantic air from the United Kingdom to Halley Bay , 1996 .

[34]  J. W. Fitzgerald,et al.  Aerosol size distributions and optical properties found in the marine boundary layer over the Atlantic Ocean , 1990 .

[35]  C. N. Hewitt,et al.  Biogenic sulphur emissions and inferred non‐sea‐salt‐sulphate cloud condensation nuclei in and around Antarctica , 1997 .

[36]  L. Pirjola.  Effects of the Increased UV Radiation and Biogenic Voc Emissions on Ultrafine Sulphate Aerosol Formation , 1998 .

[37]  J. Gras,et al.  Seasonal relationship between cloud condensation nuclei and aerosol methanesulphonate in marine air , 1991, Nature.

[38]  J. Ponche,et al.  Vapor pressures in the ternary system water‐nitric acid‐sulfuric acid at low temperature: A reexamination , 1996 .

[39]  Otto G. Raabe,et al.  Slip correction measurements of spherical solid aerosol particles in an improved Millikan apparatus , 1985 .

[40]  W. Chameides,et al.  A model study of the formation of cloud condensation nuclei in remote marine areas , 1992 .

[41]  H. B. Howell,et al.  On the Source and Composition of Cloud Nuclei in a Subsident Air Mass over the North Atlantic , 1970 .

[42]  Karl K. Sabelfeld.  Monte Carlo Methods in Boundary Value Problems. , 1991 .

[43]  R. A. Cox,et al.  Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement V , 1996 .

[44]  D. Hegg,et al.  Heterogeneous production of cloud condensation nuclei in the marine atmosphere , 1990 .

[45]  C. O'Dowd,et al.  Coupling sea‐salt and sulphate interactions and its impact on cloud droplet concentration predictions , 1999 .

[46]  Markku Kulmala,et al.  The potential for atmospheric mixing processes to enhance the binary nucleation rate , 1998 .

[47]  Ü. Rannik,et al.  The effect of saturation fluctuations on droplet growth , 1997 .

[48]  R. Dingenen,et al.  Simulations of condensation and cloud condensation nuclei from biogenic SO2 in the remote marine boundary layer , 1992 .

[49]  J. Lowe,et al.  Modeling heterogeneous sulphate production in maritime stratiform clouds , 2000 .

[50]  M. H. Smith,et al.  Submicron particle, radon, and soot carbon characteristics over the northeast Atlantic , 1993 .

[51]  P. Quinn,et al.  New particle formation in the marine boundary layer , 1992 .

[52]  J. Seinfeld,et al.  Ternary nucleation of H2SO4, NH3, and H2O in the atmosphere , 1999 .

[53]  J. Seinfeld,et al.  A study of processes that govern the maintenance of aerosols in the marine boundary layer , 1999 .

[54]  J. Seinfeld,et al.  The relationship between DMS flux and CCN concentration in remote marine regions , 1994 .

[55]  L. Sabinina,et al.  Die Oberflächenspannung des Systems Schwefelsäure—Wasser , 1935 .

[56]  C. O'Dowd,et al.  The relative importance of non‐sea‐salt sulphate and sea‐salt aerosol to the marine cloud condensation nuclei population: An improved multi‐component aerosol‐cloud droplet parametrization , 1999 .

[57]  M. Andreae,et al.  Biogenic sulfur emissions and aerosols over the tropical South Atlantic: 3. Atmospheric dimethylsulfide, aerosols and cloud condensation nuclei , 1995 .

[58]  D. Simpson,et al.  Long-period modelling of photochemical oxidants in Europe. Model calculations for July 1985 , 1992 .

[59]  J. Seinfeld,et al.  Nucleation of sulfuric acid-water and methanesulfonic acid-water solution particles: Implications for the atmospheric chemistry of organosulfur species , 1988 .

[60]  D. Hegg.  Particle production in clouds , 1991 .

[61]  Bandy,et al.  Particle nucleation in the tropical boundary layer and its coupling to marine sulfur sources , 1998, Science.

[62]  Leonard K. Peters,et al.  Binary Homogeneous Nucleation: Temperature and Relative Humidity Fluctuations, Nonlinearity, and Aspects of New Particle Production in the Atmosphere , 1994 .

[63]  R. Charlson,et al.  Bistability of CCN concentrations and thermodynamics in the cloud-topped boundary layer , 1990, Nature.

[64]  H. Sievering,et al.  Ozone oxidation of sulfur in sea‐salt aerosol particles during the Azores Marine Aerosol and Gas Exchange experiment , 1995 .

[65]  J. W. Fitzgerald,et al.  Marine boundary layer measurements of new particle formation and the effects nonprecipitating clouds have on aerosol size distribution , 1994 .

[66]  Jonathan P. Taylor,et al.  The impact of ship-produced aerosols on the microstructure and albedo of warm marine stratocumulus clouds: A test of MAST hypotheses 1i and 1ii , 2000 .

[67]  F. Raes,et al.  Ion-induced aerosol formation in a H2O-H2SO4 system—II. Numerical calculations and conclusions , 1986 .

[68]  L. Radke,et al.  Humidity and Particle Fields Around Some Small Cumulus Clouds. , 1991 .

[69]  W. Chameides,et al.  CCN formation from DMS oxidation without SO2 acting as an intermediate , 1993 .

[70]  J. Seinfeld,et al.  Aerosol production and growth in the marine boundary layer , 1994 .

[71]  Roger Atkinson,et al.  Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III - gas phase reactions of inorganic halogens , 2006 .

[72]  G. Wilemski.  Composition of the critical nucleus in multicomponent vapor nucleation , 1984 .

[73]  S. Friedlander,et al.  A general correlation for deposition of suspended particles from turbulent gases to completely rough surfaces , 1985 .

[74]  N. Fuchs,et al.  HIGH-DISPERSED AEROSOLS , 1971 .

[75]  A. Slingo,et al.  Sensitivity of the Earth's radiation budget to changes in low clouds , 1990, Nature.

[76]  M. H. Smith,et al.  Physicochemical properties of aerosols over the northeast Atlantic: Evidence for wind‐speed‐related submicron sea‐salt aerosol production , 1993 .

[77]  P. Quinn,et al.  Physical properties of marine boundary layer aerosol particles of the mid-Pacific in relation to sources and meteorological transport , 1996 .

[78]  M. Kulmala.  Simulating The Formation of Acid Aerosols , 1990 .

[79]  M. Andreae,et al.  Biogenic sulfur emissions and aerosols over the tropical South , 1994 .

[80]  J. Klett,et al.  Microphysics of Clouds and Precipitation , 1978, Nature.

[81]  Robert Wood,et al.  Evolution of the aerosol, cloud, and boundary layer dynamic and thermodynamic characteristics during the second Lagrangian experiment of ACE-2 , 2000 .

[82]  Roger Atkinson,et al.  Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement IV: IUPAC subcommittee on gas kinetic data evaluation for atmospheric chemistry , 1992 .