Estimates of Cl atom concentrations and hydrocarbon kinetic reactivity in surface air at Appledore Island, Maine (USA), during International Consortium for Atmospheric Research on Transport and Transformation/Chemistry of Halogens at the Isles of Shoals

Average hydroxyl radical (OH) to chlorine atom (Cl·) ratios ranging from 45 to 119 were determined from variability‐lifetime relationships for selected nonmethane hydrocarbons (NMHC) in surface air from six different transport sectors arriving at Appledore Island, Maine, during July 2004. Multiplying these ratios by an assumed average OH concentration of 2.5 × 106 cm−3 yielded estimates of Cl· concentrations of 2.2 to 5.6 × 104 cm−3. Summed reaction rates of methane and more than 30 abundant NMHCs with OH and Cl· suggest that Cl· reactions increased the kinetic reactivity of hydrocarbons by 16% to 30% over that due to OH alone in air associated with the various transport sectors. Isoprene and other abundant biogenic alkenes were the most important hydrocarbon contributors after methane to overall kinetic reactivity

Nanoparticle growth following photochemical α‐ and β‐pinene oxidation at Appledore Island during International Consortium for Research on Transport and Transformation/Chemistry of Halogens at the Isles of Shoals 2004

Nanoparticle events were observed 48 times in particle size distributions at Appledore Island during the International Consortium for Atmospheric Research on Transport and Transformation/Chemistry of Halogens on the Isles of Shoals (ICARTT/CHAiOS) field campaign from 2 July to 12 August of 2004. Eighteen of the nanoparticle events showed particle growth and occurred during mornings when peaks in mixing ratios of α‐ and β‐pinene and ozone made production of condensable products from photochemical oxidation probable. Many pollutants and other potential precursors for aerosol formation were also at elevated mixing ratios during these events, including NO, HNO3, NH3, HCl, propane, and several other volatile organic carbon compounds. There were no consistent changes in particle composition, although both submicron and supermicron particles included high maximum concentrations of methane sulfonate, sulfate, iodide, nitrate, and ammonium during these events. Nanoparticle growth continued over several hours with a nearly linear rate of increase of diameter with time. The observed nanoparticle growth rates varied from 3 to 13 nm h−1. Apparent nanoparticle aerosol mass fractions (yields) were estimated to range from less than 0.0005 to almost 1 using α‐ and β‐pinene as the presumed particle source. These apparent high aerosol mass fractions (yields) at low changes in aerosol mass are up to two orders of magnitude greater than predictions from extrapolated laboratory parameterizations and may provide a more accurate assessment of secondary organic aerosol formation for estimating the growth of nanoparticles in global models

Global impact of nitrate photolysis in sea-salt aerosol on NOx, OH, and O3 in the marine boundary layer

Recent field studies have suggested that sea-salt particulate nitrate (NITs) photolysis may act as a significant local source of nitrogen oxides (NOx) over oceans. We present a study of the global impact of this process on oxidant concentrations in the marine boundary layer (MBL) using the GEOS-Chem model, after first updating the model to better simulate observed gas-particle phase partitioning of nitrate in the marine boundary layer. Model comparisons with long-term measurements of NOx from the Cape Verde Atmospheric Observatory (CVAO) in the eastern tropical North Atlantic provide support for an in situ source of NOx from NITs photolysis, with NITs photolysis coefficients about 25-50 times larger than corresponding HNO3 photolysis coefficients. Short-term measurements of nitrous acid (HONO) at this location show a clear daytime peak, with average peak mixing ratios ranging from 3 to 6 pptv. The model reproduces the general shape of the diurnal HONO profile only when NITs photolysis is included, but the magnitude of the daytime peak mixing ratio is under-predicted. This under-prediction is somewhat reduced if HONO yields from NITs photolysis are assumed to be close to unity. The combined NOx and HONO analysis suggests that the upper limit of the ratio of NITs : HNO3 photolysis coefficients is about 100. The largest simulated relative impact of NITs photolysis is in the tropical and subtropical marine boundary layer, with peak local enhancements ranging from factors of 5 to 20 for NOx, 1.2 to 1.6 for OH, and 1.1 to 1.3 for ozone. Since the spatial extent of the sea-salt aerosol (SSA) impact is limited, global impacts on NOx, ozone, and OH mass burdens are small ( ∼ 1-3 %). We also present preliminary analysis showing that particulate nitrate photolysis in accumulation-mode aerosols (predominantly over continental regions) could lead to ppbv-level increases in ozone in the continental boundary layer. Our results highlight the need for more comprehensive long-term measurements of NOx, and related species like HONO and sea-salt particulate nitrate, to better constrain the impact of particulate nitrate photolysis on marine boundary layer oxidant chemistry. Further field and laboratory studies on particulate nitrate photolysis in other aerosol types are also needed to better understand the impact of this process on continental boundary layer oxidant chemistry

The geochemical cycling of reactive chlorine through the marine troposphere

Heterogeneous reactions involving sea‐salt aerosol in the marine troposphere are the major global source for volatile inorganic chlorine. We measured reactant and product species hypothesized to be associated with these chemical transformations as a function of phase, particle size, and altitude over the North Atlantic Ocean during the summer of 1988. Concentrations of HCl were typically less than 1.0 ppbv near the sea surface and decreased with altitude and with distance from the U.S. east coast. Concentrations of Cl volatilized from aerosols were generally equivalent to the corresponding concentrations of HCl and ranged from less than detection limits to 125 nmol m−3 STP. Highest absolute and percentage losses of particulate Cl were typically associated with elevated concentrations of anthropogenic combustion products. Concentrations of product nss SO42− and N03− in coarse aerosol fractions indicate that on average only 38% of measured Cl− deficits could be accounted for by the combined effects of acid‐base desorption and reactions involving nonacidic N gases. We hypothesize a mechanism for the Cl loss initiated by reaction of O3 at sea‐salt aerosol surfaces, generating Cl2 followed by rapid photochemical conversion of Cl2 to HCl via Cl atoms (Cl˙) and eventual recapture of HCl by the aerosol. Simulations with a zero‐dimension (0‐D) photochemical model suggest that oxidation by Cl˙ may be an important tropospheric sink for dimethyl sulfide and hydrocarbons. Under low‐NOx conditions, the rapid cycling of reactive Cl would provide a catalytic loss mechanism for O3, which would possibly explain the low O3 concentrations often observed above the world\u27s oceans

An intercomparison of measurement systems for vapor and particulate phase concentrations of formic and acetic acids

During June 1986, eight systems for measuring vapor phase and four for measuring particulate phase concentrations of formic acid (HCOOH) and acetic acid (CH_3COOH) were intercompared in central Virginia. HCOOH and CH_3COOH vapors were sampled by condensate, mist, Chromosorb 103 GC resin, NaOH-coated annular denuders, NaOH impregnated quartz filters, K_2CO_3 and Na_2CO_3 impregnated cellulose filters, and Nylasorb membranes. Atmospheric aerosol was collected on Teflon and Nuclepore filters using both hi-vol and lo-vol systems to measure particulate phase concentrations. Samples were collected during 31 discrete day and night intervals of 0.5–2 hour duration over a 4-day period. Performance of the mist chamber and K_2CO_3 impregnated filter techniques were also evaluated using zero air and ambient air spiked with HCOOH_g, CH_3COOH_g, and formaldehyde (CH_2O_g) from permeation sources. Results of this intercomparison show significant systematic and episodic artifacts among many currently deployed measurement systems for HCOOH_g and CH_3COOH_g. The spiking experiments revealed no significant interferences for the mist chamber technique and results generated by the mist chamber and denuder techniques were statistically indistinguishable. The condensate technique showed general agreement with the mist chamber and denuder methods, but episodic bias between these systems was inferred from large and significant differences observed during the first day of sampling. Nylasorb membranes are unacceptable for collecting carboxylic acid vapors as they did not retain HCOOH_g and CH_3COOH_g quantitatively. Strong base impregnated filter and GC resin sampling techniques are prone to large positive interferences apparently resulting, in part, from reactions involving CH_2O_g to generate HCOOH and CH_3COOH subsequent to collection. Significant bias presumably associated with differences in postcollection handling was observed for particulate phase measurements by participating groups. Analytical bias did not contribute significantly to differences in vapor and particulate phase measurements

V.: The 1935–2003 Air Temperature Record from the Summit of Mount

ABSTRACT Meteorological observations have been taken continuously at the summit of Mount Washington since 1932. Results of an analysis of the air temperature record over the 1935-2003 period show a statistically significant increase in mean temperature of ϳ0.3°C, while the diurnal temperature range has decreased by ϳ0.15°C. The decadal structure evident in the record reveals that, in contrast to North American trends, the summit experienced relatively cool temperatures in the 1940s. The late 1980s and early 1990s were relatively warm on the summit, in agreement with North American decadal trends. The times of daily maximum and minimum temperatures show that the summit climate is dominantly influenced by boundary layer processes 30% of the time and free air circulation 50% of the time. No evidence of a "weekend effect" was found

Horizontal diffusion and new production in the Sargasso Sea

Estimates of vertical particulate carbon flux and inorganic nitrogen input from rain events were evaluated in relation to horizontal diffusion during a short‐term (4 days) study in the Sargasso Sea. Productivity (∼300 mg C m−2 d−1) and particulate organic C flux (l‐ratio of 0.17) from sediment trap arrays were similar to those recently documented in this region. The drifters traversed the periphery of a small anticyclonic eddy, and an estimate of horizontal diffusivity (∼3 to 10 × 104 cm2 s−1) was derived from relative drifter separation. The corresponding length scale (a few kilometers) and time scale (a day) is related to the effective collection area from which drifting sediment traps can sample the surrounding environment. Measurements of inorganic nitrogen from two rain events were similar to those in a more extensive series of observations from Bermuda. The summer Bermuda data are used to evaluate the inorganic nitrogen input to the oligotrophic surface waters with respect to phytoplankton uptake rates and horizontal diffusion. For small, convective rain events, diffusion may be as important as phyloplankton uptake in reducing nitrogen concentrations to ambient nanomolar levels

Comment on “Aqueous phase chemical processes in deliquescent sea-salt aerosols: A mechanism that couples the atmospheric cycles of S and sea salt” by W. L. Chameides and A. W. Stelson

Engineering and Applied Science

The geochemical cycling of reactive chlorine through the marine troposphere

Heterogeneous reactions involving sea‐salt aerosol in the marine troposphere are the major global source for volatile inorganic chlorine. We measured reactant and product species hypothesized to be associated with these chemical transformations as a function of phase, particle size, and altitude over the North Atlantic Ocean during the summer of 1988. Concentrations of HCl were typically less than 1.0 ppbv near the sea surface and decreased with altitude and with distance from the U.S. east coast. Concentrations of Cl volatilized from aerosols were generally equivalent to the corresponding concentrations of HCl and ranged from less than detection limits to 125 nmol m STP. Highest absolute and percentage losses of particulate Cl were typically associated with elevated concentrations of anthropogenic combustion products. Concentrations of product nss SO and N0 in coarse aerosol fractions indicate that on average only 38% of measured Cl deficits could be accounted for by the combined effects of acid‐base desorption and reactions involving nonacidic N gases. We hypothesize a mechanism for the Cl loss initiated by reaction of O at sea‐salt aerosol surfaces, generating Cl followed by rapid photochemical conversion of Cl to HCl via Cl atoms (Cl˙) and eventual recapture of HCl by the aerosol. Simulations with a zero‐dimension (0‐D) photochemical model suggest that oxidation by Cl˙ may be an important tropospheric sink for dimethyl sulfide and hydrocarbons. Under low‐NO conditions, the rapid cycling of reactive Cl would provide a catalytic loss mechanism for O, which would possibly explain the low O concentrations often observed above the world's oceans.Engineering and Applied Science