Abstract. A database of 15,617 point measurements of dimethylsulfide (DMS) in surface waters along with lesser amounts of data for aqueous and particulate dirhethylsulfoniopropionate concentration, chlorophyll concentration, sea surface salinity and temperature, and wind speed has been assembled. The database was processed to create a series of climatological annual and monthly 1øxl ø latitude-longitude squares of data. The results were compared to published fields of geophysical and biological parameters. No significant correlation was found between DMS and these parameters, and no simple algorithm could be found to create monthly fields of sea surface DMS concentration based on these parameters. Instead, an annual map of sea surface DMS was produced using an algorithm similar to that employed by Conkright et al. [1994]. In this approach, a first-guess field of DMS sea surface concentration measurements is created and then a correction to this field is generated based on actual measurements. Monthly sea surface grids of DMS were obtained using a similar scheme, but the sparsity of DMS measurements made the method difficult to implement. A scheme was used which projected actual data into months of the year where no data were otherwise present.
The most important chemical cleaning agent of the atmosphere is the hydroxyl radical, OH. It determines the oxidizing power of the atmosphere, and thereby controls the removal of nearly all gaseous atmospheric pollutants. The atmospheric supply of OH is limited, however, and could be overcome by consumption due to increasing pollution and climate change, with detrimental feedback effects. To date, the high variability of OH concentrations has prevented the use of local observations to monitor possible trends in the concentration of this species. Here we present and analyse long-term measurements of atmospheric OH concentrations, which were taken between 1999 and 2003 at the Meteorological Observatory Hohenpeissenberg in southern Germany. We find that the concentration of OH can be described by a surprisingly linear dependence on solar ultraviolet radiation throughout the measurement period, despite the fact that OH concentrations are influenced by thousands of reactants. A detailed numerical model of atmospheric reactions and measured trace gas concentrations indicates that the observed correlation results from compensations between individual processes affecting OH, but that a full understanding of these interactions may not be possible on the basis of our current knowledge of atmospheric chemistry. As a consequence of the stable relationship between OH concentrations and ultraviolet radiation that we observe, we infer that there is no long-term trend in the level of OH in the Hohenpeissenberg data set.
During the summer of 1988, measurements of photochemical trace species were made at a coordinated network of seven rural sites in the eastern United States and Canada. At six of these sites concurrent measurements of ozone and the sum of the reactive nitrogen species, NOy, were made, and at four of the sites a measure for the reaction products of the NO x oxidation was obtained. Common to all sites, ozone, in photochemically aged air during the summer, shows an increase with increasing NOy levels, from a background value of 30-40 parts per billion by volume (ppbv)at NOy mixing ratios below 1 ppbv to values between 70 to 100 ppbv at NOy levels of 10 ppbv. Ozone correlates even more closely with the products of the NOx oxidation. The correlations from the different sites agree closely at mixing ratios of the oxidation products below 5 ppbv, but systematic differences appear at higher levels. Variations in the biogenic hydrocarbon emissions may explain these differences. IntroductionElevated and potentially harmful levels of ozone are being found in many rural areas of North America during summer. Daily maximum 03 levels measured in rural areas are often comparable to those found in urban areas and daily average levels can exceed urban levels. There is substantial evidence from field measurements and model calculations that most of this ozone is being produced photochemically from ozone precursors emitted within the region [Research Triangle Institute, 1975; Vukovich et al., 1977Vukovich et al., , 1985Cleveland et al., 1977;Spicer et al., 1979;Wolff and Lioy, 1980;Fehsenfeld et al., 1983;Kelly et al., 1984;Liu et al., 1987]. A similar situation appears to exist for western Europe [Cox et al., 1975;Guicherit and Van Dop, 1977;Hov, 1984]. The photochemical processes responsible for these high levels are thought to be quite similar to the processes that operate in urban photochemical smog but with important differences. In
[1] A High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was evaluated for its ability to quantify submicron sea salt mass concentrations. The evaluation included both laboratory and field studies. Quantification of the sea salt signal in the HR-ToF-AMS was achieved by taking the 23 Na 35 Cl + ion as a surrogate for sea salt and then identifying a calibration scaling factor through a comparison with mono-disperse laboratory generated sea salt aerosol. Ambient sea salt concentrations calculated using this method agreed well with those obtained by ion chromatography of filter samples, following a 1:1 regression slope and a correlation coefficient R = 0.93. A key advantage of this AMS-based method is that it allows for high time resolution measurements of sea salt (5 min) along with the speciation of other chemical compounds, including primary organics contributing to sea spray. The high-time resolution sea salt measurement capability enabled the quantification of sea salt mass in both increasing and decreasing wind speed regimes up to 26 m s À1 . A mass flux source function was also derived and found to have a power law wind speed dependency with an exponent of 3.1 for increasing winds and 2.3 for decreasing winds. Comparison of the mass flux relationship in this study suggests that previous schemes based on the Monahan whitecap-wind speed approach significantly over-estimate the submicron mass flux. Both the whitecap-wind speed component and the differential whitecap-aerosol productivity component of the source flux function contribute toward the over-estimation.
Abstract. Ambient aerosol size distributions (> 3 nm) and OH, H 2 SO 4 , and terpene concentrations were measured from April 1998 to August 2000 at a rural continental site in southern Germany. New particle formation (NPF) events were detected on 18% of all days, typically during midday hours under sunny and dry conditions. The number of newly formed particles correlated significantly with solar irradiance and ambient levels of H 2 SO 4 . A pronounced anticorrelatation of NPF events with the pre-existing particle surface area was identified in the cold season, often associated with the advection of dry and relatively clean air masses from southerly directions (Alps). Estimates of the particle formation rate based on observations were around 1 cm −3 s −1 , being in agreement with the predictions of ternary homogeneous H 2 SO 4 -NH 3 -H 2 O nucleation within a few orders of magnitude. The experimentally determined nucleation mode particle growth rates were on average 2.6 nm h −1 , with a fraction of 0.7 nm h −1 being attributed to the cocondensation of H 2 SO 4 -H 2 O-NH 3 . The magnitude of nucleation mode particle growth was neither significantly correlated to H 2 SO 4 , nor to the observed particle formation rate. Turn-over rate calculations of measured monoterpenes and aromatic hydrocarbons suggest that especially the oxidation products of monoterpenes have the capacity to contribute to the growth of nucleation mode particles. Although a large number of precursor gases, aerosol and meteorological parameters were measured, the ultimate key factors controlling the occurence of NPF events could not be identified.
[1] Nitrous acid and OH were measured concurrently with a number of other atmospheric components and relevant photolysis frequencies during two campaigns at the Meteorological Observatory Hohenpeissenberg (980 m a.s.l.) in summer 2002 and 2004. On most of the 26 measurement days the HNO 2 concentration surprisingly showed a broad maximum around noon (on average 100 pptv) and much lower concentrations during the night ($30 pptv). The results indicate a strong unknown daytime source of HNO 2 with a production rate on the order of 2-4 Â 10 6 cm À3 s À1. The data demonstrate an important contribution of HNO 2 to local HO x levels over the entire day, comparable with the photolysis of O 3 and HCHO. On average during the 2004 campaign, 42% of integrated photolytic HO x formation is attributable to HNO 2 photolysis. Citation: Acker, K.,
[1] High-time resolution measurements of primary marine organic sea-spray physico-chemical properties reveal an apparent dichotomous behavior in terms of water uptake: specifically sea-spray aerosol enriched in organic matter possesses a low hydroscopic Growth Factor (GF∼1.25) while simultaneously having a cloud condensation nucleus/ condensation nuclei (CCN/CN) activation efficiency of between 83% at 0.25% supersaturation and 100% at 0.75%. In contrast, the activation efficiency of particles dominated by non-sea-salt (nss)-sulfate ranged between 48-100% over supersaturation range of 0.25%-1%. Simultaneous retrieval of Cloud Droplet Number Concentration (CDNC) during primary organic aerosol plumes reveals CDNC concentrations of 350 cm −3 for organic mass concentrations 3-4 mg m −3 . It is demonstrated that the retrieved high CDNCs under clean marine conditions can only be explained by organic seaspray and corroborates the high CCN activation efficiency associated with primary organics. It is postulated that marine hydrogels are responsible for this dichotomous behavior.
[1] Atmospheric concentrations of gaseous sulfuric acid (H 2 SO 4 ), methane sulfonic acid (MSA), and hydroxyl radicals (OH) were measured by chemical ionization mass spectrometry (CIMS) during the second New Particle Formation and Fate in the Coastal Environment (PARFORCE) campaign in June 1999 at Mace Head, Ireland. Overall median concentrations in marine background air were 1.5, 1.2, and 0.12 ϫ 10 6 cm Ϫ3 , respectively. H 2 SO 4 was also present at night indicating significant contributions from nonphotochemical sources. A strong correlation was found between daytime OH and H 2 SO 4 levels in clean marine air suggesting a fast local production of H 2 SO 4 from sulfur precursor gases. Steady state balance calculations of ambient H 2 SO 4 levels agreed with measured concentrations if either very low H 2 SO 4 sticking coefficients (0.02-0.03) or sources in addition to the SO 2 ϩ OH reaction were assumed. Overall, variations in ambient H 2 SO 4 levels showed no correlation with either the tidal cycle or ultrafine particle (UFP) concentrations. However, on particular days an anticorrelation between H 2 SO 4 and UFP levels was occasionally observed providing evidence for the contribution of H 2 SO 4 to new particle formation and/or particle growth. Gaseous MSA concentrations were inversely correlated with dew point temperature reflecting a highly sensitive gas-particle partitioning equilibrium of this compound. The present observations seriously question the general use of MSA as a conservative tracer to infer the relative production yield of H 2 SO 4 from dimethylsulfide (DMS) oxidation. MSA/H 2 SO 4 concentration ratios typically ranged between 0.06 and 1.0 in marine air at ground level. Measured diel OH profiles showed a significant deviation from concurrent variations of the ozone photolysis frequency. They also showed up to 1 order of magnitude lower values compared to OH concentrations calculated with a simple photochemical box model. These differences were most pronounced during particle nucleation events occurring on sunny days around noon and at low tide. The present results suggest that both the oxidation capacity and the particle formation potential in the coastal boundary layer were significantly affected by reactions of unknown compounds prevailing in this type of environment.
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