Measurements in marine stratocumulus over the northeast Pacific help scientists unravel the mysteries of this important cloud regime.T he stratocumulus-topped boundary layer (hereafter the STBL), which prevails in the subtropics in regions where the underlying ocean is much colder than the overlying atmosphere, is thought to be an important component of the climate system. Perhaps most striking is its impact on the radiative balance at the top of the atmosphere. The seasonally averaged net cloud radiative forcing from the STBL has been estimated to be as large as 70 W nr 2 (Stephens and Greenwald 1991), more than an order of magnitude larger than the radiative forcing associated with a doubling of atmospheric C0 2 . This means that even rather subtle sensitivities of the STBL to changes in the properties of the atmospheric aero-

Abstract. We present air-sea fluxes of oxygenated volatile organics compounds (OVOCs) quantified by eddy covariance (EC) during the Atlantic Meridional Transect cruise in 2012. Measurements of acetone, acetaldehyde, and methanol in air as well as in water were made in several different oceanic provinces and over a wide range of wind speeds (1-18 m s −1 ). The ocean appears to be a net sink for acetone in the higher latitudes of the North Atlantic but a source in the subtropics. In the South Atlantic, seawater acetone was near saturation relative to the atmosphere, resulting in essentially zero net flux. For acetaldehyde, the two-layer model predicts a small oceanic emission, which was not well resolved by the EC method. Chemical enhancement of air-sea acetaldehyde exchange due to aqueous hydration appears to be minor. The deposition velocity of methanol correlates linearly with the transfer velocity of sensible heat, confirming predominant airside control. We examine the relationships between the OVOC concentrations in air as well as in water, and quantify the gross emission and deposition fluxes of these gases.

Fast measurements of three scalars, ozone, dimethyl sulfide (DMS), and total water, are used to investigate the entrainment process in the stratocumulus-topped boundary layer (STBL) observed over the eastern subtropical Pacific during the second Dynamics and Chemistry of Marine Stratocumulus Experiment (DYCOMS-II). Direct measurement of the flux profiles by eddy covariance is used to estimate the entrainment velocity, the average rate at which the boundary layer grows diabatically via incorporation of overlying free tropospheric air. The entrainment velocities observed over the course of the mission, which took place during July 2001, ranged from 0.12 to 0.72 cm s−1, and appear to outpace the estimated large-scale subsidence as the boundary layer advects over warmer sea surface temperatures. Observed entrainment velocities display only a weak correlation with the buoyancy Richardson number defined at the inversion, which suggests that processes other than inversion strength, such as wind shear, might play a larger role in driving entrainment in the STBL than previously recognized. This study is the first to use DMS as an entrainment tracer because the high-rate mass spectrometric technique has only recently been developed. The biogenic sulfur compound shows great promise for such investigations in marine environments because the free tropospheric concentrations are virtually nonexistent, and it therefore serves as an unambiguous marker of boundary layer air. As such, individual mixing events can be analyzed to determine the mixing fraction of boundary layer and free tropospheric air, and in several such cases buoyancy reversal was observed despite the absence of large-scale dissipation of the cloud field as postulated by cloud-top entrainment instability. Moreover, the redundancy attained in using three separate scalars allows for an investigation of the average height scales above the inversion from where air is blended into the STBL, and this tends to be less than 80 m above the mean inversion height, implying that the entrainment process occurs on very small scales.

[1] During the 2007 UK SOLAS Deep Ocean Gas Exchange Experiment in the northeast Atlantic Ocean, we conducted the first ever study of the effect of a deliberately released surfactant (oleyl alcohol) on gas transfer velocities (k w ) in the open ocean. Exchange rates were estimated with the 3 He/SF 6 dual tracer technique and from measured sea-to-air DMS fluxes and surface water concentrations. A total of seven k w estimates derived from 3 He/SF 6 were made, two of which were deemed to be influenced by the surfactant. These exhibited suppression from ∼5% to 55% at intermediate wind speeds (U 10 ) in the range 7.2-10.7 m s −1 . Similarly, k w determined from DMS data (k DMS ) was also depressed by the surfactant; suppression ranged from ∼39% at 5.0 m s −1 to ∼24% at 10.8 m s −1. Surfactant thus has the potential to measurably suppress gas exchange rates even at moderate to high wind speeds.

SUMMARYThe rst research ight of the second Dynamics and Chemistry of Marine Stratocumulus eld study is analysed. This case attracted our interest because it showed a consistently deepening cloud layer despite macroscopic conditions which previous work has suggested should be an indication of cloud thinning or breakup. Detailed analysis of the ight data shows that despite the cloud-top entrainment instability parameter being well beyond its critical value the cloud did indeed deepen through the night. Our best estimates show little indication of rapid changes in cloud top, while cloud base was found to be lowering at a rate of several metres per hour. This evolution, and independent measurements of trace-gas budgets, imply an entrainment rate of 0 0039 0 001 m s 1 . This is compared to entrainment rates from recently proposed parametrizations (forced by the observed forcing of the cloud layer) which range from 0.002 to 0.008 m s 1 . Two of the parametrizations we test reproduce the observed entrainment rates within their stated uncertainties, although subsequent tests show that one of these rules exhibits sensitivities to changes in the environmental conditions which are dif cult to justify. Large-eddy simulation of the observed case was able to reproduce the macroscopic evolution of the layer, but in doing so had some dif culty in maintaining the observed mixing-line structure at cloud top. A comparison of the observed and simulated turbulent structure show these to be broadly consistent, although there is an indication that the structure of the simulated turbulence differs from the observations near the ow boundaries, particularly at cloud top.

Abstract. Mass spectrometric measurement of DMS by atmospheric pressure ionization with an isotopically labeled standard (APIMS-ILS) is a sensitive method with sufficient bandpass for direct flux measurements by eddy correlation. Use of an isotopically labeled internal standard greatly reduces instrumental drift, improving accuracy and precision. APIMS-ILS has been used in several recent campaigns to study ocean-atmosphere gas transfer and the chemical budget of DMS in the marine boundary layer. This paper provides a comprehensive description of the method and errors associated with DMS flux measurement from ship platforms. The APIMS-ILS instrument used by most groups today has a sensitivity of 100-200 counts s −1 pptv −1 , which is shown to be more than sufficient for flux measurement by eddy covariance. Mass spectral backgrounds (blanks) are determined by stripping DMS from ambient air with gold. The instrument is found to exhibit some high frequency signal loss, with a half-power frequency of ≈1 Hz, but a correction based on an empirically determined instrument response function is presented. Standard micrometeorological assumptions of steady state and horizontal uniformity are found to be appropriate for DMS flux measurement, but rapid changes in mean DMS mixing ratio may serve as a warning that measured flux does not represent the true surface flux. In addition, bias in surface flux estimates arising from the flux divergence is not generally significant in the surface layer, but under conditions of lowered inversion and high flux may become so. The effects of error in motion corrections and of vertical motion within the surface layer concentration gradient are discussed and the estimated maximum error from these effects is ≤18%.

Here we present first eddy covariance (EC) measurements of fluxes of glyoxal, the smallest α-dicarbonyl product of hydrocarbon oxidation, and a precursor for secondary organic aerosol (SOA). The unique physical and chemical properties of glyoxal -i.e., high solubility in water (effective Henry's law constant, K H = 4.2 × 10 5 M atm −1 ) and short atmospheric lifetime (∼ 2 h at solar noon) -make it a unique indicator species for organic carbon oxidation in the marine atmosphere. Previous reports of elevated glyoxal over oceans remain unexplained by atmospheric models. Here we describe a Fast Light-Emitting Diode Cavity-Enhanced Differential Optical Absorption Spectroscopy (Fast LED-CE-DOAS) instrument to measure diurnal variations and EC fluxes of glyoxal and inform about its unknown sources. The fast in situ sensor is described, and first results are presented from a cruise deployment over the eastern tropical Pacific Ocean (20 • N to 10 • S; 133 to 85 • W) as part of the Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOCs (TORERO) field experiment (January to March 2012). The Fast LED-CE-DOAS is a multispectral sensor that selectively and simultaneously measures glyoxal (CHOCHO), nitrogen dioxide (NO 2 ), oxygen dimers (O 4 ), and water vapor (H 2 O) with ∼ 2 Hz time resolution (Nyquist frequency ∼ 1 Hz) and a precision of ∼ 40 pptv Hz −0.5 for glyoxal. The instrument is demonstrated to be a "whitenoise" sensor suitable for EC flux measurements. Fluxes of glyoxal are calculated, along with fluxes of NO 2 , H 2 O, and O 4 , which are used to aid the interpretation of the glyoxal fluxes. Further, highly sensitive and inherently calibrated glyoxal measurements are obtained from temporal averaging of data (e.g., detection limit smaller than 2.5 pptv in an hour). The campaign average mixing ratio in the Southern Hemisphere (SH) is found to be 43 ± 9 pptv glyoxal, which is higher than the Northern Hemisphere (NH) average of 32 ± 6 pptv (error reflects variability over multiple days). The diurnal variation of glyoxal in the marine boundary layer (MBL) is measured for the first time, and mixing ratios vary by ∼ 8 pptv (NH) and ∼ 12 pptv (SH) over the course of 24 h. Consistently, maxima are observed at sunrise (NH: 35 ± 5 pptv; SH: 47 ± 7 pptv), and minima at dusk (NH: 27 ± 5 pptv; SH: 35 ± 8 pptv). In both hemispheres, the daytime flux was directed from the atmosphere into the ocean, indicating that the ocean is a net sink for glyoxal during the day. After sunset the ocean was a source for glyoxal to the atmosphere (positive flux) in the SH; this primary ocean source was operative throughout the night. In the NH, the nighttime flux was positive only shortly after sunset and negative during most of the night. Positive EC fluxes of soluble glyoxal over oceans indicate the presence of an ocean surface organic microlayer (SML) and locate a glyoxal source within the SML. The origin of most atmospheric glyoxal, and possibly other oxygenated hydrocarbons over tropical oceans, remains unexplained and w...

We present here vertical fluxes of oxygenated volatile organic compounds (OVOCs) measured with eddy covariance (EC) during the period of March to July 2012 near the southwest coast of the United Kingdom. The performance of the proton-transfer-reaction mass spectrometer (PTR-MS) for flux measurement is characterized, with additional considerations given to the homogeneity and stationarity assumptions required by EC. Observed mixing ratios and fluxes of OVOCs (specifically methanol, acetaldehyde, and acetone) vary significantly with time of day and wind direction. Higher mixing ratios and fluxes of acetaldehyde and acetone are found in the daytime and from the direction of a forested park, most likely due to light-driven emissions from terrestrial plants. Methanol mixing ratio and flux do not demonstrate consistent diel variability, suggesting sources in addition to plants. We estimate air–sea exchange and photochemical rates of these compounds, which are compared to measured vertical fluxes. For acetaldehyde, the mean (1σ) mixing ratio of 0.13 (0.02) ppb at night may be maintained by oceanic emission, while photochemical destruction outpaces production during the day. Air–sea exchange and photochemistry are probably net sinks of methanol and acetone in this region. Their nighttime mixing ratios of 0.46 (0.20) and 0.39 (0.08) ppb appear to be affected more by terrestrial emissions and long-distance transport, respectively