Measurements of OVOC fluxes by eddy covariance using a proton-transfer-reaction mass spectrometer – method development at a coastal site

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 (1 sigma) mixing ratio of 0.13 (0.02) ppb at night may be maintained by oceanic emission, while photochemical destruction out-paces 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.

Quantification of oxygenated volatile organic compounds in seawater by membrane inlet-proton transfer reaction/mass spectrometry

The role of the ocean in the cycling of oxygenated volatile organic compounds (OVOCs) remains largely unanswered due to a paucity of datasets. We describe the method development of a membrane inlet-proton transfer reaction/mass spectrometer (MI-PTR/MS) as an efficient method of analysing methanol, acetaldehyde and acetone in seawater. Validation of the technique with water standards shows that the optimised responses are linear and reproducible. Limits of detection are 27 nM for methanol, 0.7 nM for acetaldehyde and 0.3 nM for acetone. Acetone and acetaldehyde concentrations generated by MI-PTR/MS are compared to a second, independent method based on purge and trap-gas chromatography/flame ionisation detection (P&T-GC/FID) and show excellent agreement. Chromatographic separation of isomeric species acetone and propanal permits correction to mass 59 signal generated by the PTR/MS and overcomes a known uncertainty in reporting acetone concentrations via mass spectrometry. A third bioassay technique using radiolabelled acetone further supported the result generated by this method. We present the development and optimisation of the MI-PTR/MS technique as a reliable and convenient tool for analysing seawater samples for these trace gases. We compare this method with other analytical techniques and discuss its potential use in improving the current understanding of the cycling of oceanic OVOCs.

Development and validation of a shipboard system for measuring high-resolution vertical profiles of aqueous dimethylsulfide concentrations using chemical ionization mass spectrometry

A sampling and analytical system has been developed for shipboard measurements of high-resolution vertical profiles of the marine trace gas dimethylsulfide (DMS). The system consists of a tube attached to a CTD with a peristaltic pump on deck that delivers seawater to a membrane equilibrator and atmospheric pressure chemical ionization mass spectrometer (Eq-APCIMS). This allows profiling DMS concentrations to a depth of 50 m, with a depth resolution of 1.3-2 m and a detection limit of nearly 0.1 nmol L-1. The seawater is also plumbed to allow parallel operation of additional continuous instruments, and simultaneous collection of discrete samples for complementary analyses. A valve alternates delivery of seawater from the vertical profiler and the ship�s underway intake, thereby providing high-resolution measurements in both the vertical and horizontal dimensions. Tests conducted on various cruises in the Mediterranean Sea, Atlantic, Indian, and Pacific Oceans show good agreement between the Eq-APCIMS measurements and purge and trap gas chromatography with flame photometric detection (GC-FPD) and demonstrate that the delivery of seawater from the underway pump did not significantly affect endogenous DMS concentrations. Combination of the continuous flow DMS analysis with high-frequency hydrographic, optical, biological and meteorological measurements will greatly improve the spatial/temporal resolution of seagoing measurements and improve our understanding of DMS cycling.

Air-sea exchange of methanol and acetone during HiWinGS: Estimation of air phase, water phase gas transfer velocities

The air-sea fluxes of methanol and acetone were measured concurrently using a proton-transfer-reaction mass spectrometer (PTR-MS) with the eddy covariance (EC) technique during the High Wind Gas Exchange Study (HiWinGS) in 2013. The seawater concentrations of these compounds were also measured twice daily with the same PTR-MS coupled to a membrane inlet. Dissolved concentrations near the surface ranged from 7 to 28 nM for methanol and from 3 to 9 nM for acetone. Both gases were consistently transported from the atmosphere to the ocean as a result of their low sea surface saturations. The largest influxes were observed in regions of high atmospheric concentrations and strong winds (up to 25 m s(-1)). Comparison of the total air-sea transfer velocity of these two gases (K-a), along with the in situ sensible heat transfer rate, allows us to constrain the individual gas transfer velocity in the air phase (k(a)) and water phase (k(w)). Among existing parameterizations, the scaling of k(a) from the COARE model is the most consistent with our observations. The k(w) we estimated is comparable to the tangential (shear driven) transfer velocity previously determined from measurements of dimethyl sulfide. Lastly, we estimate the wet deposition of methanol and acetone in our study region and evaluate the lifetimes of these compounds in the surface ocean and lower atmosphere with respect to total (dry plus wet) atmospheric deposition.

Vertical fluxes and atmospheric cycling of methanol, acetaldehyde, and acetone in a coastal environment

We present here vertical fluxes of methanol, acetaldehyde, and acetone measured directly with eddy covariance (EC) during March to July 2012 near the southwest coast of the UK. 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. Concentrations and fluxes of these compounds vary significantly with time of day and wind direction. Higher values of acetaldehyde and acetone are usually observed in the daytime and from the direction of a forested park, most likely due to light-driven emissions from terrestrial plants. Methanol concentration and flux do not demonstrate clear 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 (1�) concentration 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 concentrations of 0.46 (0.20) and 0.39 (0.08) ppb appear to be affected more by terrestrial emissions and long distance transport, respectively.