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.

Air–sea fluxes of oxygenated volatile organic compounds across the Atlantic Ocean

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.

Annual study of oxygenated volatile organic compounds in UK shelf waters

We performed an annual study of oxygenated volatile organic compound (OVOC) seawater concentrations at a site off Plymouth, UK in the Western English Channel over the period of February 2011–March 2012. Acetone concentrations ranged from 2–10 nM (nanomole/L) in surface waters with a maximum observed in summer. Concentrations correlated positively with net shortwave radiation and UV light, suggestive of photochemically linked acetone production. We observed a clear decline in acetone concentrations below the mixed layer. Acetaldehyde varied between 4–37 nM in surface waters with higher values observed in autumn and winter. Surface concentrations of methanol ranged from 16–78 nM, but no clear annual cycle was observed. Methanol concentrations exhibited considerable inter-annual variability. We estimate consistent deposition to the sea surface for acetone and methanol but that the direction of the acetaldehyde flux varies during the year.

Some Ecological Consequences Of The Physiological And Biochemical Effects Of Petroleum Compounds On Marine Mollusks

The problems of relating the results of experiments in the laboratory to events in nature are twofold: to equate the response to a single variable (hydrocarbons) with the natural variability in the biological material in a multivariate environment, and to consider whether the response established experimentally has any relevance to the animal's chances of survival and reproduction (i.e. its fitness) in the natural population. Recent studies of the effects of petroleum hydrocarbons on marine invertebrates are reviewed, with an emphasis on the physiological and cytochemical responses by bivalve molluscs. The dose-response relations that emerge suggest the intensity of the 'signal' that must be detected in nature if the chronic, sublethal effects of petroleum pollution are to be measured. The natural variability in these physiological and cytochemical processes are then reviewed and the main causes of variability in natural populations, both endogenous and exogenous, discussed. These results indicate the extent of the `noise' above which the signal from possible pollution effects must be detected. The results from recent field studies on the common mussel, Mytilus edulis, are discussed. The results are as complex as expected, but it proves possible to reduce the variance in the measured responses so that pollution effects, including those due to hydrocarbons, can be detected. The ecological consequences of the observed effects of petroleum hydrocarbons are then discussed in terms of reproductive effort and reproductive value. Considerable variation between populations exists here also and this can be used to help in the interpretation of the extent of the impact of the environment on the ecology of the population. The result is to place the findings of the laboratory experiments in an ecological context of natural variability and of the physiological costs of adaptation.