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.

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.

Microbial acetone oxidation in coastal seawater

Acetone is an important oxygenated volatile organic compound (OVOC) in the troposphere where it influences the oxidizing capacity of the atmosphere. However, the air-sea flux is not well quantified, in part due to a lack of knowledge regarding which processes control oceanic concentrations, and, specifically whether microbial oxidation to CO2 represents a significant loss process. We demonstrate that 14C labeled acetone can be used to determine microbial oxidation to 14CO2. Linear microbial rates of acetone oxidation to CO2 were observed for between 0.75-3.5 h at a seasonally eutrophic coastal station located in the western English Channel (L4). A kinetic experiment in summer at station L4 gave a Vmax of 4.1 pmol L-1 h-1, with a Km constant of 54 pM. We then used this technique to obtain microbial acetone loss rates ranging between 1.2 and 42 pmol L-1 h-1.(monthly averages) over an annual cycle at L4, with maximum rates observed during winter months. The biological turnover time of acetone (in situ concentration divided by microbial oxidation rate) in surface waters varied from ~3 days in February 2011, when in situ concentrations were 3 ± 1 nM, to >240 days in June 2011, when concentrations were more than twofold higher at 7.5 ± 0.7 nM. These relatively low marine microbial acetone oxidation rates, when normalized to in situ concentrations, suggest that marine microbes preferentially utilize other OVOCs such as methanol and acetaldehyde.

Seasonal variability in microbial methanol utilisation in coastal waters of the western English Channel

Methanol is ubiquitous in seawater and the most abundant oxygenated volatile organic compound (OVOC) in the atmosphere where it influences oxidising capacity and ozone formation. Marine methylotrophic bacteria utilise methanol in seawater both as an energy and/or growth substrate. This work represents the first fully resolved seasonal study of marine microbial methanol uptake dynamics. Rates of microbial methanol dissimilation in coastal surface waters of the UK varied between 0.7 – 11.2 nmol l-1 h-1 and reached a maximum in February. Rates of microbial methanol assimilation varied between 0.04 – 2.64 x 10-2 nmol l-1 h-1 and reached a maximum in August. Temporal variability in microbial methanol uptake rates shows that methanol assimilation and dissimilation display opposing seasonal cycles, although overall <1% of methanol was assimilated. Correlative approaches with 16S rRNA pyrosequencing data suggested that bacteria of the SAR11 clade and Rhodobacterales could be significantly influencing rates of methanol dissimilation and assimilation, respectively, at station L4 in the western English Channel

Seasonal variability in microbial methanol utilisation in coastal waters of the western English Channel

Methanol is ubiquitous in seawater and the most abundant oxygenated volatile organic compound (OVOC) in the atmosphere where it influences oxidising capacity and ozone formation. Marine methylotrophic bacteria utilise methanol in seawater both as an energy and/or growth substrate. This work represents the first fully resolved seasonal study of marine microbial methanol uptake dynamics. Rates of microbial methanol dissimilation in coastal surface waters of the UK varied between 0.7 – 11.2 nmol l-1 h-1 and reached a maximum in February. Rates of microbial methanol assimilation varied between 0.04 – 2.64 x 10-2 nmol l-1 h-1 and reached a maximum in August. Temporal variability in microbial methanol uptake rates shows that methanol assimilation and dissimilation display opposing seasonal cycles, although overall <1% of methanol was assimilated. Correlative approaches with 16S rRNA pyrosequencing data suggested that bacteria of the SAR11 clade and Rhodobacterales could be significantly influencing rates of methanol dissimilation and assimilation, respectively, at station L4 in the western English Channel

Methanol acetaldehyde and acetone in the surface waters of the Atlantic Ocean

Oceanic methanol, acetaldehyde, and acetone concentrations were measured during an Atlantic Meridional Transect (AMT) cruise from the UK to Chile (49°N to 39°S) in 2009. Methanol (48–361 nM) and acetone (2–24 nM) varied over the track with enrichment in the oligotrophic Northern Atlantic Gyre. Acetaldehyde showed less variability (3–9 nM) over the full extent of the transect. These oxygenated volatile organic compounds (OVOCs) were also measured subsurface, with methanol and acetaldehyde mostly showing homogeneity throughout the water column. Acetone displayed a reduction below the mixed layer. OVOC concentrations did not consistently correlate with primary production or chlorophyll-a levels in the surface Atlantic Ocean. However, we did find a novel and significant negative relationship between acetone concentration and bacterial leucine incorporation, suggesting that acetone might be removed by marine bacteria as a source of carbon. Microbial turnover of both acetone and acetaldehyde was confirmed. Modeled atmospheric data are used to estimate the likely air-side OVOC concentrations. The direction and magnitude of air-sea fluxes vary for all three OVOCs depending on location. We present evidence that the ocean may exhibit regions of acetaldehyde under-saturation. Extrapolation suggests that the Atlantic Ocean represents an overall source of these OVOCs to the atmosphere at 3, 3, and 1 Tg yr−1 for methanol, acetaldehyde, and acetone, respectively.

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.