Separating N2O production and consumption in intact agricultural soil cores at different moisture contents and depths.

Agricultural soils are a major source of the potent greenhouse gas and ozone depleting substance, N2O. To implement management practices that minimize microbial N2O production and maximize its consumption (i.e., complete denitrification), we must understand the interplay between simultaneously occurring biological and physical processes, especially how this changes with soil depth. Meaningfully disentangling of these processes is challenging and typical N2O flux measurement techniques provide little insight into subsurface mechanisms. In addition, denitrification studies are often conducted on sieved soil in altered O2 environments which relate poorly to in situ field conditions. Here, we developed a novel incubation system with headspaces both above and below the soil cores and field-relevant O2 concentrations to better represent in situ conditions. We incubated intact sandy clay loam textured agricultural topsoil (0-10 cm) and subsoil (50-60 cm) cores for 3-4 days at 50% and 70% water-filled pore space, respectively. 15N-N2O pool dilution and an SF6 tracer were injected below the cores to determine the relative diffusivity and the net N2O emission and gross N2O emission and consumption fluxes. The relationship between calculated fluxes from the below and above soil core headspaces confirmed that the system performed well. Relative diffusivity did not vary with depth, likely due to the preservation of preferential flow pathways in the intact cores. Gross N2O emission and uptake also did not differ with depth but were higher in the drier cores, contrary to expectation. We speculate this was due to aerobic denitrification being the primary N2O consuming process and simultaneously occurring denitrification and nitrification both producing N2O in the drier cores. We provide further evidence of substantial N2O consumption in drier soil but without net negative N2O emissions. The results from this study are important for the future application of the 15N-N2O pool dilution method and N budgeting and modelling, as required for improving management to minimize N2O losses.

Winter weather controls net influx of atmospheric CO2 on the north-west European shelf.

Shelf seas play an important role in the global carbon cycle, absorbing atmospheric carbon dioxide (CO2) and exporting carbon (C) to the open ocean and sediments. The magnitude of these processes is poorly constrained, because observations are typically interpolated over multiple years. Here, we used 298500 observations of CO2 fugacity (fCO2) from a single year (2015), to estimate the net influx of atmospheric CO2 as 26.2 ± 4.7 Tg C yr-1 over the open NW European shelf. CO2 influx from the atmosphere was dominated by influx during winter as a consequence of high winds, despite a smaller, thermally-driven, air-sea fCO2 gradient compared to the larger, biologically-driven summer gradient. In order to understand this climate regulation service, we constructed a carbon-budget supplemented by data from the literature, where the NW European shelf is treated as a box with carbon entering and leaving the box. This budget showed that net C-burial was a small sink of 1.3 ± 3.1 Tg C yr-1, while CO2 efflux from estuaries to the atmosphere, removed the majority of river C-inputs. In contrast, the input from the Baltic Sea likely contributes to net export via the continental shelf pump and advection (34.4 ± 6.0 Tg C yr-1).

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 (14)C labeled acetone can be used to determine microbial oxidation to (14)CO2. 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 V max of 4.1 pmol L(-1) h(-1), with a K m 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.

Atmospheric deposition of methanol over the Atlantic Ocean.

In the troposphere, methanol (CH3OH) is present ubiquitously and second in abundance among organic gases after methane. In the surface ocean, methanol represents a supply of energy and carbon for marine microbes. Here we report direct measurements of air-sea methanol transfer along a ∼10,000-km north-south transect of the Atlantic. The flux of methanol was consistently from the atmosphere to the ocean. Constrained by the aerodynamic limit and measured rate of air-sea sensible heat exchange, methanol transfer resembles a one-way depositional process, which suggests dissolved methanol concentrations near the water surface that are lower than what were measured at ∼5 m depth, for reasons currently unknown. We estimate the global oceanic uptake of methanol and examine the lifetimes of this compound in the lower atmosphere and upper ocean with respect to gas exchange. We also constrain the molecular diffusional resistance above the ocean surface-an important term for improving air-sea gas exchange models.

Gradients in microbial methanol uptake: productive coastal upwelling waters to oligotrophic gyres in the Atlantic Ocean.

Methanol biogeochemistry and its importance as a carbon source in seawater is relatively unexplored. We report the first microbial methanol carbon assimilation rates (k) in productive coastal upwelling waters of up to 0.117±0.002 d(-1) (~10 nmol l(-1 )d(-1)). On average, coastal upwelling waters were 11 times greater than open ocean northern temperate (NT) waters, eight times greater than gyre waters and four times greater than equatorial upwelling (EU) waters; suggesting that all upwelling waters upon reaching the surface (≤20 m), contain a microbial population that uses a relatively high amount of carbon (0.3-10 nmol l(-1 )d(-1)), derived from methanol, to support their growth. In open ocean Atlantic regions, microbial uptake of methanol into biomass was significantly lower, ranging between 0.04-0.68 nmol l(-1 )d(-1). Microbes in the Mauritanian coastal upwelling used up to 57% of the total methanol for assimilation of the carbon into cells, compared with an average of 12% in the EU, and 1% in NT and gyre waters. Several methylotrophic bacterial species were identified from open ocean Atlantic waters using PCR amplification of mxaF encoding methanol dehydrogenase, the key enzyme in bacterial methanol oxidation. These included Methylophaga sp., Burkholderiales sp., Methylococcaceae sp., Ancylobacter aquaticus, Paracoccus denitrificans, Methylophilus methylotrophus, Methylobacterium oryzae, Hyphomicrobium sp. and Methylosulfonomonas methylovora. Statistically significant correlations for upwelling waters between methanol uptake into cells and both chlorophyll a concentrations and methanol oxidation rates suggest that remotely sensed chlorophyll a images, in these productive areas, could be used to derive total methanol biological loss rates, a useful tool for atmospheric and marine climatically active gas modellers, and air-sea exchange scientists.

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.

Microbial methanol uptake in northeast Atlantic waters.

Methanol is the predominant oxygenated volatile organic compound in the troposphere, where it can significantly influence the oxidising capacity of the atmosphere. However, we do not understand which processes control oceanic concentrations, and hence, whether the oceans are a source or a sink to the atmosphere. We report the first methanol loss rates in seawater by demonstrating that (14)C-labelled methanol can be used to determine microbial uptake into particulate biomass, and oxidation to (14)CO(2). We have found that methanol is used predominantly as a microbial energy source, but also demonstrated its use as a carbon source. We report biological methanol oxidation rates between 2.1 and 8.4 nmol l(-1) day(-1) in surface seawater of the northeast Atlantic. Kinetic experiments predict a V(max) of up to 29 nmol l(-1) day(-1), with a high affinity K(m) constant of 9.3 nM in more productive coastal waters. We report surface concentrations of methanol in the western English channel of 97±8 nM (n=4) between May and June 2010, and for the wider temperate North Atlantic waters of 70±13 nM (n=6). The biological turnover time of methanol has been estimated between 7 and 33 days, although kinetic experiments suggest a 7-day turnover in more productive shelf waters. Methanol uptake rates into microbial particles significantly correlated with bacterial and phytoplankton parameters, suggesting that it could be used as a carbon source by some bacteria and possibly some mixotrophic eukaryotes. Our results provide the first methanol loss rates from seawater, which will improve the understanding of the global methanol budget.

Ocean acidification and marine trace gas emissions.

The oceanic uptake of man-made CO(2) emissions is resulting in a measureable decrease in the pH of the surface oceans, a process which is predicted to have severe consequences for marine biological and biogeochemical processes [Caldeira K, Wickett ME (2003) Nature 425:365; The Royal Society (2005) Policy Document 12/05 (Royal Society, London)]. Here, we describe results showing how a doubling of current atmospheric CO(2) affects the production of a suite of atmospherically important marine trace gases. Two CO(2) treatments were used during a mesocosm CO(2) perturbation experiment in a Norwegian fjord (present day: approximately 380 ppmv and year 2100: approximately 750 ppmv), and phytoplankton blooms were stimulated by the addition of nutrients. Seawater trace gas concentrations were monitored over the growth and decline of the blooms, revealing that concentrations of methyl iodide and dimethylsulfide were significantly reduced under high CO(2.) Additionally, large reductions in concentrations of other iodocarbons were observed. The response of bromocarbons to high CO(2) was less clear cut. Further research is now required to understand how ocean acidification might impact on global marine trace gas fluxes and how these impacts might feed through to changes in the earth's future climate and atmospheric chemistry.