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Abstract. The flux of dimethylsulfide (DMS) to the atmosphere is generally inferred using water sampled at or below 2 m depth, thereby excluding any concentration anomalies at the air-sea interface. Two independent techniques were used to assess the potential for near-surface DMS enrichment to influence DMS emissions and also identify the factors influencing enrichment. DMS measurements in productive frontal waters over the Chatham Rise, east of New Zealand, did not identify any significant gradients between 0.01 and 6 m in sub-surface seawater, whereas DMS enrichment in the sea-surface microlayer was variable, with a mean enrichment factor (EF; the concentration ratio between DMS in the sea-surface microlayer and in sub-surface water) of 1.7. Physical and biological factors influenced sea-surface microlayer DMS concentration, with high enrichment (EF > 1.3) only recorded in a dinoflagellate-dominated bloom, and associated with low to medium wind speeds and near-surface temperature gradients. On occasion, high DMS enrichment preceded periods when the air-sea DMS flux, measured by eddy covariance, exceeded the flux calculated using National Oceanic and Atmospheric Administration (NOAA) CoupledOcean Atmospheric Response Experiment (COARE) parameterized gas transfer velocities and measured sub-surface seawater DMS concentrations. The results of these two independent approaches suggest that air-sea emissions may be influenced by near-surface DMS production under certain conditions, and highlight the need for further study to constrain the magnitude and mechanisms of DMS production in the sea-surface microlayer.

Abstract. Establishing the relationship between marine boundary layer (MBL) aerosols and surface water biogeochemistry is required to understand aerosol and cloud production processes over the remote ocean and represent them more accurately in earth system models and global climate projections. This was addressed by the SOAP (Surface Ocean Aerosol Production) campaign, which examined air-sea interaction over biologically productive frontal waters east of New Zealand. This overview details the objectives, regional context, sampling strategy and provisional findings of a pilot study, PreSOAP, in austral summer 2011 and the following SOAP voyage in late austral summer 2012. Both voyages characterized surface water and MBL composition in three phytoplankton blooms of differing species composition and biogeochemistry, with significant regional correlation observed between chlorophyll a and DMSsw. Surface seawater dimethylsulfide (DMSsw) and associated air-sea DMS flux showed spatial variation during the SOAP voyage, with maxima of 25 nmol L −1 and 100 µmol m −2 d −1 , respectively, recorded in a dinoflagellate bloom. Inclusion of SOAP data in a regional DMSsw compilation indicates that the current climatological mean is an underestimate for this region of the southwest Pacific. Estimation of the DMS gas transfer velocity (k DMS ) by independent techniques of eddy covariance and gradient flux showed good agreement, although both exhibited periodic deviations from model estimates. Flux anomalies were related to surface warming and sea surface microlayer enrichment and also reflected the heterogeneous distribution of DMSsw and the associated flux footprint. Other aerosol precursors measured included the halides and various volatile organic carbon compounds, with first measurements of the short-lived gases glyoxal and methylglyoxal in pristine Southern Ocean marine air indicating an unidentified local source. The application of a real-time clean sector, contaminant markers and a common aerosol inlet facilitated multi-sensor measurement of uncontaminated air. Aerosol characterization identified variable Aitken mode and consistent submicron-sized accumulation and coarse modes. Submicron aerosol mass was dominated by secondary particles containing ammonium sulfate/bisulfate under light winds, with an increase in sea salt under higher wind speeds. MBL measurements and chamber experiments identified a significant organic component in primary and secondary aerosols. Comparison of SOAP aerosol number and size distributionsPublished by Copernicus Publications on behalf of the European Geosciences Union. 13646 C. S. Law et al.: Overview and preliminary results of the SOAP campaign reveals an underprediction in GLOMAP (GLObal Model of Aerosol Processes)-mode aerosol number in clean marine air masses, suggesting a missing marine aerosol source in the model. The SOAP data will be further examined for evidence of nucleation events and also to identify relationships between MBL composition and surface ocean biogeochemistry that may pr...

Methane emission was measured from 10 dairy cows and 12 wether sheep grazing kikuyu

Daily methane emission from 12 Romney-cross-bred ewes and 10 lactating Friesian dairy cows, rotationally grazed on perennial ryegrass/white clover dominant pastures, was measured during four seasons of a year (September, November, March, and June/July). Methane emission was measured from each animal for 5 consecutive days in each measurement period using the sulphur hexafluoride tracer gas technique. The pastures varied significantly in chemical composition between seasons, generally decreasing in protein, soluble sugars, and digestibility and increasing in acid detergent fibre (ADF) and neutral detergent fibre (NDF) as the grasses flowered in November, with an increase in protein and a decrease in soluble sugars in March, a trend that continued through to June/July. Methane emission (g/day) from dairy cows was significantly different (P < 0.001) between seasons, being high at peak A02021 ;

Summary Methane emissions from ruminant livestock are responsible for 45 % of New Zealand’s combined CO2‐equivalent greenhouse gas inventory, and arise principally from sheep. Using a flock of 6‐month old sheep (20 ha–1) grazing abundant pasture, we compare micrometeorological measurements of net methane emission rates with measurements from individual sheep based on a sulphur‐hexafluoride tracer technique. Individual sheep emission rates were highly variable and averaged 19.5 ± 4.8 (SD) g CH4 sheep–1 d–1, or 39 ± 9.6 mg CH4 m–2 d–1 on an areal basis. Emission rates were poorly correlated with animal live weight or dry matter intake but represented an average dietary energy loss of 3.6%.  Methane fluxes from the surface were determined as half hourly averages by a flux‐gradient technique using temperature and methane gradients. Soil methane consumption was measured using chambers and found to be negligible (< 0.09 mg CH4 m–2 d–1) in comparison with the animal contribution. Daily net emission rates averaged 46 mg m–2 d–1 and exhibited a broad peak in the early afternoon which corresponded with animal activity patterns. On average, net emisssion rates were 40% higher during the day than at night. Stable nocturnal conditions led to a separation of the micrometeorological measurements from the methane source and hence highly variable results. Based on two corroborating techniques, the average net methane emission rate was c. 43 mg CH4 m–2 d–1 or 155 kg CH4 ha–1 y–1.

Abstract. The oceanic frontal region above the Chatham Rise east of New Zealand was investigated during the late austral summer season in February and March 2012. Despite its potential importance as a source of marine-originating and climate-relevant compounds, such as dimethyl sulfide (DMS) and its algal precursor dimethylsulfoniopropionate (DMSP), little is known of the processes fuelling the reservoirs of these sulfur (S) compounds in the water masses bordering the subtropical front (STF). This study focused on two opposing short-term fates of DMSP-S following its uptake by microbial organisms (either its conversion into DMS or its assimilation into bacterial biomass) and has not considered dissolved non-volatile degradation products. Sampling took place in three phytoplankton blooms (B1, B2, and B3) with B1 and B3 occurring in relatively nitraterich, dinoflagellate-dominated subantarctic waters, and B2 occurring in nitrate-poor subtropical waters dominated by coccolithophores. Concentrations of total DMSP (DMSP t ) and DMS were high across the region, up to 160 and 14.5 nmol L −1 , respectively. Pools of DMSP t showed a strong association with overall phytoplankton biomass proxied by chlorophyll a (r s = 0.83) likely because of the persistent dominance of dinoflagellates and coccolithophores, both DMSP-rich taxa. Heterotrophic microbes displayed low S assimilation from DMSP (less than 5 %) likely because their S requirements were fulfilled by high DMSP availability. Rates of bacterial protein synthesis were significantly correlated with concentrations of dissolved DMSP (DMSP d , r s = 0.86) as well as with the microbial conversion efficiency of DMSP d into DMS (DMS yield, r s = 0.84). Estimates of the potential contribution of microbially mediated rates of DMS production (0.1-27 nmol L −1 day −1 ) to the near-surface concentrations of DMS suggest that bacteria alone could not have sustained DMS pools at most stations, indicating an important role for phytoplankton-mediated DMS production. The findings from this study provide crucial information on the distribution and cycling of DMS and DMSP in a critically under-sampled area of the global ocean, and they highlight the importance of oceanic fronts as hotspots of the production of marine biogenic S compounds.

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