Mingxi Yang

Atmospheric deposition of methanol over the Atlantic Ocean

Significance Transport of gases between the ocean and the atmosphere has profound implications for our environment and the Earth’s climate. An example of this transport is the oceanic uptake of carbon dioxide, which has buffered us from a higher concentration of this greenhouse gas in the atmosphere while also causing ocean acidification. Here we describe the first direct measurements of air–sea methanol transfer. Atmospheric methanol, a ubiquitous and abundant organic gas of primarily terrestrial origin, is observed to be transported over thousands of kilometers and deposited over the ocean, where it is likely consumed by marine microbes. We quantify the rate of methanol deposition and examine the governing processes near the air–sea interface. 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.

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 (Ka), along with the in situ sensible heat transfer rate, allows us to constrain the individual gas transfer velocity in the air phase (ka) and water phase (kw). Among existing parameterizations, the scaling of ka from the COARE model is the most consistent with our observations. The kw 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.

Exploiting satellite earth observation to quantify current global oceanic DMS flux and its future climate sensitivity

We used coincident Envisat RA2 and AATSR temperature and wind speed data from 2008/2009 to calculate the global net sea-air flux of dimethyl sulfide (DMS), which we estimate to be 19.6 Tg S a−1. Our monthly flux calculations are compared to open ocean eddy correlation measurements of DMS flux from 10 recent cruises, with a root mean square difference of 3.1 μmol m−2 day−1. In a sensitivity analysis, we varied temperature, salinity, surface wind speed, and aqueous DMS concentration, using fixed global changes as well as CMIP5 model output. The range of DMS flux in future climate scenarios is discussed. The CMIP5 model predicts a reduction in surface wind speed and we estimate that this will decrease the global annual sea-air flux of DMS by 22% over 25 years. Concurrent changes in temperature, salinity, and DMS concentration increase the global flux by much smaller amounts. The net effect of all CMIP5 modelled 25 year predictions was a 19% reduction in global DMS flux. 25 year DMS concentration changes had significant regional effects, some positive (Southern Ocean, North Atlantic, Northwest Pacific) and some negative (isolated regions along the Equator and in the Indian Ocean). Using satellite-detected coverage of coccolithophore blooms, our estimate of their contribution to North Atlantic DMS emissions suggests that the coccolithophores contribute only a small percentage of the North Atlantic annual flux estimate, but may be more important in the summertime and in the northeast Atlantic.

Air exposure of coral is a significant source of dimethylsulfide (DMS) to the atmosphere

Corals are prolific producers of dimethylsulfoniopropionate (DMSP). High atmospheric concentrations of the DMSP breakdown product dimethylsulfide (DMS) have been linked to coral reefs during low tides. DMS is a potentially key sulfur source to the tropical atmosphere, but DMS emission from corals during tidal exposure is not well quantified. Here we show that gas phase DMS concentrations (DMSgas) increased by an order of magnitude when three Indo-Pacific corals were exposed to air in laboratory experiments. Upon re-submersion, an additional rapid rise in DMSgas was observed, reflecting increased production by the coral and/or dissolution of DMS-rich mucus formed by the coral during air exposure. Depletion in DMS following re-submersion was likely due to biologically-driven conversion of DMS to dimethylsulfoxide (DMSO). Fast Repetition Rate fluorometry showed downregulated photosynthesis during air exposure but rapid recovery upon re-submersion, suggesting that DMS enhances coral tolerance to oxidative stress during a process that can induce photoinhibition. We estimate that DMS emission from exposed coral reefs may be comparable in magnitude to emissions from other marine DMS hotspots. Coral DMS emission likely comprises a regular and significant source of sulfur to the tropical marine atmosphere, which is currently unrecognised in global DMS emission estimates and Earth System Models.

Air-Sea Exchange of Biogenic Volatile Organic Compounds and the Impact on Aerosol Particle Size Distributions

We report simultaneous, underway eddy covariance measurements of the vertical flux of isoprene, total monoterpenes, and dimethyl sulfide (DMS) over the Northern Atlantic Ocean during fall. Mean isoprene and monoterpene sea-to-air vertical fluxes were significantly lower than mean DMS fluxes. While rare, intense monoterpene sea-to-air fluxes were observed, coincident with elevated monoterpene mixing ratios. A statistically significant correlation between isoprene vertical flux and short wave radiation was not observed, suggesting that photochemical processes in the surface microlayer did not enhance isoprene emissions in this study region. Calculations of secondary organic aerosol production rates (P_(SOA)) for mean isoprene and monoterpene emission rates sampled here indicate that P_(SOA) is on average <0.1 µg m^(-3)d^(-1). Despite modest P_(SOA), low particle number concentrations permit a sizable role for condensational growth of monoterpene oxidation products in altering particle size distributions and the concentration of cloud condensation nuclei during episodic monoterpene emission events from the ocean.This work was supported by a National Science Foundation (NSF) CAREER Award (Grant No. AGS-1151430)

Attribution of Atmospheric Sulfur Dioxide over the English Channel to Dimethylsulfide and Changing Ship Emissions

Atmospheric sulfur dioxide (SO2) was measured continuously from the Penlee Point Atmospheric Observatory (PPAO) near Plymouth, United Kingdom, between May 2014 and November 2015. This coastal site is exposed to marine air across a wide wind sector. The predominant southwesterly winds carry relatively clean background Atlantic air. In contrast, air from the southeast is heavily influenced by exhaust plumes from ships in the English Channel as well as near Plymouth Sound. A new International Maritime Organization (IMO) regulation came into force in January 2015 to reduce the maximum allowed sulfur content in ships’ fuel 10-fold in sulfur emission control areas such as the English Channel. Our observations suggest a 3-fold reduction in shipemitted SO2 from 2014 to 2015. Apparent fuel sulfur content calculated from coincidental SO2 and carbon dioxide (CO2) peaks from local ship plumes show a high level of compliance to the IMO regulation (> 95 %) in both years (∼ 70 % of ships in 2014 were already emitting at levels below the 2015 cap). Dimethyl sulfide (DMS) is an important source of atmospheric SO2 even in this semi-polluted region. The relative contribution of DMS oxidation to the SO2 burden over the English Channel increased from about one-third in 2014 to about one-half in 2015 due to the reduction in ship sulfur emissions. Our diel analysis suggests that SO2 is removed from the marine atmospheric boundary layer in about half a day, with dry deposition to the ocean accounting for a quarter of the total loss.

Wind Speed and Sea State Dependencies of Air‐Sea Gas Transfer: Results From the High Wind Speed Gas Exchange Study (HiWinGS)

A variety of physical mechanisms are jointly responsible for facilitating air-sea gas transfer through turbulent processes at the atmosphere-ocean interface. The nature and relative importance of these mechanisms evolves with increasing wind speed. Theoretical and modeling approaches are advancing, but the limited quantity of observational data at high wind speeds hinders the assessment of these efforts. The HiWinGS project successfully measured gas transfer coefficients (k660) with coincident wave statistics under conditions with hourly mean wind speeds up to 24 m s−1 and significant wave heights to 8 m. Measurements of k660 for carbon dioxide (CO2) and dimethylsulfide (DMS) show an increasing trend with respect to 10-meter neutral wind speed (U10N), following a power-law relationship of the form: k660 co2~U10N1.68 and k660 dms~U10N1.33. Among seven high wind speed events, CO2 transfer responded to the intensity of wave breaking, which depended on both wind speed and sea state in a complex manner, with k660 co2 increasing as the wind sea approaches full development. A similar response is not observed for DMS. These results confirm the importance of breaking waves and bubble injection mechanisms in facilitating CO2 transfer. A modified version of the Coupled Ocean-Atmosphere Response Experiment Gas transfer algorithm (COAREG ver. 3.5), incorporating a sea state-dependent calculation of bubble-mediated transfer, successfully reproduces the mean trend in observed k660 with wind speed for both gases. Significant suppression of gas transfer by large waves was not observed during HiWinGS, in contrast to results from two prior field programs.

Stratus 9/VOCALS ninth setting of the Stratus Ocean Reference Station & VOCALS Regional Experiment

Abstract : The Woods Hole Oceanographic Institution (WHOI) Hawaii Ocean Timeseries (HOT) Site (WHOTS), 100 km north of Oahu, Hawaii, is intended to provide long-term, high-quality air-sea fluxes as a part of the NOAA Climate Observation Program. The WHOTS mooring also serves as a coordinated part of the HOT program, contributing to the goals of observing heat, fresh water and chemical fluxes at a site representative of the oligotrophic North Pacific Ocean. The approach is to maintain a surface mooring outfitted for meteorological and oceanographic measurements by successive mooring turnarounds. These observations will be used to investigate air-sea interaction processes related to climate variability. This report documents recovery of the WHOTS-4 mooring and deployment of the fifth mooring (WHOTS-5). Both moorings used Surlyn foam buoys as the surface element and were outfitted with two Air-Sea Interaction Meteorology (ASIMET) systems. Each ASIMET system measures, records, and transmits via Argos satellite the surface meteorological variables necessary to compute air-sea fluxes of heat, moisture and momentum. The upper 155 m of the moorings were outfitted with oceanographic sensors for the measurement of temperature, conductivity and velocity. A pCO2 system was installed on the WHOTS-5 buoy. The WHOTS mooring turnaround was done between 3 and 11 June 2008. Operations began with deployment of the WHOTS-5 mooring. This was followed by meteorological intercomparisons and CTDs at the WHOTS-4 site. A period of calmer weather was taken advantage of to recover WHOTS-4 on 6 June 2008. The Kilo Moana then returned to the WHOTS-5 mooring for CTD operations and meteorological intercomparisons. This report describes these cruise operations, as well as some of the in-port operations and pre-cruise buoy preparations.

Evaluating Operational AVHRR Sea Surface Temperature Data at the Coastline Using Benthic Temperature Loggers

The nearshore coastal ocean is one of the most dynamic and biologically productive regions on our planet, supporting a wide range of ecosystem services. It is also one of the most vulnerable regions, increasingly exposed to anthropogenic pressure. In the context of climate change, monitoring changes in nearshore coastal waters requires systematic and sustained observations of key essential climate variables (ECV), one of which is sea surface temperature (SST). As temperature influences physical, chemical and biological processes within coastal systems, accurate monitoring is crucial for detecting change. SST is an ECV that can be measured systematically from satellites. Yet, owing to a lack of adequate in situ data, the accuracy and precision of satellite SST at the coastline are not well known. In a prior study, we attempted to address this by taking advantage of in situ SST measurements collected by a group of surfers. Here, we make use of a three year time-series (2014–2017) of in situ water temperature measurements collected using a temperature logger (recording every 30 min) deployed within a kelp forest (∼3 m below chart datum) at a subtidal rocky reef site near Plymouth, UK. We compared the temperature measurements with three other independent in situ SST datasets in the region, from two autonomous buoys located ∼7 km and ∼33 km from the coastline, and from a group of surfers at two beaches near the kelp site. The three datasets showed good agreement, with discrepancies consistent with the spatial separation of the sites. The in situ SST measurements collected from the kelp site and the two autonomous buoys were matched with operational Advanced Very High Resolution Radiometer (AVHRR) EO SST passes, all within 1 h of the in situ data. By extracting data from the closest satellite pixel to the three sites, we observed a significant reduction in the performance of AVHRR at retrieving SST at the coastline, with root mean square differences at the kelp site over twice that observed at the two offshore buoys. Comparing the in situ water temperature data with pixels surrounding the kelp site revealed the performance of the satellite data improves when moving two to three pixels offshore and that this improvement was better when using an SST algorithm that treats each pixel independently in the retrieval process. At the three sites, we related differences between satellite and in situ SST data with a suite of atmospheric variables, collected from a nearby atmospheric observatory, and a high temporal resolution land surface temperature (LST) dataset. We found that differences between satellite and in situ SST at the coastline (kelp site) were well correlated with LST and solar zenith angle; implying contamination of the pixel by land is the principal cause of these larger differences at the coastline, as opposed to issues with atmospheric correction. This contamination could be either from land directly within the pixel, potentially impacted by errors in geo-location, or possibly through thermal adjacency effects. Our results demonstrate the value of using benthic temperature loggers for evaluating satellite SST data in coastal regions, and highlight issues with retrievals at the coastline that may inform future improvements in operational products.