Christa Marandino

Ship‐based measurement of air‐sea CO2 exchange by eddy covariance

A system for the shipboard measurement of air-sea CO2 fluxes by eddy covariance was developed and tested. The system was designed to reduce two major sources of experimental uncertainty previously reported. First, the correction for in situ water vapor fluctuations (the “Webb” correction) was reduced by 97% by drying the air sample stream. Second, motion sensitivity of the gas analyzer was reduced by using an open-path type sensor that was converted to a closed-path configuration to facilitate drying of the air stream. High-quality CO2 fluxes were obtained during 429 14 min flux intervals during two cruises in the North Atlantic. The results suggest that the gas analyzer resolved atmospheric CO2 fluctuations well below its RMS noise level. This noise was uncorrelated with the vertical wind and therefore filtered out by the flux calculation. Using climatological data, we estimate that the techniques reported here could enable high-quality measurements of air-sea CO2 flux over much of the world oceans.

Air-Sea Gas Exchange Of Co2 and Dms In the North Atlantic By Eddy Covariance

We report the first simultaneous eddy covariance flux measurements of CO2 and dimethylsulfide (DMS) over the open ocean for two North Atlantic cruises. After normalization for Schmidt number, the two gases give essentially identical gas transfer coefficients and wind speed dependences for the wind speed range 2–10 ms−1. The data indicate a linear relationship between the gas transfer coefficient and mean wind speed, with measured gas transfer coefficients slightly above the Wanninkhof (1992) parameterization, particularly at low wind speeds.

Space-based retrievals of air-sea gas transfer velocities using altimeters: Calibration for dimethyl sulfide

This study is the first to directly correlate gas transfer velocity, measured at sea using the eddy-correlation (EC) technique, and satellite altimeter backscattering. During eight research cruises in different parts of the world, gas transfer velocity of dimethyl sulfide (DMS) was measured. The sample times and locations were compared with overpass times and locations of remote sensing satellites carrying Ku-band altimeters: ERS-1, ERS-2, TOPEX, POSEIDON, GEOSAT Follow-On, JASON-1, JASON-2 and ENVISAT. The result was 179 pairs of gas transfer velocity measurements and backscattering coefficients. An inter-calibration of the different altimeters significantly reduced data scatter. The inter-calibrated data was best fitted to a quadratic relation between the inverse of the backscattering coefficients and the gas transfer velocity measurements. A gas transfer parameterization based on backscattering, corresponding with sea surface roughness, might be expected to perform better than wind speed-based parameterizations. Our results, however, did not show improvement compared to direct correlation of shipboard wind speeds. The relationship of gas transfer velocity to satellite-derived backscatter, or wind speed, is useful to provide retrieval algorithms. Gas transfer velocity (cm/hr), corrected to a Schmidt number of 660, is proportional to wind speed (m/s). The measured gas transfer velocity is controlled by both the individual water-side and air-side gas transfer velocities. We calculated the latter using a numerical scheme, to derive water-side gas transfer velocity. DMS is sufficiently soluble to neglect bubble-mediated gas transfer, thus, the DMS transfer velocities could be applied to estimate water-side gas transfer velocities through the unbroken surface of any other gas Key Points: - Show relations between altimeter data and field values of air-sea gas transfer - DMS gas transfer velocity can be used to estimate direct gas transfer of any gas - Direct gas transfer velocity (for Sc = 660) is roughly double 10 m wind speed

Short-Lived Trace Gases in the Surface Ocean and the Atmosphere

The two-way exchange of trace gases between the ocean and the atmosphere is important for both the chemistry and physics of the atmosphere and the biogeochemistry of the oceans, including the global cycling of elements. Here we review these exchanges and their importance for a range of gases whose lifetimes are generally short compared to the main greenhouse gases and which are, in most cases, more reactive than them. Gases considered include sulphur and related compounds, organohalogens, non-methane hydrocarbons, ozone, ammonia and related compounds, hydrogen and carbon monoxide. Finally, we stress the interactivity of the system, the importance of process understanding for modeling, the need for more extensive field measurements and their better seasonal coverage, the importance of inter-calibration exercises and finally the need to show the importance of air-sea exchanges for global cycling and how the field fits into the broader context of Earth System Science.

Seasonal variability of methyl iodide in the Kiel Fjord

From October 2008 to November 2010, CH3I concentrations were measured in the Kiel Fjord together with potentially related biogeochemical and physical parameters. A repeating seasonal cycle of CH3I was observed with highest concentrations in summer (ca. 8.3 pmol L−1; June and July) and lowest concentrations in winter (ca. 1.5 pmol L−1; December to February). A strong positive correlation at zero lag between [CH3I] and solar radiation (R2 = 0.93) was observed, whereas correlations with other variables (SST, Chlorophyll a) were weaker, and they lagged CH3I by ca. 1 month. These results appear consistent with the hypothesis that SSR is the primary forcing of CH3I production in surface seawater, possibly through a photochemical pathway. A mass balance of the monthly averaged data was used to infer mean rates of daily net production (Pnet) and losses for CH3I over the year. The sea-to-air flux of CH3I in the Kiel Fjord averaged 3.1 nmol m−2 d−1, the mean chemical loss rate was 0.047 pmol L−1 d−1, and Pnet varied systematically from winter to summer (from 0 to 0.6 pmol L−1 d−1). Pnet was correlated at zero lag with SST, SSR, and Chla (R2 = 0.55, 0.67, and 0.73, respectively, p << 0.01). The lagged cross-correlation analysis indicated that SSR led Pnet by 1 month, whereas the strongest cross correlations with Chla were at lags of 0 to +1 month, and SST lagged Pnet by 1 month. The broad seasonal peak of Pnet makes it difficult to determine the key factor controlling CH3I net production using in situ concentration data alone.

Correction to “Oceanic uptake and the global atmospheric acetone budget”

] In the paper ‘‘Oceanic uptake and the global atmo-spheric acetone budget’’ by C. A. Marandino et al. (Geo-phys. Res. Lett., 32, L15806, doi:10.1029/2005GL023285)it was recently determined that a calculation error was madeduring flux data processing. The flux data has been reproc-essed and all the values in both the text and figures havebeen recomputed. The qualitative discussion and conclu-sions remain the same. After the data was reprocessed, itwas determined that the low frequency correction could bemodified. Instead of eliminating the power at frequencieslower than 5E-3 Hz in all of the records, a low frequencydiagnostic was created to assess whether the record shouldbe retained at all. This diagnostic was the ratio between theflux at the 5E-3 Hz cutoff and the full flux (i.e. no cutoff). Ifthe ratio indicated a difference greater than 30%, the recordwas not included in the final dataset. The entire dataprocessing procedure will be published in the Journal ofGeophysical Research [Marandino et al., 2006]. A secondcalculationerrorwasfoundintheuncertaintyanalysisfortheglobal acetone sink budget. Corrected versions of Table 1and Figures 1–3 from the original paper are given. Anadditional table (Table 2) has been included listing therecomputed values of several quantities discussed in theoriginal paper.

A time series of incubation experiments to examine the production and loss of CH3I in surface seawater

In order to investigate production pathways of methyl iodide and controls on emissions from the surface ocean, a set of repeated in vitro incubation experiments were performed over an annual cycle in the context of a time series of in situ measurements in Kiel Fjord (54.3°N, 10.1°E). The incubation experiments revealed a diurnal variation of methyl iodide in samples exposed to natural light, with maxima during day time and losses during night hours. The amplitude of the daily accumulation varied seasonally and was not affected by filtration (0.2 µm), consistent with a photochemical pathway for CH3I production. The methyl iodide loss rate at nighttime correlates with the concentration accumulated during daytime suggesting a first-order loss mechanism (R2 = 0.29, p << 0.01). Daily (24 h) net production (Pnet) was similar in magnitude between in vitro and in situ mass balances. However, the estimated gross production (Pgross) of methyl iodide ranged from −0.07 to 2.24 pmol L−1 d−1 and was up to 5 times higher in summer than Pnet calculated from the in situ study. The large excess of Pgross over Pnet in summer revealed by the incubation experiments is a consequence of large losses of CH3I by as-yet uncharacterized processes (e.g., biological degradation or chemical pathways other than Cl− substitution).

Transport Variability of Very Short Lived Substances From the West Indian Ocean to the Stratosphere

Halogen- and sulfur-containing compounds are supersaturated in the surface ocean, which results in their emission to the atmosphere. These compounds can be transported to the stratosphere, where they impact ozone, the background aerosol layer, and climate. In this study we calculate the seasonal and interannual variability of transport from the West Indian Ocean (WIO) surface to the stratosphere for 2000-2016 with the Lagrangian transport model FLEXPART using ERA-Interim meteorological fields. We investigate the transport relevant for very short lived substances (VSLS) with tropospheric lifetimes corresponding to dimethylsulfide (1 day), methyl iodide (CH3I, 3.5 days), bromoform (CHBr3, 17 days), and dibromomethane (CH2Br2, 150 days). The stratospheric source gas injection of VSLS tracers from the WIO shows a distinct annual cycle associated with the Asian monsoon. Over the 16-year time series, a slight increase in source gas injection from the WIO to the stratosphere is found for all VSLS tracers and during all seasons. The interannual variability shows a relationship with sea surface temperatures in the WIO as well as the El Nino-Southern Oscillation. During boreal spring of El Nino, enhanced stratospheric injection of VSLS from the tropical WIO is caused by positive sea surface temperature anomalies and enhanced vertical uplift above the WIO. During boreal fall of La Nina, strong injection is related to enhanced atmospheric upward motion over the East Indian Ocean and a prolonged Indian summer monsoon season. Related physical mechanisms and uncertainties are discussed in this study

The influence of air-sea fluxes on atmospheric aerosols during the summer monsoon over the tropical Indian Ocean

During the summer monsoon, the western tropical Indian Ocean is predicted to be a hot spot for dimethylsulfide emissions, the major marine sulfur source to the atmosphere, and an important aerosol precursor. Other aerosol relevant fluxes, such as isoprene and sea spray, should also be enhanced, due to the steady strong winds during the monsoon. Marine air masses dominate the area during the summer monsoon, excluding the influence of continentally derived pollutants. During the SO234-2/235 cruise in the western tropical Indian Ocean from July to August 2014, directly measured eddy covariance DMS fluxes confirm that the area is a large source of sulfur to the atmosphere (cruise average 9.1 μmol m−2 d−1). The directly measured fluxes, as well as computed isoprene and sea spray fluxes, were combined with FLEXPART backward and forward trajectories to track the emissions in space and time. The fluxes show a significant positive correlation with aerosol data from the Terra and Suomi-NPP satellites, indicating a local influence of marine emissions on atmospheric aerosol numbers.

Correction to “Eddy correlation measurements of the air/sea flux of dimethylsulfide over the North Pacific Ocean”

[1] In the paper ‘‘Eddy correlation measurements of the air/sea flux of dimethylsulfide over the North Pacific Ocean’’ by C. A. Marandino et al. (Journal of Geophysical Research, 112, D03301, doi:10.1029/2006JD007293, 2007), the Wanninkhof [1992] parameterization in Figure 13 was calculated incorrectly. The revised Figure 13 is included. The discussion and conclusions of the original paper are not impacted by this change.