ALBERT

Description: Halocarbons from oceanic sources contribute to halogens in the troposphere, and can be transported into the stratosphere where they take part in ozone depletion. This paper presents distribution and sources in the equatorial Atlantic from June and July 2011 of the four compounds bromoform (CHBr3), dibromomethane (CH2Br2), methyl iodide (CH3I) and diiodomethane (CH2I2). Enhanced biological production during the Atlantic Cold Tongue (ACT) season, indicated by phytoplankton pigment concentrations, led to elevated concentrations of CHBr3 of up to 44.7 pmol L−1 and up to 9.2 pmol L−1 for CH2Br2 in surface water, which is comparable to other tropical upwelling systems. While both compounds correlated very well with each other in the surface water,CH2Br2 was often more elevated in greater depth than CHBr3, which showed maxima in the vicinity of the deep chlorophyll maximum. The deeper maximum of CH2Br2 indicates an additional source in comparison to CHBr3 or a slower degradation of CH2Br2. Concentrations of CH3I of up to 12.8 pmol L−1 in the surface water were measured. In contrary to expectations of a predominantly photochemical source in the tropical ocean, its distribution was mostly in agreement with biological parameters, indicating a~biological source. CH2I2 was very low in the near surface water with maximum concentrations of only 3.7 pmol L−1, and the observed anticorrelation with global radiation was likely due to its strong photolysis. CH2I2 showed distinct maxima in deeper waters similar to CH2Br2. For the first time, diapycnal fluxes of the four halocarbons from the upper thermocline into and out of the mixed layer were determined. These fluxes were low in comparison to the halocarbon sea-to-air fluxes. This indicates that despite the observed maximum concentrations at depth, production in the surface mixed layer is the main oceanic source for all four compounds and has an influence on emissions into the atmosphere. The calculated production rates of the compounds yield 34 (CHBr3), 10 (CH2Br2), 21 (CH3I) and 384 (CH2I2) pmol m−3 h−1 in the whole mixed layer.

Description: The availability of light in the ocean is an important parameter for the determination of phytoplankton photosynthesis processes and primary production from satellite data. It is also a useful parameter for other applications, e.g. the determination of heat fluxes. In this study, a method was developed utilising the vibrational Raman scattering (VRS) effect of water molecules to determine the number of photons available in the ocean water, which is expressed by the depth integrated scalar irradiance E0. Radiative transfer simulations with the SCIATRAN fully coupled ocean–atmosphere radiative transfer model (RTM) show clearly the relationship of E0 with the strength of the VRS signal measured at the top of the atmosphere (TOA). Taking advantage of VRS structures in hyper-spectral satellite measurements, a retrieval technique to derive E0 in the wavelength region from 390 to 444.5 nm was developed. This approach uses the weighting function differential optical absorption spectroscopy (WF-DOAS) technique, applied to TOA radiances, measured by the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY). Based on the approach of Vountas et al. (2007), where the DOAS method was used to fit modelled spectra of VRS, the method was improved by using the weighting function of VRS (VRS-WF) in the DOAS fit. This was combined with a look-up table (LUT) technique, where the E0 value was obtained for each VRS satellite fit directly. The VRS-WF and the LUT were derived from calculations with the SCIATRAN RTM (Rozanov et al., 2014). RTM simulations for different chlorophyll a concentrations and illumination conditions clearly show that low fit factors of VRS retrieval results correspond to low amounts of light in the water column and vice versa. Exemplarily, 1 month of SCIAMACHY data were processed and a global map of the depth integrated scalar irradiance E0 was retrieved. Spectral structures of VRS were clearly identified in the radiance measurements of SCIAMACHY. The fitting approach led to consistent results and the WF-DOAS algorithm results of VRS correlated clearly with the chlorophyll concentration in case-I water. Comparisons of the diffuse attenuation coefficient, extracted by VRS fit results, with the established GlobColour Kd(490) product show consistent results.

Description: The availability of light in the ocean is an important parameter for the determination of phytoplankton photosynthesis processes and primary production from satellite data. It is also a useful parameter for other applications, e.g. the determination of heat fluxes. In this study, a method was developed utilising the vibrational Raman scattering (VRS) effect of water molecules to determine the amount of photons available in the ocean water, which is expressed by the depth integrated scalar irradiance E0. Radiative transfer simulations with the fully coupled ocean–atmosphere Radiative Transfer Model (RTM) SCIATRAN show clearly the relationship of E0 to the strength of the VRS signal measured at the top of the atmosphere (TOA). Taking advantage of VRS structures in hyper-spectral satellite measurements a retrieval technique to derive E0 in the wavelength region from 390 to 444.5 nm was developed. This approach uses the Weighting Function Differential Optical Absorption Spectroscopy (WF-DOAS) technique, applied to TOA radiances, measured by the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY). Based on the approach of Vountas et al. (2007), where the DOAS method was used to fit modelled spectra of VRS, the method was improved by using the weighting function of VRS (VRS-WF) in the DOAS fit. This was combined with a look-up table (LUT) technique, where the E0 value was obtained for each VRS satellite fit directly. The VRS-WF and the LUT were derived from calculations with the RTM SCIATRAN (Rozanov et al., 2014). RTM simulations for different chlorophyll a concentrations and illumination conditions clearly show, that low fit factors of VRS retrieval results correspond to low amounts of light in the water column and vice versa. Exemplary, one month of SCIAMACHY data were processed and a global map of the depth integrated scalar irradiance E0 was retrieved. Spectral structures of VRS were clearly identified in the radiance measurements of SCIAMACHY. The fitting approach led to consistent results and the WF-DOAS algorithm results of VRS correlated clearly with the chlorophyll concentration in case-I water. Comparisons of the diffuse attenuation coefficient, extracted by VRS fit results, with the established GlobColour Kd (490) product show consistent results.

Description: The composition and abundance of algal pigments provide information on phytoplankton community characteristics such as photoacclimation, overall biomass and taxonomic composition. In particular, pigments play a major role in photoprotection and in the light-driven part of photosynthesis. Most phytoplankton pigments can be measured by high-performance liquid chromatography (HPLC) techniques applied to filtered water samples. This method, as well as other laboratory analyses, is time consuming and therefore limits the number of samples that can be processed in a given time. In order to receive information on phytoplankton pigment composition with a higher temporal and spatial resolution, we have developed a method to assess pigment concentrations from continuous optical measurements. The method applies an empirical orthogonal function (EOF) analysis to remote-sensing reflectance data derived from ship-based hyperspectral underwater radiometry and from multispectral satellite data (using the Medium Resolution Imaging Spectrometer – MERIS – Polymer product developed by Steinmetz et al., 2011) measured in the Atlantic Ocean. Subsequently we developed multiple linear regression models with measured (collocated) pigment concentrations as the response variable and EOF loadings as predictor variables. The model results show that surface concentrations of a suite of pigments and pigment groups can be well predicted from the ship-based reflectance measurements, even when only a multispectral resolution is chosen (i.e., eight bands, similar to those used by MERIS). Based on the MERIS reflectance data, concentrations of total and monovinyl chlorophyll a and the groups of photoprotective and photosynthetic carotenoids can be predicted with high quality. As a demonstration of the utility of the approach, the fitted model based on satellite reflectance data as input was applied to 1 month of MERIS Polymer data to predict the concentration of those pigment groups for the whole eastern tropical Atlantic area. Bootstrapping explorations of cross-validation error indicate that the method can produce reliable predictions with relatively small data sets (e.g., 〈 50 collocated values of reflectance and pigment concentration). The method allows for the derivation of time series from continuous reflectance data of various pigment groups at various regions, which can be used to study variability and change of phytoplankton composition and photophysiology.

Description: This study highlights recent advances and challenges of applying coupled physical-biogeochemical modeling for investigating the distribution of the key phytoplankton groups in the Southern Ocean, an area of strong interest for understanding biogeochemical cycling and ecosystem functioning under present climate change. Our simulations of the phenology of various Phytoplankton Functional Types (PFTs) are based on a version of the Darwin biogeochemical model coupled to the Massachusetts Institute of Technology (MIT) general circulation model (Darwin-MITgcm). The ecological module version was adapted for the Southern Ocean by: 1) improving coccolithophores abundance relative to the original model by introducing a high affinity for nutrients and an ability to escape grazing control for coccolithophores; 2) including two different (small vs. large) size classes of diatoms; and 3) accounting for two distinct life stages for Phaeocystis (single cell vs. colonial). This new model configuration describes best the competition and co-occurrence of the PFTs in the Southern Ocean. It improves significantly relative to an older version the agreement of the simulated abundance of the coccolithophores and diatoms with in situ scanning electron microscopy observations in the Subantarctic Zone as well as with in situ diatoms and haptophytes (including coccolithophores and Phaeocystis) chlorophyll a concentrations within the Patagonian Shelf and along the Western Antarctic Peninsula obtained by diagnostic pigment analysis. The modeled Southern Ocean PFT dominance also agrees well with satellite-based PFT information.

Description: We use isoprene and related field measurements from three different ocean data sets together with remotely sensed satellite data to model global marine isoprene emissions. We show that using monthly mean satellite derived chl-a concentrations to parameterize isoprene with a constant chl-a normalized isoprene production rate underpredicts the measured oceanic isoprene concentration by a mean factor of 19 ± 12. Improving the model by using phytoplankton functional type dependent production values and by decreasing the bacterial degradation rate of isoprene in the water column results in only a slight underestimation (factor 1.7 ± 1.2). We calculate global isoprene emissions of 0.21 Tg C for 2014 using this improved model, which is twice the value calculated using the original model. Nonetheless, the sea-to-air fluxes have to be at least one order of magnitude higher to account for measured atmospheric isoprene mixing ratios. These findings suggest that there is at least one missing oceanic source of isoprene influencing the atmospheric concentrations and, therefore, effecting the importance of marine derived isoprene as a precursor to remote marine boundary layer particle formation.

Description: Halocarbons, halogenated short-chained hydrocarbons, are produced naturally in the oceans by biological and chemical processes. They are emitted from surface seawater into the atmosphere, where they take part in numerous chemical processes such as ozone destruction and the oxidation of mercury and dimethyl sulfide. Here we present oceanic and atmospheric halocarbon data for the Peruvian upwelling obtained during the M91 cruise onboard the research vessel Meteor in December 2012. Surface waters during the cruise were characterized by moderate concentrations of bromoform (CHBr3) and dibromomethane (CH2Br2) correlating with diatom biomass derived from marker pigment concentrations, which suggests this phytoplankton group as likely source. Concentrations measured for the iodinated compounds methyl iodide (CH3I) of up to 35.4 pmol L−1, chloroiodomethane (CH2ClI) of up to 58.1 pmol L−1 and diiodomethane (CH2I2) of up to 32.4 pmol L−1 in water samples were much higher than previously reported for the tropical Atlantic upwelling systems. Iodocarbons also correlated with the diatom biomass and even more significantly with dissolved organic matter (DOM) components measured in the surface water. Our results suggest a biological source of these compounds as significant driving factor for the observed large iodocarbon concentrations. Elevated atmospheric mixing ratios of CH3I (up to 3.2 ppt), CH2ClI (up to 2.5 ppt) and CH2I2 (3.3 ppt) above the upwelling were correlated with seawater concentrations and high sea-to-air fluxes. The enhanced iodocarbon production in the Peruvian upwelling contributed significantly to tropospheric iodine levels.

Description: The climate active trace-gas carbonyl sulfide (OCS) is the most abundant sulfur gas in the atmosphere. A missing source in its atmospheric budget is currently suggested, resulting from an upward revision of the vegetation sink in top-down approaches. Oceanic emissions have been proposed to close the resulting gap in the atmospheric budget. We present a bottom-up approach including new observations of OCS in surface waters of the tropical Atlantic, Pacific and Indian oceans to show that direct OCS emissions are insufficient to account for the missing source. Extrapolation of our observations using a biogeochemical box model suggests oceanic net uptake instead of emission for the entire tropical ocean area and, further, a global ocean source strength well below that suggested by top-down estimates. This bottom-up estimate of oceanic emissions has implications for using OCS as a proxy for terrestrial CO2 uptake, which is currently hampered by the inadequate quantification of atmospheric OCS sources and sinks.

Description: A suite of oxygenated volatile organic compounds (OVOCs – acetaldehyde, acetone, propanal, butanal and butanone) were measured concurrently in the surface water and atmosphere of the South China Sea and Sulu Sea in November 2011. A strong correlation was observed between all OVOC concentrations in the surface seawater along the entire cruise track, except for acetaldehyde, suggesting similar sources and sinks in the surface ocean. Additionally, several phytoplankton groups, such as haptophytes or pelagophytes, were also correlated to all OVOCs indicating that phytoplankton may be an important source for marine OVOCs in the South China and Sulu Seas. Humic and protein like fluorescent dissolved organic matter (FDOM) components seemed to be additional precursors for butanone and acetaldehyde. The atmospheric OVOC mixing ratios were relative high compared with literature values, suggesting the coastal region of North Borneo as a local hot spot for atmospheric OVOCs. The flux of atmospheric OVOCs was largely into the ocean for all 5 gases, with a few important exceptions near the coast of Borneo. The calculated amount of OVOCs entrained into the ocean seemed to be an important source of OVOCs to the surface ocean. When the fluxes were out of the ocean, marine OVOCs were found to be enough to control the local measured OVOC distribution in the atmosphere. Based on our model calculations, at least 0.4 ppb of marine derived acetone and butanone can reach the upper troposphere, where they may have an important influence on hydrogen oxide radical formation over the western Pacific Ocean.

Description: Halocarbons from oceanic sources contribute to halogens in the troposphere, and can be transported into the stratosphere where they take part in ozone depletion. This paper presents distribution and sources in the equatorial Atlantic from June and July 2011 of the four compounds bromoform (CHBr3), dibromomethane (CH2Br2), methyl iodide (CH3I) and diiodomethane (CH2I2). Enhanced biological production during the Atlantic Cold Tongue (ACT) season, indicated by phytoplankton pigment concentrations, led to elevated concentrations of CHBr3 of up to 44.7 and up to 9.2 pmol L−1 for CH2Br2 in surface water, which is comparable to other tropical upwelling systems. While both compounds correlated very well with each other in the surface water, CH2Br2 was often more elevated in greater depth than CHBr3, which showed maxima in the vicinity of the deep chlorophyll maximum. The deeper maximum of CH2Br2 indicates an additional source in comparison to CHBr3 or a slower degradation of CH2Br2. Concentrations of CH3I of up to 12.8 pmol L−1 in the surface water were measured. In contrary to expectations of a predominantly photochemical source in the tropical ocean, its distribution was mostly in agreement with biological parameters, indicating a biological source. CH2I2 was very low in the near surface water with maximum concentrations of only 3.7 pmol L−1. CH2I2 showed distinct maxima in deeper waters similar to CH2Br2. For the first time, diapycnal fluxes of the four halocarbons from the upper thermocline into and out of the mixed layer were determined. These fluxes were low in comparison to the halocarbon sea-to-air fluxes. This indicates that despite the observed maximum concentrations at depth, production in the surface mixed layer is the main oceanic source for all four compounds and one of the main driving factors of their emissions into the atmosphere in the ACT-region. The calculated production rates of the compounds in the mixed layer are 34 ± 65 pmol m−3 h−1 for CHBr3, 10 ± 12 pmol m−3 h−1 for CH2Br2, 21 ± 24 pmol m−3 h−1 for CH3I and 384 ± 318 pmol m−3 h−1 for CH2I2 determined from 13 depth profiles.