ALBERT

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 coastal upwelling system off the coast of Peru is characterized by high biological activity and a pronounced subsurface oxygen minimum zone, as well as associated emissions of atmospheric trace gases such as N2O, CH4 and CO2. From 3 to 23 December 2012, R/V Meteor (M91) cruise took place in the Peruvian upwelling system between 4.59 and 15.4° S, and 82.0 to 77.5° W. During M91 we investigated the composition of the sea-surface microlayer (SML), the oceanic uppermost boundary directly subject to high solar radiation, often enriched in specific organic compounds of biological origin like chromophoric dissolved organic matter (CDOM) and marine gels. In the SML, the continuous photochemical and microbial recycling of organic matter may strongly influence gas exchange between marine systems and the atmosphere. We analyzed SML and underlying water (ULW) samples at 38 stations focusing on CDOM spectral characteristics as indicator of photochemical and microbial alteration processes. CDOM composition was characterized by spectral slope (S) values and excitation–emission matrix fluorescence (EEMs), which allow us to track changes in molecular weight (MW) of DOM, and to determine potential DOM sources and sinks. Spectral slope S varied between 0.012 to 0.043 nm−1 and was quite similar between SML and ULW, with no significant differences between the two compartments. Higher S values were observed in the ULW of the southern stations below 15° S. By EEMs, we identified five fluorescent components (F1–5) of the CDOM pool, of which two had excitation/emission characteristics of amino-acid-like fluorophores (F1, F4) and were highly enriched in the SML, with a median ratio SML : ULW of 1.5 for both fluorophores. In the study region, values for CDOM absorption ranged from 0.07 to 1.47 m−1. CDOM was generally highly concentrated in the SML, with a median enrichment with respect to the ULW of 1.2. CDOM composition and changes in spectral slope properties suggested a local microbial release of DOM directly in the SML as a response to light exposure in this extreme environment. In a conceptual model of the sources and modifications of optically active DOM in the SML and underlying seawater (ULW), we describe processes we think may take place (Fig. 1); the production of CDOM of higher MW by microbial release through growth, exudation and lysis in the euphotic zone, includes the identified fluorophores (F1, F2, F3, F4, F5). Specific amino-acid-like fluorophores (F1, F4) accumulate in the SML with respect to the ULW, as photochemistry may enhance microbial CDOM release by (a) photoprotection mechanisms and (b) cell-lysis processes. Microbial and photochemical degradation are potential sinks of the amino-acid-like fluorophores (F1, F4), and potential sources of reworked and more refractory humic-like components (F2, F3, F5). In the highly productive upwelling region along the Peruvian coast, the interplay of microbial and photochemical processes controls the enrichment of amino-acid-like CDOM in the SML. We discuss potential implications for air–sea gas exchange in this area.

Description: The sea-surface microlayer (SML) is at the uppermost surface of the ocean, linking the hydrosphere with the atmosphere. The presence and enrichment of organic compounds in the SML have been suggested to influence air–sea gas exchange processes as well as the emission of primary organic aerosols. Here, we report on organic matter components collected from an approximately 50 µm thick SML and from the underlying water (ULW),  ∼  20 cm below the SML, in December 2012 during the SOPRAN METEOR 91 cruise to the highly productive, coastal upwelling regime off the coast of Peru. Samples were collected at 37 stations including coastal upwelling sites and off-shore stations with less organic matter and were analyzed for total and dissolved high molecular weight (〉 1 kDa) combined carbohydrates (TCCHO, DCCHO), free amino acids (FAA), total and dissolved hydrolyzable amino acids (THAA, DHAA), transparent exopolymer particles (TEP), Coomassie stainable particles (CSPs), total and dissolved organic carbon (TOC, DOC), total and dissolved nitrogen (TN, TDN), as well as bacterial and phytoplankton abundance. Our results showed a close coupling between organic matter concentrations in the water column and in the SML for almost all components except for FAA and DHAA that showed highest enrichment in the SML on average. Accumulation of gel particles (i.e., TEP and CSP) in the SML differed spatially. While CSP abundance in the SML was not related to wind speed, TEP abundance decreased with wind speed, leading to a depletion of TEP in the SML at about 5 m s−1. Our study provides insight to the physical and biological control of organic matter enrichment in the SML, and discusses the potential role of organic matter in the SML for air–sea exchange processes.

Description: Halocarbons 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 zone 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 is a 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 a 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. During the first part of the cruise, the enhanced iodocarbon production in the Peruvian upwelling contributed significantly to tropospheric iodine levels, while this contribution was considerably smaller during the second part.

Description: The interface layer between ocean and atmosphere is only a couple of micrometers thick but plays a critical role in climate relevant processes, including the air-sea exchange of gas and heat and the emission of primary organic aerosols (POA). Recent findings suggest that low-level cloud formation above the Arctic Ocean may be linked to organic polymers produced by marine microorganisms. Sea ice harbors high amounts of polymeric substances that are produced by cells growing within the sea-ice brine. Here, we report from a research cruise to the central Arctic Ocean in 2012. Our study shows that microbial polymers accumulate at the air-sea interface when the sea ice melts. Proteinaceous compounds represented the major fraction of polymers supporting the formation of a gelatinous interface microlayer and providing a hitherto unrecognized potential source of marine POA. Our study indicates a novel link between sea ice-ocean and atmosphere that may be sensitive to climate change.

Description: About 5 trillion plastic particles are present in our oceans, from the macro to the micro size. Like any other aquatic particulate, plastics and microplastics can create a micro-environment, within which microbial and chemical conditions differ significantly from the surrounding water. Despite the high and increasing abundance of microplastics in the ocean, their influence on the transformation and composition of marine organic matter is largely unknown. Chromophoric dissolved organic matter (CDOM) is the photo-reactive fraction of the marine dissolved organic matter (DOM) pool. Changes in CDOM quality and quantity have impacts on marine microbial dynamics and the underwater light environment. One major source of CDOM is produced by marine bacteria through their alteration of pre-existing DOM substrates. In a series of microcosm experiments in controlled marine conditions, we explored the impact of microplastics on the quality and quantity of microbial CDOM. In the presence of microplastics we observed an increased production of CDOM with changes in its molecular weight, which resulted from either an increased microbial CDOM production or an enhanced transformation of DOM from lower to higher molecular weight CDOM. Our results point to the possibility that marine microplastics act as localized hot spots for microbial activity, with the potential to influence marine carbon dynamics

Description: Millions of tons of riverine plastic waste enter the ocean via estuaries annually. The plastics accumulate, fragment, mix and interact with organisms in these dynamic systems, but such processes have received limited attention relative to open-ocean sites. In this Perspective, we discuss the occurrence and convergence of microplastics at estuarine fronts, focusing on their interactions with physical, geochemical and biological processes. Microplastic transformation can be enhanced within frontal systems owing to strong turbulence and interactions with sediment and biological particles, exacerbating the potential ecosystem impacts. The formation of microplastic hotspots at estuarine fronts could be a target for future plastic pollution mitigation efforts. Knowledge of the mechanics of plastic dispersal, accumulation and fate in frontal zones will, in turn, improve our understanding of plastic waste along the land–sea aquatic continuum.