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The Organic Sea-Surface Microlayer in the Upwelling Region Off the Coast of Peru and Potential Implications for Air–Sea Exchange Processes

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The Organic Sea-Surface Microlayer in the Upwelling Region Off the Coast of Peru and Potential Implications for Air–Sea Exchange Processes Biogeosciences, 13, 989–1007, 2016 www.biogeosciences.net/13/989/2016/ doi:10.5194/bg-13-989-2016 © Author(s) 2016. CC Attribution 3.0 License. The organic sea-surface microlayer in the upwelling region off the coast of Peru and potential implications for air–sea exchange processes Anja Engel and Luisa Galgani GEOMAR – Helmholtz Centre for Ocean Research Kiel, Düsternbrooker Weg 20, 24105 Kiel, Germany Correspondence to: Anja Engel ([email protected]) Received: 29 May 2015 – Published in Biogeosciences Discuss.: 9 July 2015 Revised: 23 December 2015 – Accepted: 27 January 2016 – Published: 22 February 2016 Abstract. The sea-surface microlayer (SML) is at the upper- 1 Introduction most surface of the ocean, linking the hydrosphere with the atmosphere. The presence and enrichment of organic com- The sea-surface microlayer (SML) is the uppermost layer of pounds in the SML have been suggested to influence air– the water column and the interface between the ocean and sea gas exchange processes as well as the emission of pri- the atmosphere. The accumulation of organic matter, distinct mary organic aerosols. Here, we report on organic matter physical and chemical properties and a specific organismal components collected from an approximately 50 µm thick community (neuston) distinguish the SML as a unique bio- SML and from the underlying water (ULW), ∼ 20 cm be- geochemical and ecological system. It has been suggested low the SML, in December 2012 during the SOPRAN ME- that the SML has a gel-like nature (Cunliffe and Murrell, TEOR 91 cruise to the highly productive, coastal upwelling 2009; Sieburth, 1983) of varying thickness (20–150 µm, Cun- regime off the coast of Peru. Samples were collected at 37 liffe et al., 2013) with dissolved polymeric carbohydrates and stations including coastal upwelling sites and off-shore sta- amino acids present as well as gel particles, such as trans- tions with less organic matter and were analyzed for total and parent exopolymer particles (TEP) of polysaccharidic com- dissolved high molecular weight (> 1 kDa) combined carbo- position, and Coomassie stainable particles (CSPs) of pro- hydrates (TCCHO, DCCHO), free amino acids (FAA), total teinaceous composition. These gelatinous compounds origi- and dissolved hydrolyzable amino acids (THAA, DHAA), nate from high molecular weight polymers that are released transparent exopolymer particles (TEP), Coomassie stainable form phytoplankton and bacterial cells by exudation and cell particles (CSPs), total and dissolved organic carbon (TOC, break up (Chin et al., 1998; Engel et al., 2004; Verdugo et DOC), total and dissolved nitrogen (TN, TDN), as well as al., 2004). Polysaccharide-rich gels, like TEP, were attributed bacterial and phytoplankton abundance. Our results showed a mainly to phytoplankton exudation (Passow, 2002), while close coupling between organic matter concentrations in the the production of protein-containing gels, such as CSPs, has water column and in the SML for almost all components ex- been related to cell lysis and decomposition, as well as to cept for FAA and DHAA that showed highest enrichment in the absorption of proteins onto non-proteinaceous particles the SML on average. Accumulation of gel particles (i.e., TEP (Long and Azam, 1996). Gels are transported to the SML and CSP) in the SML differed spatially. While CSP abun- by rising bubbles (Azetsu-Scott and Passow, 2004; Zhou et dance in the SML was not related to wind speed, TEP abun- al., 1998) or are produced from dissolved precursors directly dance decreased with wind speed, leading to a depletion of at the air–sea interface during surface wave action (Wurl et TEP in the SML at about 5 m s−1. Our study provides in- al., 2011). Gel particles can promote microbial biofilm for- sight to the physical and biological control of organic matter mation (Bar-Zeev et al., 2012) and mediate vertical organic enrichment in the SML, and discusses the potential role of matter transport, either to the atmosphere (Leck and Bigg, organic matter in the SML for air–sea exchange processes. 2005; Orellana et al., 2011) or to the deep ocean (Passow, 2002). Published by Copernicus Publications on behalf of the European Geosciences Union. 990 Anja Engel and Luisa Galgani: The organic sea-surface microlayer Accumulation of organic matter in the SML may be tightly derstood in order to accurately estimate trace gas fluxes from coupled to phytoplankton abundance in the water column the ocean to the atmosphere and consequences on climate. (Bigg et al., 2004; Galgani et al., 2014; Gao et al., 2012; In 2008, the VAMOS Ocean-Cloud-Atmosphere-Land Study Matrai et al., 2008). Thus, organic matter accumulation and Regional Experiment (VOCALS-REx) and the Chilean Up- composition in the SML may also reflect the sensitivity of welling Experiment (VOCALS-CUpEx) conducted between marine microorganisms in the surface ocean to environmen- Southern Peru and Northern Chile focused on the link be- tal changes, which was shown during previous mesocosms tween aerosols, clouds and precipitation as well as on physi- studies (Engel et al., 2013; Riebesell et al., 2009; Schulz cal and chemical couplings between the upper ocean and the et al., 2013). Distinct from the SML and on top of it lies lower atmosphere (Garreaud et al., 2011; Wood et al., 2011). the nanolayer, a monomolecular film, which, like the SML, During the SOPRAN cruise METEOR91 (M91), we stud- shows seasonality features with carbohydrate-rich polymeric ied organic matter components at the very sea surface since material being most abundant during the summer months properties of the SML may represent a major uncertainty for and possibly related to a combination of primary produc- gas, heat and aerosol fluxes in this specific region and in other tion (phytoplankton abundance) and photochemical and/or oceanic environments. During our cruise, organic matter con- microbial reworking of organic matter (Laß et al., 2013). centration and composition of the SML and the underlying In our study we focused on the upper micrometers of seawater were studied on 37 different stations, providing the the water–air interface that we operationally define as SML, first SML data set for the upwelling system off the coast of whose compositional changes and accumulation of organic Peru, including the first data set on gel particles in EBUSs so matter may influence two air–sea interface processes nec- far. essary to understand oceanic feedbacks on the atmosphere: sea-spray aerosol (SSA) emission and air–sea gas exchange (Cunliffe et al., 2013). During biologically productive peri- 2 Material and methods ods, a high amount of SSA with a predominant organic com- position is emitted from the ocean’s surface (O’Dowd et al., 2.1 Field information and sampling 2004). These compounds primarily reveal a polysaccharidic, gel-like composition, suggesting that the abundance and size The R/V METEOR cruise M91 studied the upwelling region of dissolved polysaccharides and marine gels in the sea sur- off the coast of Peru (Bange, 2013). Samples were collected face may influence the organic fraction of SSA (Orellana et between 4.59◦ S and 82.0◦ W, and 15.4◦ S and 77.5◦ W from al., 2011; Russell et al., 2010). It has also been shown that 3 to 23 December in 2012. The overall goal of M91 was to the presence of biogenic surface active substances (surfac- conduct an integrated biogeochemical study on the upwelling tants) in the SML leads to capillary wave damping, alters region off the coast of Peru in order to assess the importance the molecular diffusion of gases (Frew et al., 1990; Liss and of OMZs for the sea-air exchange of various climate-relevant Duce, 2005) and thereby affects gas exchange rates particu- trace gases and for tropospheric chemistry. Salinity and tem- larly at lower wind speed (Jähne and Haußecker, 1998). In perature were measured with a CTD at each station. Global this respect, the understanding of sources, composition and and UV radiation and wind speed data were retrieved from fate of biological components in the SML becomes of partic- the DShip database for the time of sampling based on the ular relevance for environments, where biological productiv- sensors installed on board. ity is high like in coastal upwelling regimes. On 37 different stations between 5 and 16◦ S off the Pe- Off the coast of Peru, the coastal upwelling region extends ruvian coast (Fig. 1), a total of 39 SML samples was col- between approximately 4 and 40◦ S. In this area, upwelling lected from a rubber boat using a glass plate sampler ac- processes are sustained by winds throughout the year but fea- cording to the original approach described by Harvey and ture high inter-annual variability induced by the El Niño– Burzell (1972). Different methods have been developed to Southern Oscillation (ENSO) cycle (Tarazona and Arntz, sample and investigate the SML. These methods do not only 2001). Eastern boundary upwelling systems (EBUSs) like differ in terms of application but also with respect to the the system off the coast of Peru are characterized by high thickness of the SML sampled as well as to selective removal biological productivity supported by deep upwelling of nutri- of certain components. Several studies evaluated these meth- ents and often associated with subsurface oxygen minimum ods against each other. A recent summary can be found in zones (OMZs). The supply of oxygen to the OMZ is largely the “Guide to best practices to study the ocean’s surface” controlled by physical (i.e., diffusive and advective) mecha- (Cunliffe and Wurl, 2014). During this study, we applied the nisms, whereas biological processes (i.e., respiration of or- glass plate technique because it allows for sampling of a rela- ganic matter) provide sinks (Lachkar and Gruber, 2011). tively large volume needed to analyze different organic com- OMZs are significant source regions for major climate- ponents while keeping the simultaneous sampling of ULW relevant gases such as carbon dioxide, methane, hydrogen minimal.
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