The production, size, and chemical composition of sea spray aerosol (SSA) particles strongly depend on seawater chemistry, which is controlled by physical, chemical, and biological processes. Despite decades of studies in marine environments, a direct relationship has yet to be established between ocean biology and the physicochemical properties of SSA. The ability to establish such relationships is hindered by the fact that SSA measurements are typically dominated by overwhelming background aerosol concentrations even in remote marine environments. Herein, we describe a newly developed approach for reproducing the chemical complexity of SSA in a laboratory setting, comprising a unique ocean-atmosphere facility equipped with actual breaking waves. A mesocosm experiment was performed in natural seawater, using controlled phytoplankton and heterotrophic bacteria concentrations, which showed SSA size and chemical mixing state are acutely sensitive to the aerosol production mechanism, as well as to the type of biological species present. The largest reduction in the hygroscopicity of SSA occurred as heterotrophic bacteria concentrations increased, whereas phytoplankton and chlorophyll-a concentrations decreased, directly corresponding to a change in mixing state in the smallest (60-180 nm) size range. Using this newly developed approach to generate realistic SSA, systematic studies can now be performed to advance our fundamental understanding of the impact of ocean biology on SSA chemical mixing state, heterogeneous reactivity, and the resulting climaterelevant properties.clouds | marine aerosols | biologically active | cloud condensation nuclei | ice nucleation

An ammonia-oxidizing, carbon-fixing archaeon, Candidatus ''Nitrosopumilus maritimus,'' recently was isolated from a salt-water aquarium, definitively confirming that chemoautotrophy exists among the marine archaea. However, in other incubation studies, pelagic archaea also were capable of using organic carbon. It has remained unknown what fraction of the total marine archaeal community is autotrophic in situ. If archaea live primarily as autotrophs in the natural environment, a large ammonia-oxidizing population would play a significant role in marine nitrification. Here we use the natural distribution of radiocarbon in archaeal membrane lipids to quantify the bulk carbon metabolism of archaea at two depths in the subtropical North Pacific gyre. Our compound-specific radiocarbon data show that the archaea in surface waters incorporate modern carbon into their membrane lipids, and archaea at 670 m incorporate carbon that is slightly more isotopically enriched than inorganic carbon at the same depth. An isotopic mass balance model shows that the dominant metabolism at depth indeed is autotrophy (83%), whereas heterotrophic consumption of modern organic carbon accounts for the remainder of archaeal biomass. These results reflect the in situ production of the total community that produces tetraether lipids and are not subject to biases associated with incubation and͞or culture experiments. The data suggest either that the marine archaeal community includes both autotrophs and heterotrophs or is a single population with a uniformly mixotrophic metabolism. The metabolic and phylogenetic diversity of the marine archaea warrants further exploration; these organisms may play a major role in the marine cycles of nitrogen and carbon.biomarkers ͉ carbon isotopes ͉ microbial ecology ͉ nitrogen cycle ͉ oceanography N onthermophilic archaea represent up to 40% of the free-living prokaryotic community in the water column of the world's oceans (1-6), but until recently there has been limited information about the sources of carbon and energy that fuel these organisms (7-11). The characteristic membrane lipids of planktonic archaea include glycerol dialkyl glycerol tetraethers (GDGTs) (12). These compounds are ubiquitous in marine sediments and ocean water (12-15). The relative abundance of individual GDGTs recovered from sediments is used to reconstruct sea-surface temperatures (16)(17)(18). This distribution, known as TEX 86 , has been shown through experimental manipulation of surface-water mesocosm experiments to respond to changes in incubation temperature (18). In addition, the ␦ 13 C values of GDGTs display a remarkably constant offset from ␦ 13 C values of dissolved inorganic carbon (DIC) over a range of settings and geologic time (13,(19)(20)(21). The collective metabolic activities of the numerous archaea in the ocean are likely to play a significant role in the cycling of organic carbon (OC) and nutrients, and their membrane lipids show significant utility for paleoceanography. However, neither the metabolic requiremen...

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This paper describes the application of a novel, practical approach for isolation of individual compounds from complex organic matrices for natural abundance radiocarbon measurement. This is achieved through the use of automated preparative capillary gas chromatography (PCGC) to separate and recover sufficient quantities of individual target compounds for 14 C analysis by accelerator mass spectrometry (AMS). We developed and tested this approach using a suite of samples (plant lipids, petroleums) whose ages spanned the 14 C time scale and which contained a variety of compound types (fatty acids, sterols, hydrocarbons). Comparison of individual compound and bulk radiocarbon signatures for the isotopically homogeneous samples studied revealed that ∆ 14 C values generally agreed well ((10%). Background contamination was assessed at each stage of the isolation procedure, and incomplete solvent removal prior to combustion was the only significant source of additional carbon. Isotope fractionation was addressed through compound-specific stable carbon isotopic analyses. Fractionation of isotopes during isolation of individual compounds was minimal (<5‰ for δ 13 C), provided the entire peak was collected during PCGC. Trapping of partially coeluting peaks did cause errors, and these results highlight the importance of conducting stable carbon isotopic measurements of each trapped compound in concert with AMS for reliable radiocarbon measurements. The addition of carbon accompanying derivatization of functionalized compounds (e.g., fatty acids and sterols) prior to chromatographic separation represents a further source of potential error. This contribution can be removed using a simple isotopic mass balance approach. Based on these preliminary results, the PCGC-based approach holds promise for accurately determining 14 C ages on compounds specific to a given source within complex, heterogeneous samples.

Dissolved organic matter (DOM) in the oceans is one of the largest pools of reduced carbon on Earth, comparable in size to the atmospheric CO 2 reservoir. A vast number of compounds are present in DOM, and they play important roles in all major element cycles, contribute to the storage of atmospheric CO 2 in the ocean, support marine ecosystems, and facilitate interactions between organisms. At the heart of the DOM cycle lie molecular-level relationships between the individual compounds in DOM and the members of the ocean microbiome that produce and consume them. In the past, these connections have eluded clear definition because of the sheer numerical complexity of both DOM molecules and microorganisms. Emerging tools in analytical chemistry, microbiology, and informatics are breaking down the barriers to a fuller appreciation of these connections. Here we highlight questions being addressed using recent methodological and technological developments in those fields and consider how these advances are transforming our understanding of some of the most important reactions of the marine carbon cycle.dissolved organic matter | marine microbes | cyberinfrastructure