Exploring Variability of Trichodesmium Photophysiology Using Multi-Excitation Wavelength Fast Repetition Rate Fluorometry.

Fast repetition rate fluorometry (FRRf) allows for rapid non-destructive assessment of phytoplankton photophysiology in situ yet has rarely been applied to Trichodesmium. This gap reflects long-standing concerns that Trichodesmium (and other cyanobacteria) contain pigments that are less effective at absorbing blue light which is often used as the sole excitation source in FRR fluorometers-potentially leading to underestimation of key fluorescence parameters. In this study, we use a multi-excitation FRR fluorometer (equipped with blue, green, and orange LEDs) to investigate photophysiological variability in Trichodesmium assemblages from two sites. Using a multi-LED measurement protocol (447+519+634 nm combined), we assessed maximum photochemical efficiency (F v /F m ), functional absorption cross section of PSII (σ PSII ), and electron transport rates (ETRs) for Trichodesmium assemblages in both the Northwest Pacific (NWP) and North Indian Ocean in the vicinity of Sri Lanka (NIO-SL). Evaluating fluorometer performance, we showed that use of a multi-LED measuring protocol yields a significant increase of F v /F m for Trichodesmium compared to blue-only excitation. We found distinct photophysiological differences for Trichodesmium at both locations with higher average F v /F m as well as lower σ PSII and non-photochemical quenching (NPQ NSV ) observed in the NWP compared to the NIO-SL (Kruskal-Wallis t-test df = 1, p < 0.05). Fluorescence light response curves (FLCs) further revealed differences in ETR response with a lower initial slope (α ETR ) and higher maximum electron turnover rate ( E T R P S I I m a x ) observed for Trichodesmium in the NWP compared to the NIO-SL, translating to a higher averaged light saturation E K (= E T R P S I I m a x /α ETR ) for cells at this location. Spatial variations in physiological parameters were both observed between and within regions, likely linked to nutrient supply and physiological stress. Finally, we applied an algorithm to estimate primary productivity of Trichodesmium using FRRf-derived fluorescence parameters, yielding an estimated carbon-fixation rate ranging from 7.8 to 21.1 mgC mg Chl-a-1 h-1 across this dataset. Overall, our findings demonstrate that capacity of multi-excitation FRRf to advance the application of Chl-a fluorescence techniques in phytoplankton assemblages dominated by cyanobacteria and reveals novel insight into environmental regulation of photoacclimation in natural Trichodesmium populations.

Experimental Techniques to Assess Coral Physiology in situ Under Global and Local Stressors: Current Approaches and Novel Insights.

Coral reefs are declining worldwide due to global changes in the marine environment. The increasing frequency of massive bleaching events in the tropics is highlighting the need to better understand the stages of coral physiological responses to extreme conditions. Moreover, like many other coastal regions, coral reef ecosystems are facing additional localized anthropogenic stressors such as nutrient loading, increased turbidity, and coastal development. Different strategies have been developed to measure the health status of a damaged reef, ranging from the resolution of individual polyps to the entire coral community, but techniques for measuring coral physiology in situ are not yet widely implemented. For instance, while there are many studies of the coral holobiont response in single or limited-number multiple stressor experiments, they provide only partial insights into metabolic performance under more complex and temporally and spatially variable natural conditions. Here, we discuss the current status of coral reefs and their global and local stressors in the context of experimental techniques that measure core processes in coral metabolism (respiration, photosynthesis, and biocalcification) in situ, and their role in indicating the health status of colonies and communities. We highlight the need to improve the capability of in situ studies in order to better understand the resilience and stress response of corals under multiple global and local scale stressors.

Metabolic performance and thermal and salinity tolerance of the coral Platygyra carnosa in Hong Kong waters.

Stress-tolerant coral species, such as Platygyra spp., are considered to be well adapted to survive in marginal reefs, but their physiological response to short term exposure to abnormally high temperature and lowered salinity remains poorly understood. Using non-invasive techniques to quantitatively assess the health of Platygyra carnosa (e.g. respiration, photosynthesis, biocalcification and whiteness), we identified the plasticity of its energetics and physiological limits. Although these indicators suggest that it can survive to increasing temperature (25-32 °C), its overall energetics were seriously diminished at temperatures >30 °C. In contrast, it was well adapted to hyposaline waters (31-21 psu) but with reduced biocalcification, indicating short term adaptation for expected future changes in salinity driven by increased amounts and intensities of precipitation. Our findings provide useful insights to the effect of these climate drivers on P. carnosa metabolism and thus better forecast changes in their health status under future climate change scenarios.

Future HAB science: Directions and challenges in a changing climate.

There is increasing concern that accelerating environmental change attributed to human-induced warming of the planet may substantially alter the patterns, distribution and intensity of Harmful Algal Blooms (HABs). Changes in temperature, ocean acidification, precipitation, nutrient stress or availability, and the physical structure of the water column all influence the productivity, composition, and global range of phytoplankton assemblages, but large uncertainty remains about how integration of these climate drivers might shape future HABs. Presented here are the collective deliberations from a symposium on HABs and climate change where the research challenges to understanding potential linkages between HABs and climate were considered, along with new research directions to better define these linkages. In addition to the likely effects of physical (temperature, salinity, stratification, light, changing storm intensity), chemical (nutrients, ocean acidification), and biological (grazer) drivers on microalgae (senso lato), symposium participants explored more broadly the subjects of cyanobacterial HABs, benthic HABs, HAB effects on fisheries, HAB modelling challenges, and the contributions that molecular approaches can bring to HAB studies. There was consensus that alongside traditional research, HAB scientists must set new courses of research and practices to deliver the conceptual and quantitative advances required to forecast future HAB trends. These different practices encompass laboratory and field studies, long-term observational programs, retrospectives, as well as the study of socioeconomic drivers and linkages with aquaculture and fisheries. In anticipation of growing HAB problems, research on potential mitigation strategies should be a priority. It is recommended that a substantial portion of HAB research among laboratories be directed collectively at a small sub-set of HAB species and questions in order to fast-track advances in our understanding. Climate-driven changes in coastal oceanographic and ecological systems are becoming substantial, in some cases exacerbated by localized human activities. That, combined with the slow pace of decreasing global carbon emissions, signals the urgency for HAB scientists to accelerate efforts across disciplines to provide society with the necessary insights regarding future HAB trends.

Effects of increasing temperature and acidification on the growth and competitive success of Alexandrium catenella from the Gulf of Maine.

Climate driven increases in ocean temperature and pCO2 have the potential to alter the growth and prevalence of future Harmful Algal Blooms (HABs), but systematic studies on how climate drivers influence toxic algal species relative to non-toxic phytoplankton are lacking. In particular, little is known about how future climate scenarios will affect the growth of the toxic dinoflagellate Alexandrium catenella, which is responsible for the paralytic shellfish poisoning (PSP) events that threaten the health and economy of coastal communities in the Gulf of Maine and elsewhere. The growth responses of A. catenella and two other naturally co-occurring dinoflagellates in the Gulf of Maine-Scrippsiella sp., and Amphidinium carterae-were studied in mono and mixed species cultures. Experimental treatments tested the effects of elevated temperature (20 °C), lower pH (7.8), and the combination of elevated temperature and lower pH on growth rates relative to those in near-current conditions (15 °C; pH 8.1). Growth rates of A. catenella decreased under elevated temperature and lower pH conditions, a response that was largely attributable to the effect of temperature. In contrast, growth rates of Scrippsiella sp. and A. carterae increased under elevated temperature and lower pH conditions, with temperature also being the primary driver of the response. These trends did not change substantially when these species were grown in mixed cultures (A. catenella + Scrippsiella sp., and A. catenella + A. carterae), indicating that allelopathic or competitive interactions did not affect the experimental outcome under the conditions tested. These findings suggest that A. catenella blooms may become less prevalent in the southern regions of the Gulf of Maine, but potentially more prevalent in the northeastern regions of the Gulf of Maine with continued climate change.

Insensitivities of a subtropical productive coastal plankton community and trophic transfer to ocean acidification: Results from a microcosm study.

Ocean acidification (OA) has potential to affect marine phytoplankton in ways that are partly understood, but there is less knowledge about how it may alter the coupling to secondary producers. We investigated the effects of OA on phytoplankton primary production, and its trophic transfer to zooplankton in a subtropical eutrophic water (Wuyuan Bay, China) under present day (400 µatm) and projected end-of-century (1000 µatm) pCO2 levels. Net primary production was unaffected, although OA did lead to small decreases in growth rates. OA had no measurable effect on micro-/mesozooplankton grazing rates. Elevated pCO2 had no effect on phytoplankton fatty acid (FA) concentrations during exponential phase, but saturated FAs increased relative to the control during declining phase. FA profiles of mesozooplankton were unaffected. Our findings show that short-term exposure of plankton communities in eutrophic subtropical waters to projected end-of-century OA conditions has little effect on primary productivity and trophic linkage to mesozooplankton.

The successional formation and release of domoic acid in a Pseudo-nitzschia bloom in the Juan de Fuca Eddy: A drifter study.

Blooms of Pseudo-nitzschia species are frequent, but presently unpredictable, in the Juan de Fuca Eddy region off the coasts of Washington (US) and British Columbia (Canada). This upwelling eddy region is proposed to be the bloom commencement site, before cells are entrained into the coastal surface currents. During a shipboard study, we characterized the different stages of the Pseudo-nitzschia bloom development from its initiation and intensification, to its eventual sinking and dissipation. Specifically, we followed a water mass using lagrangian ARGOS-tracked drifters released at the eddy water mass and quantified production of dissolved and particulate domoic acid, and the physiological status of the Pseudo-nitzschia cells with regards to photosynthesis, nutrient needs and sinking rates, along with its relationship with competing species - in this case, the marine euglenoid, Eutreptiella spp. The drifter study allows for an interpretation of the presence or absence of Pseudo-nitzschia and domoic acid against active environmental factors - particularly copper and iron.

Characterization of oceanic Noctiluca blooms not associated with hypoxia in the Northeastern Arabian Sea.

Intense blooms of the heterotrophic dinoflagellate, green Noctiluca scintillans, have been reported annually in the Northern Arabian Sea since the early 2000s. Although not known to produce organic toxins, these blooms are still categorized as a harmful due to their association with massive fish mortalities. Recent work has attributed these blooms to the vertical expansion of the oxygen minimum zone, driven by cultural eutrophication from major coastal cities in western India. As diatoms are preferred prey of green Noctiluca scintillans, more frequent blooms of this mixotroph will likely impact the productivity of important fisheries in the region. The present study uses a satellite algorithm to determine the distribution of both diatom and green Noctiluca blooms in the Northeastern Arabian Sea from 2009 to 2016. The results from shipboard microscopy of phytoplankton community composition were used to validate the satellite estimates. The satellite algorithm showed 76% accuracy for detection of green Noctiluca and 92% for diatoms. Shipboard measurements and data from biogeochemical-Argo floats were used to assess the relationship between oxygen concentrations and green Noctiluca blooms in the Northeastern Arabian Sea. Regardless of the presence of a Noctiluca bloom, the dissolved oxygen in the photic zone was always >70% saturated, with an average oxygen saturation >90%. The variability in the relative abundance of diatoms and green Noctiluca is not correlated with changes in oxygen concentration. These findings provide no evidence that cultural eutrophication has contributed to the decadal scale shifts in plankton composition in the Northeastern Arabian Sea oceanic waters. Conversely, the climatic warming of surface waters would have intensified stratification, thereby reducing net nutrient flux to the photic zone and decreasing silicate to nitrate ratios (Si:N); both factors that could increase the competitive advantage of the mixotroph, green Noctiluca, over diatoms. If so, the decadal-scale trajectory of phytoplankton community composition in the Northeastern Arabian Sea may be a harbinger of future climate-driven change in other productive oceanic systems.

The fatty acid content of plankton is changing in subtropical coastal waters as a result of OA: Results from a mesocosm study.

Ocean Acidification (OA) effects on marine plankton are most often considered in terms of inorganic carbon chemistry, but decreasing pH may influence other aspects of cellular metabolism. Here we present the effects of OA on the fatty acid (FA) content and composition of an artificial phytoplankton community (Phaeodactylum tricornutum, Thalassiosira weissflogii, and Emiliania huxleyi) in a fully replicated, ∼4 m3 mesocosm study in subtropical coastal waters (Wuyuan Bay, China, 24.52°N, 117.18°E) at present day (400 µatm) and elevated (1000 µatm) pCO2 concentrations. Phytoplankton growth occurred in three phases during the 33-day experiment: an initial exponential growth leading to senescence and a subsequent decline phase. Phytoplankton sampled from these mesocosms were fed to mesozooplankton collected by net haul from Wuyuan Bay. Concentrations of saturated fatty acids (SFA) in both phytoplankton and mesozooplankton remained high under acidified and non-acidified conditions. However, polyunsaturated fatty acids (PUFA) and monounsaturated fatty acids (MUFA) increased significantly more under elevated pCO2 during the late exponential phase (Day 13), indicating increased nutritional value for zooplankton and higher trophic levels. Indeed, uptake rates of the essential FA docosahexaenoic acid (C20:5n3, DHA) increased in mesozooplankton under acidified conditions. However, mesozooplankton grazing rates decreased overall with elevated pCO2. Our findings show that these selected phytoplankton species have a relatively high tolerance to acidification in terms of FA production, and local mesozooplankton in these subtropical coastal waters can maintain their FA composition under end of century ocean acidification conditions.

Algae as nutritional and functional food sources: revisiting our understanding.

Global demand for macroalgal and microalgal foods is growing, and algae are increasingly being consumed for functional benefits beyond the traditional considerations of nutrition and health. There is substantial evidence for the health benefits of algal-derived food products, but there remain considerable challenges in quantifying these benefits, as well as possible adverse effects. First, there is a limited understanding of nutritional composition across algal species, geographical regions, and seasons, all of which can substantially affect their dietary value. The second issue is quantifying which fractions of algal foods are bioavailable to humans, and which factors influence how food constituents are released, ranging from food preparation through genetic differentiation in the gut microbiome. Third is understanding how algal nutritional and functional constituents interact in human metabolism. Superimposed considerations are the effects of harvesting, storage, and food processing techniques that can dramatically influence the potential nutritive value of algal-derived foods. We highlight this rapidly advancing area of algal science with a particular focus on the key research required to assess better the health benefits of an alga or algal product. There are rich opportunities for phycologists in this emerging field, requiring exciting new experimental and collaborative approaches.

Environmental dynamics of red Noctiluca scintillans bloom in tropical coastal waters.

An intense bloom of red Noctiluca scintillans (NS) occurred off the Rushikulya estuarine region along the east coast of India, an important site for mass nesting events of the vulnerable Olive Ridley sea turtle. At its peak, densities of NS were 3.3×10(5) cells-l(-1), with low relative abundance of other phytoplankton. The peak bloom coincided with high abundance of gelatinous planktivores which may have facilitated bloom development by their grazing on other zooplankton, particularly copepods. Ammonium concentrations increased by approximately 4-fold in the later stages of bloom, coincident with stable NS abundance and chlorophyll concentrations in the nano- and microplankton. This increase likely was attributable to release of intracellular ammonium accumulated through NS grazing. Dissolved oxygen concentrations decreased in sub-surface waters to near hypoxia. Micro-phytoplankton increasingly dominated chlorophyll-a biomass as the bloom declined, with diminishing picoplankton abundance likely the result of high predation by the ciliate Mesodinium rubrum. Together, these data illustrate factors that can disrupt ecosystem balance in this critically important Indian coastal region.

Harmful algal blooms and climate change: Learning from the past and present to forecast the future.

Climate change pressures will influence marine planktonic systems globally, and it is conceivable that harmful algal blooms may increase in frequency and severity. These pressures will be manifest as alterations in temperature, stratification, light, ocean acidification, precipitation-induced nutrient inputs, and grazing, but absence of fundamental knowledge of the mechanisms driving harmful algal blooms frustrates most hope of forecasting their future prevalence. Summarized here is the consensus of a recent workshop held to address what currently is known and not known about the environmental conditions that favor initiation and maintenance of harmful algal blooms. There is expectation that harmful algal bloom (HAB) geographical domains should expand in some cases, as will seasonal windows of opportunity for harmful algal blooms at higher latitudes. Nonetheless there is only basic information to speculate upon which regions or habitats HAB species may be the most resilient or susceptible. Moreover, current research strategies are not well suited to inform these fundamental linkages. There is a critical absence of tenable hypotheses for how climate pressures mechanistically affect HAB species, and the lack of uniform experimental protocols limits the quantitative cross-investigation comparisons essential to advancement. A HAB "best practices" manual would help foster more uniform research strategies and protocols, and selection of a small target list of model HAB species or isolates for study would greatly promote the accumulation of knowledge. Despite the need to focus on keystone species, more studies need to address strain variability within species, their responses under multifactorial conditions, and the retrospective analyses of long-term plankton and cyst core data; research topics that are departures from the norm. Examples of some fundamental unknowns include how larger and more frequent extreme weather events may break down natural biogeographic barriers, how stratification may enhance or diminish HAB events, how trace nutrients (metals, vitamins) influence cell toxicity, and how grazing pressures may leverage, or mitigate HAB development. There is an absence of high quality time-series data in most regions currently experiencing HAB outbreaks, and little if any data from regions expected to develop HAB events in the future. A subset of observer sites is recommended to help develop stronger linkages among global, national, and regional climate change and HAB observation programs, providing fundamental datasets for investigating global changes in the prevalence of harmful algal blooms. Forecasting changes in HAB patterns over the next few decades will depend critically upon considering harmful algal blooms within the competitive context of plankton communities, and linking these insights to ecosystem, oceanographic and climate models. From a broader perspective, the nexus of HAB science and the social sciences of harmful algal blooms is inadequate and prevents quantitative assessment of impacts of future HAB changes on human well-being. These and other fundamental changes in HAB research will be necessary if HAB science is to obtain compelling evidence that climate change has caused alterations in HAB distributions, prevalence or character, and to develop the theoretical, experimental, and empirical evidence explaining the mechanisms underpinning these ecological shifts.

Thalassiosira spp. community composition shifts in response to chemical and physical forcing in the northeast Pacific Ocean.

Diatoms are genetically diverse unicellular photosynthetic eukaryotes that are key primary producers in the ocean. Many of the over 100 extant diatom species in the cosmopolitan genus Thalassiosira are difficult to distinguish in mixed populations using light microscopy. Here, we examine shifts in Thalassiosira spp. composition along a coastal to open ocean transect that encountered a 3-month-old Haida eddy in the northeast Pacific Ocean. To quantify shifts in Thalassiosira species composition, we developed a targeted automated ribosomal intergenic spacer analysis (ARISA) method to identify Thalassiosira spp. in environmental samples. As many specific fragment lengths are indicative of individual Thalassiosira spp., the ARISA method is a useful screening tool to identify changes in the relative abundance and distribution of specific species. The method also enabled us to assess changes in Thalassiosira community composition in response to chemical and physical forcing. Thalassiosira spp. community composition in the core of a 3-month-old Haida eddy remained largely (>80%) similar over a 2-week period, despite moving 24 km southwestward. Shifts in Thalassiosira species correlated with changes in dissolved iron (Fe) and temperature throughout the sampling period. Simultaneously tracking community composition and relative abundance of Thalassiosira species within the physical and chemical context they occurred allowed us to identify quantitative linkages between environmental conditions and community response.

In situ strain-level detection and identification of Vibrio parahaemolyticus using surface-enhanced Raman spectroscopy.

The outer membrane of a bacterium is composed of chemical and biological components that carry specific molecular information related to strains, growth stages, expressions to stimulation, and maybe even geographic differences. In this work, we demonstrate that the biochemical information embedded in the outer membrane can be used for rapid detection and identification of pathogenic bacteria using surface-enhanced Raman spectroscopy (SERS). We used seven different strains of the marine pathogen Vibrio parahaemolyticus as a model system. The strains represent four genetically distinct clades isolated from clinical and environmental sources in Washington, U.S.A. The unique quasi-3D (Q3D) plasmonic nanostructure arrays, optimized using finite-difference time-domain (FDTD) calculations, were used as SERS-active substrates for sensitive and reproducible detection of these bacteria. SERS barcodes were generated on the basis of SERS spectra and were used to successfully detect individual strains in both blind samples and mixtures. The sensing and detection methods developed in this work could have broad applications in the areas of environmental monitoring, biomedical diagnostics, and homeland security.

A profile of an endosymbiont-enriched fraction of the coral Stylophora pistillata reveals proteins relevant to microbial-host interactions.

This study examines the response of Symbiodinium sp. endosymbionts from the coral Stylophora pistillata to moderate levels of thermal "bleaching" stress, with and without trace metal limitation. Using quantitative high throughput proteomics, we identified 8098 MS/MS events relating to individual peptides from the endosymbiont-enriched fraction, including 109 peptides meeting stringent criteria for quantification, of which only 26 showed significant change in our experimental treatments; 12 of 26 increased expression in response to thermal stress with little difference affected by iron limitation. Surprisingly, there were no significant increases in antioxidant or heat stress proteins; those induced to higher expression were generally involved in protein biosynthesis. An outstanding exception was a massive 114-fold increase of a viral replication protein indicating that thermal stress may substantially increase viral load and thereby contribute to the etiology of coral bleaching and disease. In the absence of a sequenced genome for Symbiodinium or other photosymbiotic dinoflagellate, this proteome reveals a plethora of proteins potentially involved in microbial-host interactions. This includes photosystem proteins, DNA repair enzymes, antioxidant enzymes, metabolic redox enzymes, heat shock proteins, globin hemoproteins, proteins of nitrogen metabolism, and a wide range of viral proteins associated with these endosymbiont-enriched samples. Also present were 21 unusual peptide/protein toxins thought to originate from either microbial consorts or from contamination by coral nematocysts. Of particular interest are the proteins of apoptosis, vesicular transport, and endo/exocytosis, which are discussed in context of the cellular processes of coral bleaching. Notably, the protein complement provides evidence that, rather than being expelled by the host, stressed endosymbionts may mediate their own departure.

Characterization of putative iron responsive genes as species-specific indicators of iron stress in thalassiosiroid diatoms.

Iron (Fe) availability restricts diatom growth and primary production in large areas of the oceans. It is a challenge to assess the bulk Fe nutritional health of natural diatom populations, since species can differ in their physiological and molecular responses to Fe limitation. We assayed expression of selected genes in diatoms from the Thalassiosira genus to assess their potential utility as species-specific molecular markers to indicate Fe status in natural diatom assemblages. In this study, we compared the expression of the photosynthetic genes encoding ferredoxin (a Fe-requiring protein) and flavodoxin (a Fe-free protein) in culture experiments with Fe replete and Fe stressed Thalassiosira pseudonana (CCMP 1335) isolated from coastal waters and Thalassiosira weissflogii (CCMP 1010) isolated from the open ocean. In T. pseudonana, expression of flavodoxin and ferredoxin genes were not sensitive to Fe status but were found to display diel periodicities. In T. weissflogii, expression of flavodoxin was highly responsive to iron levels and was only detectable when cultures were Fe limited. Flavodoxin genes have been duplicated in most diatoms with available genome data and we show that T. pseudonana has lost its copy related to the Fe-responsive copy in T. weissflogii. We also examined the expression of genes for a putative high affinity, copper (Cu)-dependent Fe uptake system in T. pseudonana. Our results indicate that genes encoding putative Cu transporters, a multi-Cu oxidase, and a Fe reductase are not linked to Fe status. The expression of a second putative Fe reductase increased in Fe limited cultures, but this gene was also highly expressed in Fe replete cultures, indicating it may not be a useful marker in the field. Our findings highlight that Fe metabolism may differ among diatoms even within a genus and show a need to validate responses in different species as part of the development pipeline for genetic markers of Fe status in field populations.

Iron enrichment stimulates toxic diatom production in high-nitrate, low-chlorophyll areas.

Oceanic high-nitrate, low-chlorophyll environments have been highlighted for potential large-scale iron fertilizations to help mitigate global climate change. Controversy surrounds these initiatives, both in the degree of carbon removal and magnitude of ecosystem impacts. Previous open ocean enrichment experiments have shown that iron additions stimulate growth of the toxigenic diatom genus Pseudonitzschia. Most Pseudonitzschia species in coastal waters produce the neurotoxin domoic acid (DA), with their blooms causing detrimental marine ecosystem impacts, but oceanic Pseudonitzschia species are considered nontoxic. Here we demonstrate that the sparse oceanic Pseudonitzschia community at the high-nitrate, low-chlorophyll Ocean Station PAPA (50 degrees N, 145 degrees W) produces approximately 200 pg DA L(-1) in response to iron addition, that DA alters phytoplankton community structure to benefit Pseudonitzschia, and that oceanic cell isolates are toxic. Given the negative effects of DA in coastal food webs, these findings raise serious concern over the net benefit and sustainability of large-scale iron fertilizations.

Determining subnanomolar iron concentrations in oceanic seawater using a siderophore-modified film analyzed by infrared spectroscopy.

Iron is a bioactive trace element in seawater that regulates photosynthetic carbon dioxide drawdown and export from surface waters by phytoplankton in upward of 40% of the world's oceans. While autonomous sensor arrays are beginning to provide high-resolution data on temporal and spatial scales for some key oceanographic parameters, current analytical methods for iron are not amenable to autonomous platforms because of the need for user involvement and wet chemistry-based approaches. As a result, very large gaps remain in our understanding of iron distribution and chemistry in seawater. Here we present a straightforward nanostructure-based method to measure dissolved iron in natural seawater. The device comprises an iron-specific chelating biomolecule, desferrioxamine B (DFB), covalently immobilized on a mesoporous silica film. Changes in infrared spectral signatures of the immobilized DFB upon Fe(III) complexation provide an accurate and precise measure of iron on the surface of a chip exposed to seawater. The current system has a detection limit of approximately 50 pM for a 1-L sample at pH 1.7 and was used to measure dissolved iron in subarctic Pacific waters without interference from other elements in seawater. This technology provides a major step toward obtaining accurate iron measurements on autonomous research platforms.