The green seaweed Ulva: tomorrow's "wheat of the sea" in foods, feeds, nutrition, and biomaterials.

Ulva, a genus of green macroalgae commonly known as sea lettuce, has long been recognized for its nutritional benefits for food and feed. As the demand for sustainable food and feed sources continues to grow, so does the interest in alternative, plant-based protein sources. With its abundance along coastal waters and high protein content, Ulva spp. have emerged as promising candidates. While the use of Ulva in food and feed has its challenges, the utilization of Ulva in other industries, including in biomaterials, biostimulants, and biorefineries, has been growing. This review aims to provide a comprehensive overview of the current status, challenges and opportunities associated with using Ulva in food, feed, and beyond. Drawing on the expertise of leading researchers and industry professionals, it explores the latest knowledge on Ulva's nutritional value, processing methods, and potential benefits for human nutrition, aquaculture feeds, terrestrial feeds, biomaterials, biostimulants and biorefineries. In addition, it examines the economic feasibility of incorporating Ulva into aquafeed. Through its comprehensive and insightful analysis, including a critical review of the challenges and future research needs, this review will be a valuable resource for anyone interested in sustainable aquaculture and Ulva's role in food, feed, biomaterials, biostimulants and beyond.

Short-term effects of increased CO2, nitrate and temperature on photosynthetic activity in Ulva rigida (Chlorophyta) estimated by different pulse amplitude modulated fluorometers and oxygen evolution.

Short-term effects of pCO2 (700-380 ppm; High carbon (HC) and Low carbon (LC), respectively) and nitrate content (50-5 µM; High nitrogen (HN) and Low nitrogen (LN), respectively on photosynthesis were investigated in Ulva rigida (Chlorophyta) under solar radiation (in-situ) and in the laboratory under artificial light (ex-situ). After six days of incubation at ambient temperature (AT), algae were subjected to a 4 °C temperature increase (AT+4 °C) for 3 d. Both in-situ and ex-situ maximal electron transport rate (ETRmax) and in situ gross photosynthesis (GP), measured by O2 evolution, presented highest values under HCHN, and lowest under HCLN, across all measuring systems. Maximal quantum yield (Fv/Fm), and ETRmax of photosystem (PS) II [ETR(II)max] and PSI [ETR(I)max], decreased under HCLN at AT+4 °C. Ex situ ETR was higher than in situ ETR. At noon, Fv/Fm decreased (indicating photoinhibition), whereas ETR(II)max and maximal non-photochemical quenching (NPQmax) increased. ETR(II)max decreased under AT+ 4 °C in contrast to Fv/Fm, photosynthetic efficiency (α ETR) and saturated irradiance (EK). Thus, U. rigida exhibited a decrease in photosynthesis under acidification, changing LN, and AT+4 °C. These results emphasize the importance of studying the interaction between environmental parameters using in-situ versus ex-situ conditions, when aiming to evaluate the impact of global change on marine macroalgae.

Arsenolipids are not uniformly distributed within two brown macroalgal species Saccharina latissima and Alaria esculenta.

Brown macroalgae Saccharina latissima (30-40 individuals) and Alaria esculenta (15-20 individuals) were collected from natural populations in winter in Iceland. The algal thalli were sectioned into different parts (e.g. holdfast, stipe, old frond, young frond and sori-containing frond sections) that differed in age and biological function. The work elucidated that arsenic (As) was not uniformly distributed within the two brown macroalgal species, with lower levels of total As were found in the stipe/midrib compared to other thallus parts. The arsenosugars mirrored the total arsenic in the seaweed mainly due to AsSugSO3 being the most abundant As species. However, arsenic speciation using parallel HPLC-ICP-MS/ESI-MS elucidated that the arsenic-containing lipids (AsL) had a different distribution where the arsenosugarphospholipids (AsPL) differed by approximately a factor of 4 between the sections containing the lowest and highest concentrations of AsPLs. When placing the sections in order of metabolic activity and an estimate of tissue age, there appeared to be a relationship between the activity and AsPLs, with lower levels of AsPLs in oldest parts. This is the first time such a relationship has been shown for AsLs. Hence, by applying sophisticated analytical techniques, it was possible to gain a deeper understanding of arsenolipids in seaweed.

Nutraceuticals to promote neuronal plasticity in response to corticosterone-induced stress in human neuroblastoma cells.

Objectives: To search for novel compounds that will protect neuronal cells under stressed conditions that may help to restore neuronal plasticity. Methods: A model of corticosterone (CORT)-induced stress in human neuroblastoma cells (SH-SY5Y) was used to compare the efficacy of 6 crude extracts and 10 pure compounds (6 polyphenols, 2 carotenoids, 1 amino acid analogue, and 1 known antidepressant drug) to increase neuronal plasticity and to decrease cytotoxicity. Results: Astaxanthin (among pure compounds) and phlorotannin extract of Fucus vesiculosus (among crude extracts) showed a maximum increase in cell viability in the presence of excess CORT. BDNF-VI mRNA expression in SH-SY5Y cells was significantly improved by pretreatment with quercetine, astaxanthin, curcumin, fisetin, and resveratrol. Among crude extracts, xanthohumol, phlorotannin extract (Ecklonia cava), petroleum ether extract (Nannochloropsis oculata), and phlorotannin extract (F. vesiculosus) showed a significant increase in BDNF-VI mRNA expression. CREB1 mRNA expression was significantly improved by astaxanthin, ß-carotene, curcumin, and fluoxetine whereas none of the crude extracts caused significant improvement. As an adjunct of fluoxetine, phlorotannin extract (F. vesiculosus), ß-carotene, and xanthohumol have resulted in significant improvement in BDNF-VI mRNA expression and CREB1 mRNA expression was significantly improved by phlorotannin extract (F. vesiculosus). Significant improvement in mature BDNF protein expression by phlorotannin extract (F. vesiculosus) and ß-carotene as an adjunct of fluoxetine confirm their potential to promote neuronal plasticity against CORT-induced stress. Discussion: The carotenoids, flavonoids, namely quercetine, curcumin, and low molecular weight phlorotannin-enriched extract of F. vesiculosus may serve as potential neuroprotective agents promoting neuronal plasticity in vitro. Graphical abstract: Cascade of events associated with disturbed homeostatic balance of glucocorticoids and impact of phlorotannin extract (F. vesiculosus) and ß-carotene in restoring neuronal plasticity. Abbreviation: TrKB, tropomyosin receptor kinase B; P-ERK, phosphorylated extracellular signal-related kinase; PI3K, phosphatidylinositol 3-kinase; Akt, protein kinase B; Ca++/CaMK, calcium/calmodulin-dependent protein kinase; pCREB, phosphorylated cAMP response element-binding protein; CRE, cAMP response elements, CORT, corticosterone; and BDNF; brain-derived neurotrophic factor.

Microbial Population Changes in Decaying Ascophyllum nodosum Result in Macroalgal-Polysaccharide-Degrading Bacteria with Potential Applicability in Enzyme-Assisted Extraction Technologies.

Seaweeds are of significant interest in the food, pharmaceutical, and agricultural industries as they contain several commercially relevant bioactive compounds. Current extraction methods for macroalgal-derived metabolites are, however, problematic due to the complexity of the algal cell wall which hinders extraction efficiencies. The use of advanced extraction methods, such as enzyme-assisted extraction (EAE), which involve the application of commercial algal cell wall degrading enzymes to hydrolyze the cell wall carbohydrate network, are becoming more popular. Ascophyllum nodosum samples were collected from the Irish coast and incubated in artificial seawater for six weeks at three different temperatures (18 °C, 25 °C, and 30 °C) to induce decay. Microbial communities associated with the intact and decaying macroalga were examined using Illumina sequencing and culture-dependent approaches, including the novel ichip device. The bacterial populations associated with the seaweed were observed to change markedly upon decay. Over 800 bacterial isolates cultured from the macroalga were screened for the production of algal cell wall polysaccharidases and a range of species which displayed multiple hydrolytic enzyme activities were identified. Extracts from these enzyme-active bacterial isolates were then used in EAE of phenolics from Fucus vesiculosus and were shown to be more efficient than commercial enzyme preparations in their extraction efficiencies.

Variability in iodine in temperate seaweeds and iodine accumulation kinetics of Fucus vesiculosus and Laminaria digitata (Phaeophyceae, Ochrophyta).

The biogeochemistry of iodine in temperate coastal ecosystems is largely mediated by macroalgae, which act as a major biological sink and source of iodine. Their capacity to accumulate, retain and release iodine has been associated with abiotic and biotic stressors, but quantitative information is limited. We evaluated the seasonal iodine retention capacity of eleven macroalgal species belonging to different systematic groups, collected from two sites in Ireland. Iodine accumulation and retention were then further quantified in Fucus vesiculosus and Laminaria digitata in relation to I- concentrations in seawater and temperature. In general, iodine contents were ~101 -102  µmol · (g dw)-1 for Laminariales, 100 -101  µmol · (g dw)-1 for Fucales, 10-1 -100  µmol · (g dw)-1 for Rhodophyta, and 10-1  µmol · (g dw)-1 for Chlorophyta. Typically, algal iodine contents were above average in winter and below average in summer. Iodine accumulation in F. vesiculosus and L. digitata depended on I- availability and followed the Michaelis-Menten kinetic. The ratio of maximum accumulation rate to half accumulation coefficient (ρmax : Kt ) was 2.4 times higher for F. vesiculosus than for L. digitata, suggesting that F. vesiculosus was more efficient in iodine accumulation. Both species exhibited a temperature-dependent net loss of iodine, and only an exposure to sufficient external I- concentrations compensated for this loss. This study revealed that both environmental (e.g., I- in seawater, temperature) and organismal (e.g., the status of the iodine storage pool) variables determine retention and variability in iodine in temperate seaweeds.

Impact of temperature on fatty acid composition and nutritional value in eight species of microalgae.

Microalgae are considered a sustainable source of high-value products with health benefits. Marine algae-derived omega-3 long-chain polyunsaturated fatty acids (LC-PUFA), such as eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), are considered dietary elements with effects on mental health, cognition enhancement, and cardiovascular protection. This study investigated the temperature effect on omega-3 LC-PUFA production in eight species of microalgae from various taxonomic groups, with a focus on achieving an optimal balance between omega-3 accumulation and efficient growth performance. Samples were batch-cultivated at four different temperatures, with constant light, and fatty acid methyl esters (FAME) were analyzed by gas chromatography. Several nutritional indices were calculated to assess the potential value of biomass produced for human consumption. Two promising candidates were identified suitable for batch cultivation and large-scale production: Nannochloropsis oculata for EPA and Isochrysis galbana for DHA production, with optimum productivities obtained between 14 and 20 °C, and nutritional indices falling within the range required for nutritional benefit.

Intra-thallus differentiation of fatty acid and pigment profiles in some temperate Fucales and Laminariales.

Intra-thallus variation in fatty acid and pigment contents and profiles was investigated in five species of Laminariales (Alaria esculenta, Laminaria digitata, Laminaria hyperborea, Saccharina latissima, and Saccorhiza polyschides), and three Fucales (Ascophyllum nodosum, Fucus serratus, and Himanthalia elongata). Significant variation occurred across all species and compounds examined. Total fatty acids were generally higher in the fronds, with highest levels and largest variability observed in A. nodosum (1.5% of dry weight (DW) in the base, 6.3% of DW in frond tips). Percentages of the omega-3 fatty acids 18:4 n-3 and 20:5 n-3 were generally higher in more distal parts, while 20:4 n-6 exhibited a contrasting pattern, with higher levels in basal structures and holdfasts. Trends for pigments were similar to those for fatty acids in Laminariales. In the Fucales, highest levels were detected in the mid-fronds, with lower concentrations in meristematic areas. Highest levels and greatest variability in pigments (e.g., chl a) was observed in F. serratus (1.07 mg · g(-1) DW in the base, 3.04 mg · g(-1) DW in the mid frond). Intra-thallus variability was attributed to physiological functions of the respective thallus sections, e.g., photosynthetic activity, meristematic tissue, and to variations in physical attributes of the structures investigated. Regarding potential commercial nutritional applications, fronds appeared to represent most suitable source materials, due to higher levels of pigments, polyunsaturated fatty acids, and more preferable omega-3/omega-6 ratios.

Prospects and challenges for industrial production of seaweed bioactives.

Large-scale seaweed cultivation has been instrumental in globalizing the seaweed industry since the 1950s. The domestication of seaweed cultivars (begun in the 1940s) ended the reliance on natural cycles of raw material availability for some species, with efforts driven by consumer demands that far exceeded the available supplies. Currently, seaweed cultivation is unrivaled in mariculture with 94% of annual seaweed biomass utilized globally being derived from cultivated sources. In the last decade, research has confirmed seaweeds as rich sources of potentially valuable, health-promoting compounds. Most existing seaweed cultivars and current cultivation techniques have been developed for producing commoditized biomass, and may not necessarily be optimized for the production of valuable bioactive compounds. The future of the seaweed industry will include the development of high value markets for functional foods, cosmeceuticals, nutraceuticals, and pharmaceuticals. Entry into these markets will require a level of standardization, efficacy, and traceability that has not previously been demanded of seaweed products. Both internal concentrations and composition of bioactive compounds can fluctuate seasonally, geographically, bathymetrically, and according to genetic variability even within individual species, especially where life history stages can be important. History shows that successful expansion of seaweed products into new markets requires the cultivation of domesticated seaweed cultivars. Demands of an evolving new industry based upon efficacy and standardization will require the selection of improved cultivars, the domestication of new species, and a refinement of existing cultivation techniques to improve quality control and traceability of products.

The Anti-Inflammatory Effect of Algae-Derived Lipid Extracts on Lipopolysaccharide (LPS)-Stimulated Human THP-1 Macrophages.

Algae contain a number of anti-inflammatory bioactive compounds such as omega-3 polyunsaturated fatty acids (n-3 PUFA) and chlorophyll a, hence as dietary ingredients, their extracts may be effective in chronic inflammation-linked metabolic diseases such as cardiovascular disease. In this study, anti-inflammatory potential of lipid extracts from three red seaweeds (Porphyra dioica, Palmaria palmata and Chondrus crispus) and one microalga (Pavlova lutheri) were assessed in lipopolysaccharide (LPS)-stimulated human THP-1 macrophages. Extracts contained 34%-42% total fatty acids as n-3 PUFA and 5%-7% crude extract as pigments, including chlorophyll a, ß-carotene and fucoxanthin. Pretreatment of the THP-1 cells with lipid extract from P. palmata inhibited production of the pro-inflammatory cytokines interleukin (IL)-6 (p < 0.05) and IL-8 (p < 0.05) while that of P. lutheri inhibited IL-6 (p < 0.01) production. Quantitative gene expression analysis of a panel of 92 genes linked to inflammatory signaling pathway revealed down-regulation of the expression of 14 pro-inflammatory genes (TLR1, TLR2, TLR4, TLR8, TRAF5, TRAF6, TNFSF18, IL6R, IL23, CCR1, CCR4, CCL17, STAT3, MAP3K1) by the lipid extracts. The lipid extracts effectively inhibited the LPS-induced pro-inflammatory signaling pathways mediated via toll-like receptors, chemokines and nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB) signaling molecules. These results suggest that lipid extracts from P. lutheri, P. palmata, P. dioica and C. crispus can inhibit LPS-induced inflammatory pathways in human macrophages. Therefore, algal lipid extracts should be further explored as anti-inflammatory ingredients for chronic inflammation-linked metabolic diseases.

Iodine contributes to osmotic acclimatisation in the kelp Laminaria digitata (Phaeophyceae).

Iodide (I⁻) retained by the brown macroalga Laminaria digitata at millimolar levels, possesses antioxidant activities, but the wider physiological significance of its accumulation remains poorly understood. In its natural habitat in the lower intertidal, L. digitata experiences salinity changes and osmotic homeostasis is achieved by regulating the organic osmolyte mannitol. However, I⁻ may also holds an osmotic function. Here, impacts of hypo- and hypersaline conditions on I⁻ release from, and accumulation by, L. digitata were assessed. Additionally, mannitol accumulation was determined at high salinities, and physiological responses to externally elevated iodine concentrations and salinities were characterised by chl a fluorometry. Net I⁻ release rates increased with decreasing salinity. I⁻ was accumulated at normal (35 S A) and high salinities (50 S A); this coincided with enhanced rETRmax and qP causing pronounced photoprotection capabilities via NPQ. At 50 S A elevated tissue iodine levels impeded the well-established response of mannitol accumulation and prevented photoinhibition. Contrarily, low tissue iodine levels limited photoprotection capabilities and resulted in photoinhibition at 50 S A, even though mannitol was accumulated. The results indicate a, so far, undescribed osmotic function of I⁻ in L. digitata and, thus, multifunctional principles of this halogen in kelps. The osmotic function of mannitol may have been substituted by that of I⁻ under hypersaline conditions, suggesting a complementary role of inorganic and organic solutes under salinity stress. This study also provides first evidence that iodine accumulation in L. digitata positively affects photo-physiology.

Ecotype-Specific and Correlated Seasonal Responses of Biomass Production, Non-Structural Carbohydrates, and Fatty Acids in Zostera marina.

Seagrasses, which are marine flowering plants, provide numerous ecological services and goods. Zostera marina is the most widely distributed seagrass in temperate regions of the northern hemisphere, tolerant of a wide range of environmental conditions. This study aimed to (i) examine seasonal trends and correlations between key seagrass traits such as biomass production and biochemical composition, and (ii) compare seasonal adaptation of two ecotypes of Z. marina exposed to similar environmental conditions on the west coast of Ireland. During summer, plants accumulated higher levels of energetic compounds and levels of unsaturated fatty acids (FAs) decreased. Conversely, the opposite trend was observed during colder months. These findings indicate a positive seasonal correlation between the production of non-structural carbohydrates and saturated fatty acids (SFAs), suggesting that seagrasses accumulate and utilize both energetic compounds simultaneously during favorable and unfavorable environmental conditions. The two ecotypes displayed differential seasonal responses by adjusting plant morphology and production, the utilization of energetic reserves, and modulating unsaturation levels of fatty acids in seagrass leaves. These results underscore the correlated seasonal responses of key compounds, capturing ecotype-specific environmental adaptations and ecological strategies, emphasizing the robust utility of these traits as a valuable eco-physiological tool.

LC-PUFA-enriched oil production by microalgae: accumulation of lipid and triacylglycerols containing n-3 LC-PUFA is triggered by nitrogen limitation and inorganic carbon availability in the marine haptophyte Pavlova lutheri.

In most microalgal species, triacyglycerols (TAG) contain mostly saturated and monounsaturated fatty acids, rather than PUFA, while PUFA-enriched oil is the form most desirable for dietary intake. The ability of some species to produce LC-PUFA-enriched oil is currently of specific interest. In this work, we investigated the role of sodium bicarbonate availability on lipid accumulation and n-3 LC-PUFA partitioning into TAG during batch cultivation of Pavlova lutheri. Maximum growth and nitrate uptake exhibit an optimum concentration and threshold tolerance to bicarbonate addition (~9 mM) above which both parameters decreased. Nonetheless, the transient highest cellular lipid and TAG contents were obtained at 18 mM bicarbonate, immediately after combined alkaline pH stress and nitrate depletion (day nine), while oil body and TAG accumulation were highly repressed with low carbon supply (2 mM). Despite decreases in the proportions of EPA and DHA, maximum volumetric and cellular EPA and DHA contents were obtained at this stage due to accumulation of TAG containing EPA/DHA. TAG accounted for 74% of the total fatty acid per cell, containing 55% and 67% of the overall cellular EPA and DHA contents, respectively. These results clearly demonstrate that inorganic carbon availability and elevated pH represent two limiting factors for lipid and TAG accumulation, as well as n-3 LC-PUFA partitioning into TAG, under nutrient-depleted P. lutheri cultures.

Field development of Posidonia oceanica seedlings changes under predicted acidification conditions.

Ocean acidification has been consistently evidenced to have profound and lasting impacts on marine species. Observations have shown seagrasses to be highly susceptible to future increased pCO2 conditions, but the responses of early life stages as seedlings are poorly understood. This study aimed at evaluating how projected Mediterranean Sea acidification affects the survival, morphological and biochemical development of Posidonia oceanica seedlings through a long-term field experiment along a natural low pH gradient. Future ocean conditions seem to constrain the morphological development of seedlings. However, high pCO2 exposures caused an initial increase in the degree of saturation of fatty acids in leaves and then improved the fatty acid adjustment increasing unsaturation levels in leaves (but not in seeds), suggesting a nutritional compound translocation. Results also suggested a P. oceanica structural components remodelling which may counteract the effects of ocean acidification but would not enhance seagrass seedling productivity.

Effects of high temperature and marine heat waves on seagrasses: Is warming affecting the nutritional value of Posidonia oceanica?

Primary producers nutritional content affects the entire food web. Here, changes in nutritional value associated with temperature rise and the occurrence of marine heat waves (MHWs) were explored in the endemic Mediterranean seagrass Posidonia oceanica. The variability of fatty acids (FAs) composition and carbon (C) and nitrogen (N) content were examined during summer 2021 from five Mediterranean sites located at the same latitude but under different thermal environments. The results highlighted a decrease in unsaturated FAs and C/N ratio and an increase of monounsaturated FA (MUFA) and N content when a MHW occurred. By contrast, the leaf biochemical composition seems to be adapted to local water temperature since only few significant changes in MUFA were found and N and C/N had an opposite pattern compared to when a MHW occurs. The projected increase in temperature and frequency of MHW suggest future changes in the nutritional value and palatability of leaves.

Chlorophyll a fluorescence responses of temperate Phaeophyceae under submersion and emersion regimes: a comparison of rapid and steady-state light curves.

The potential of algae to acclimate to environmental stress is commonly assessed using chlorophyll a fluorescence, with changes in parameters of photosynthesis versus irradiance (P/E) curves measured either as rapid light curves (RLC) or steady-state light curves (LC). Here, effects of emersion on primary photosynthesis of four brown macroalgae (Ascophyllum nodosum, Fucus serratus, Sargassum muticum, Laminaria digitata) were compared by applying both RLC and LC. When LC were used, photosynthetic performance was enhanced during emersion in A. nodosum and F. serratus as shown by increases in q(P), rETR(max) and E(k). By contrast, emersion had no impact on photosynthetic parameters of S. muticum and L. digitata. Relative changes in the NPQ-rETR relationship were reduced in A. nodosum, F. serratus and S. muticum, but remained unaffected in L. digitata. As none of the species developed their potential NPQ(max), corresponding values could not be determined from RLC. Using RLC, observed photosynthetic performance of F. serratus and L. digitata was reduced upon emersion, whilst values for NPQ(max) were enhanced. Only results derived from LC provide evidence for a potential physiological adaptation of brown macroalgae to their natural habitat; it is recommended using the LC protocol to detect environmental impacts on photosynthesis.

Coastal iodine emissions. 1. Release of I2 by Laminaria digitata in chamber experiments.

Tidally exposed macroalgae emit large amounts of I(2) and iodocarbons that produce hotspots of iodine chemistry and intense particle nucleation events in the coastal marine boundary layer. Current emission rates are poorly characterized, however, with reported emission rates varying by 3 orders of magnitude. In this study, I(2) emissions from 25 Laminaria digitata samples were investigated in a simulation chamber using incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). The chamber design allowed gradual extraction of seawater to simulate tidal emersion of algae. Samples were exposed to air with or without O(3) and to varying irradiances. Emission of I(2) occurred in four distinct stages: (1) moderate emissions from partially submerged samples; (2) a strong release by fully emerged samples; (3) slowing or stopping of I(2) release; and (4) later pulses of I(2) evident in some samples. Emission rates were highly variable and ranged from 7 to 616 pmol min(-1) gFW(-1) in ozone-free air, with a median value of 55 pmol min(-1) gFW(-1) for 20 samples.

Coastal iodine emissions: part 2. Chamber experiments of particle formation from Laminaria digitata-derived and laboratory-generated I2.

Laboratory studies into particle formation from Laminaria digitata macroalgae were undertaken to elucidate aerosol formation for a range of I(2) (0.3-76 ppb(v)) and O(3) (<3-96 ppb(v)) mixing ratios and light levels (E(PAR) = 15, 100, and 235 µmol photons m(-2) s(-1)). No clear pattern was observed for I(2) or aerosol parameters as a function of light levels. Aerosol mass fluxes and particle number concentrations, were, however, correlated with I(2) mixing ratios for low O(3) mixing ratios of <3 ppb(v) (R(2) = 0.7 and 0.83, respectively for low light levels, and R(2) = 0.95 and 0.98, respectively for medium light levels). Additional experiments into particle production as a function of laboratory-generated I(2), over a mixing ratio range of 1-8 ppb(v), were conducted under moderate O(3) mixing ratios (∼24 ppb(v)) where a clear, 100-fold or greater, increase in the aerosol number concentrations and mass fluxes was observed compared to the low O(3) experiments. A linear relationship between particle concentration and I(2) was found, in reasonable agreement with previous studies. Scaling the laboratory relationship to aerosol concentrations typical of the coastal boundary layer suggests a I(2) mixing ratio range of 6-93 ppt(v) can account for the observed particle production events. Aerosol number concentration produced from I(2) is more than a factor of 10 higher than that produced from CH(2)I(2) for the same mixing ratios.

Profiling phlorotannins in brown macroalgae by liquid chromatography-high resolution mass spectrometry.

INTRODUCTION: Phlorotannins, phenolic compounds produced exclusively by Phaeophyceae (brown algae), have recently been associated with a wide variety of beneficial bioactivities. Several studies have measured the total phenolic content in extracts from various species, but little characterisation of individual phlorotannin components has been demonstrated. OBJECTIVE: The purpose of this study was to develop a liquid chromatography-mass spectrometry (LC-MS) based method for rapid profiling of phlorotannins in brown algae. METHODOLOGY: Phlorotannin-enriched extracts from five phaeophyceaen species were analysed by ultrahigh-pressure liquid chromatography (UHPLC) operating in hydrophilic interaction liquid chromatography (HILIC) mode combined with high resolution mass spectrometry (HRMS). The method was optimised using an extract of Fucus vesiculosus; separation was achieved in less than 15 min. The basic mobile phase enhanced negative-ion electrospray ionisation (ESI), and generated multiply charged ions that allowed detection of high molecular weight phlorotannins. RESULTS: The phlorotannin profiles of Pelvetia canaliculata, Fucus spiralis, F. vesiculosus, Ascophyllum nodosum and Saccharina longicruris differed significantly. Fucus vesiculosus yielded a high abundance of low molecular weight (< 1200 Da) phlorotannins, while P. canaliculata exhibited a more evenly distributed profile, with moderate degrees of polymerisation ranging from 3 to 49. HRMS enabled the identification of phlorotannins with masses up to 6000 Da using a combination of accurate mass and ¹³C isotopic patterns. CONCLUSION: The UHPLC-HRMS method described was successful in rapidly profiling phlorotannins in brown seaweeds based on their degree of polymerisation. HILIC was demonstrated to be an effective separation mode, particularly for low molecular weight phlorotannins.