Ocean acidification is a global challenge that faces marine organisms in the near future with a predicted rapid drop in pH of up to 0.4 units by the end of this century. Effects of the change in ocean carbon chemistry and pH on the development, growth and fitness of marine animals are well documented. Recent evidence also suggests that a range of chemically mediated behaviours and interactions in marine fish and invertebrates will be affected. Marine animals use chemical cues, for example, to detect predators, for settlement, homing and reproduction. But, while effects of high CO conditions on these behaviours are described across many species, little is known about the underlying mechanisms, particularly in invertebrates. Here, we investigate the direct influence of future oceanic pH conditions on the structure and function of three peptide signalling molecules with an interdisciplinary combination of methods. NMR spectroscopy and quantum chemical calculations were used to assess the direct molecular influence of pH on the peptide cues, and we tested the functionality of the cues in different pH conditions using behavioural bioassays with shore crabs (Carcinus maenas) as a model system. We found that peptide signalling cues are susceptible to protonation in future pH conditions, which will alter their overall charge. We also show that structure and electrostatic properties important for receptor binding differ significantly between the peptide forms present today and the protonated signalling peptides likely to be dominating in future oceans. The bioassays suggest an impaired functionality of the signalling peptides at low pH. Physiological changes due to high CO conditions were found to play a less significant role in influencing the investigated behaviour. From our results, we conclude that the change of charge, structure and consequently function of signalling molecules presents one possible mechanism to explain altered behaviour under future oceanic pH conditions.

The effects of ocean acidification on fish are only partially understood. Studies on olfaction are mostly limited to behavioral alterations of coral reef fish; studies on temperate species and/or with economic importance are scarce. The current study evaluated the effects of short- and medium-term exposure to ocean acidification on the olfactory system of gilthead seabream ( Sparus aurata ), and attempted to explain observed differences in sensitivity by changes in the protonation state of amino acid odorants. Short-term exposure to elevated P CO 2 decreased olfactory sensitivity to some odorants, such as L-serine, L-leucine, L-arginine, L-glutamate, and conspecific intestinal fluid, but not to others, such as L-glutamine and conspecific bile fluid. Seabream were unable to compensate for high P CO 2 levels in the medium term; after 4 weeks exposure to high P CO 2 , the olfactory sensitivity remained lower in elevated P CO 2 water. The decrease in olfactory sensitivity in high P CO 2 water could be partly attributed to changes in the protonation state of the odorants and/or their receptor(s); we illustrate how protonation due to reduced pH causes changes in the charge distribution of odorant molecules, an essential component for ligand-receptor interaction. However, there are other mechanisms involved. At a histological level, the olfactory epithelium contained higher densities of mucus cells in fish kept in high CO 2 water, and a shift in pH of the mucus they produced to more neutral. These differences suggest a physiological response of the olfactory epithelium to lower pH and/or high CO 2 levels, but an inability to fully counteract the effects of acidification on olfactory sensitivity. Therefore, the current study provides evidence for a direct, medium term, global effect of ocean acidification on olfactory sensitivity in fish, and possibly other marine organisms, and suggests a partial explanatory mechanism.

This work reports for the first time the nutritional profile and antioxidant potential of the edible sea cucumber Holothuria arguinensis from the North-eastern Atlantic. H. arguinensis has high levels of protein, with the amino acids profile dominated by alanine, glycine and proline and low lysine/arginine ratios. Its carbohydrate and energetic contents are also low as well as the total lipid levels, although its lipid profile is rich in polyunsaturated fatty acids (PUFA), especially arachidonic, eicosapentaenoic and docosahexaenoic acids. In addition, H. arguinensis has high levels of calcium. The water and ethanol extracts show ability to scavenge free radicals and to chelate copper and iron ions. Our results indicate that H. arguinensis has a balanced nutritional quality suitable for human consumption. In addition, it contains compounds with antioxidant potential; thus its intake can contribute for a healthy and well-balanced diet.

Increasing atmospheric levels of carbon dioxide are largely absorbed by the world's oceans, decreasing surface water pH 1 . In combination with increasing ocean temperatures, these changes have been identified as a major sustainability threat to future marine life 2 . Interactions between marine organisms are known to depend on biomolecules, but the influence of oceanic pH on their bioavailability and functionality remains unexplored. Here we show that global change significantly impacts two ecological keystone molecules 3 in the ocean, the paralytic toxins saxitoxin (STX) and tetrodotoxin (TTX). Increasing temperatures and declining pH increase the abundance of the toxic forms of these two neurotoxins in the water. Our geospatial global model highlights where this increased toxicity could intensify the devastating impact of harmful algal blooms on ecosystems in the future, for example through an increased incidence of paralytic shellfish poisoning (PSP). We also use these results to calculate future saxitoxin toxicity levels in Alaskan clams, Saxidomus gigantea, showing critical exceedance of limits safe for consumption. Our findings for TTX and STX exemplify potential consequences of changing pH and temperature on chemicals dissolved in the sea. This reveals major implications not only for ecotoxicology, but also for chemical signals mediating species interactions such as foraging, reproduction, or predation in the ocean with unexplored consequences for ecosystem stability and ecosystem services.

In the past decade, many studies have investigated the effects of low pH/high CO2 as a proxy for ocean acidification on olfactory-mediated behaviours of marine organisms. The effects of ocean acidification on the behaviour of fish vary from very large to none at all, and most of the maladaptive behaviours observed have been attributed to changes in acid–base regulation, leading to changes in ion distribution over neural membranes, and consequently affecting the functioning of gamma-aminobutyric acid-mediated (GABAergic) neurotransmission. Here, we highlight a possible additional mechanism by which ocean acidification might directly affect olfaction in marine fish and invertebrates. We propose that a decrease in pH can directly affect the protonation, and thereby, 3D conformation and charge distribution of odorants and/or their receptors in the olfactory organs of aquatic animals. This can sometimes enhance signalling, but most of the time the affinity of odorants for their receptors is reduced in high CO2/low pH; therefore, the activity of olfactory receptor neurons decreases as measured using electrophysiology. The reduced signal reception would translate into reduced activation of the olfactory bulb neurons, which are responsible for processing olfactory information in the brain. Over longer exposures of days to weeks, changes in gene expression in the olfactory receptors and olfactory bulb neurons cause these neurons to become less active, exacerbating the problem. A change in olfactory system functioning leads to inappropriate behavioural responses to odorants. We discuss gaps in the literature and suggest some changes to experimental design in order to improve our understanding of the underlying mechanisms and their effects on the associated behaviours to resolve some current controversy in the field regarding the extent of the effects of ocean acidification on marine fish.

In this study, we assess the influence of solvation on the accuracy and reliability of isotropic nuclear magnetic shielding calculations for amino acids in comparison to experimental data. We focus particularly on the performance of solvation methods for different protonation states, as biological molecules occur almost exclusively in aqueous solution and are subject to protonation with pH. We identify significant shortcomings of current implicit solvent models and present a hybrid solvation approach that improves agreement with experimental data by taking into account the presence of direct interactions between amino acid protonation state and water molecules.

Chemically mediated interaction through so-called infochemicals (Hay, 2009;, often also referred to as semiochemicals, is arguably the oldest and most widespread form of communication (Wyatt, 2003). Infochemicals provide the basis for the vast majority of ecological processes across the tree of life in both terrestrial and aquatic ecosystems (Brönmark & Hansson, 2012;Wyatt, 2014), serving as cues or signals released into the surroundings or present on the surface of organisms (Wyatt, 2014). They cover a broad range of functions, mediating

This work makes a comparative evaluation of the biochemical profile of three sea commercial cucumber species (Holothuria mammata, H. polii and H. tubulosa) caught from different locations of the Mediterranean Sea (SE Spain). All species had high levels of moisture (from 73.6% in H. mammata to 81.2% in H. tubulosa), crude ash (from 9.61% in H. mammata to 14.7% in H. tubulosa) and protein (3.01% in H. tubulosa to 11.1% in H. mammata). They also had a low fat content, from 0.21% in H. tubulosa to 0.55% in H. mammata. Holothuria polii had intermediate values between the other two species, for all considered variables. All species had adequate protein/lipid ratios (H. mammata, 20:1; H. polii, 23:1; H. tubulosa, 14:1) and low lipid levels, enriched in omega-3 polyunsaturated fatty acids, especially arachidonic acid. The fatty acid profile suggests that H. polii is feeding on sediments more influenced by terrestrial inputs than the remaining species. Holothuria mammata and H. tubulosa are feeding on marine food sources mainly, but also with some terrestrial influence. The most abundant amino acids detected were alanine, arginine, glutamic acid, and glycine. All species had similar contents of essential amino acids (EAA) and ratios of EAA/non-essential amino acids. Holothuria tubulosa had a high content of toxic metals including Cr, Pb and Ni. This work highlights differences in compositional characteristics between different species of the same genus (Holothuria) from different locations.