ALBERT

Description: Micro-Raman spectroscopy has been used on adult bivalve shells to investigate organic and inorganic shell components but has not yet been applied to bivalve larvae. It is known that the organic matrix of larval shells contains pigments, but less is known about the presence or source of these molecules in larvae. We investigated Raman spectra of seven species of bivalve larvae to assess the types of pigments present in shells of each species and how the ratio of inorganic : organic material changes in a dorso-ventral direction. In laboratory experiments, we reared larvae of three clam species in waters containing different organic signatures to determine if larvae incorporated compounds from source waters into their shells. We found differences in spectra and pigments between most species but found less intraspecific differences. A neural network classifier for Raman spectra classified five out of seven species with greater than 85% accuracy. There were slight differences between the amount and type of pigment present along the shell, with the prodissoconch I and shell margin areas being the most variable. Raman spectra of 1-day-old larvae were found to be differentiable when larvae were reared in waters with different organic signatures. With micro-Raman spectroscopy, it may be possible to identify some unknown species in the wild and trace their natal origins, which could enhance identification accuracy of bivalve larvae and ultimately aid management and restoration efforts.

Description: INTRODUCTION: Lichens are self-sustaining partnerships comprising fungi as shape-forming partners for their enclosed symbiotic algae. They produce a tremendous diversity of metabolites (1050 metabolites described so far). OBJECTIVES: A comparison of metabolic profiles in nine lichen species belonging to three genera (Lichina, Collema and Roccella) by using an optimised extraction protocol, determination of the fragmentation pathway and the in situ localisation for major compounds in Roccella species. METHODS: Chemical analysis was performed using a complementary study combining a Taguchi experimental design with qualitative analysis by high-performance liquid chromatography coupled with mass spectrometry techniques. RESULTS: Optimal conditions to obtain the best total extraction yield were determined as follows: mortar grinding to a fine powder, two successive extractions, solid:liquid ratio (2:60) and 700 rpm stirring. Qualitative analysis of the metabolite profiling of these nine species extracted with the optimised method was corroborated using MS and MS/MS approaches. Nine main compounds were identified: 1 β-orcinol, 2 orsellinic acid, 3 putative choline sulphate, 4 roccellic acid, 5 montagnetol, 6 lecanoric acid, 7 erythrin, 8 lepraric acid and 9 acetylportentol, and several other compounds were reported. Identification was performed using the m/z ratio, fragmentation pathway and/or after isolation by NMR analysis. The variation of the metabolite profile in differently organised parts of two Roccella species suggests a specific role of major compounds in developmental stages of this symbiotic association. CONCLUSION: Metabolic profiles represent specific chemical species and depend on the extraction conditions, the kind of the photobiont partner and the in situ localisation of major compounds.

Description: Brackish coastal groundwater is enriched in Ra, which is transported to surface waters via submarine groundwater discharge (SGD). The Ra activity of the SGD end-member is influenced by a variety of environmental factors including salinity, pH, and isotope half-life. In the York River estuary (YRE), 223Ra, 224Ra, and 226Ra were measured in surface water and shallow groundwater across a range of salinities and additional Ra sources quantified (desorption and diffusion from sediments, input from tidal marshes). The Ra budget of the estuary indicated a major source of Ra that could only be satisfied by SGD. The apparent Ra flux was combined with groundwater Ra end-member activity to estimate SGD volume fluxes of 5–178 L m− 2 d− 1. Each isotope exhibited a different seasonal pattern, with significantly higher 224Ra flux during summer than winter, lower 226Ra SGD flux during summer than winter, and no seasonal differences in 223Ra SGD flux. However, the SGD 224Ra end-member activity varied with seasonal pore water salinity fluctuations, indicating end-member control on seasonal 224Ra flux. Each Ra isotope suggested a different SGD volume flux, indicating that different nuclide regeneration rates may respond to and reflect different flow mechanisms in the subterranean estuary. This work indicates that volume fluxes estimated using geochemical tracers are sensitive to SGD end-member variations and end-member variability must be well-characterized for reliable SGD flux estimates.

Description: In this paper we present an in-depth analysis and synthesis of published and newly acquired data on the chemical and isotopic composition of forearc fluids, fluid fluxes, and the associated thermal regimes in well-studied, representative erosional and accretionary subduction zone (SZ) forearcs. Evidence of large-scale fluid flow, primarily focused along faults, is manifested by widespread seafloor venting, associated biological communities, extensive authigenic carbonate formation, chemical and isotopic anomalies in pore-fluid depth-profiles, and thermal anomalies. The nature of fluid venting seems to differ at the two types of SZs. At both, fluid and gas venting sites are primarily associated with faults. The décollement and coarser-grained stratigraphic horizons are the main fluid conduits at accretionary SZs, whereas at non-accreting and erosive margins, the fluids from compaction and dehydration reactions are to a great extent partitioned between the décollement and focused conduits through the prism, respectively. The measured fluid output fluxes at seeps are high, ∼15–40 times the amount that can be produced through local steady-state compaction, suggesting that in addition, other fluid sources or non-steady-state fluid flow must be involved. Recirculation of seawater must be an important component of the overall forearc output fluid flux in SZs. The most significant chemical and isotopic characteristics of the expelled fluids relative to seawater are: Cl dilution; sulfate, Ca, and Mg depletions; and enrichments in Li, B, Si, Sr, alkalinity, and hydrocarbon concentrations, often distinctive δ18O, δD, δ7Li, δ11B, and δ37Cl values, and variable Sr isotope ratios. These characteristics provide key insights on the source of the fluid and the temperature at the source. Based on the fluid chemistry, the most often reported source temperatures reported are 120–150 °C. We estimate a residence time of the global ocean in SZs of ∼100 Myr, about five times faster than the previous estimate of ∼500 Myr by Moore and Vrolijk, similar to the residence time of ∼90 Myr for fluids in the global ridge crest estimated by Elderfield and Schultz, and ∼3 times longer than the 20–36 Myr estimate by German and von Damm and Mottl. Based on this extrapolated fluid reflux to the global ocean, subduction zones are an important source and sink for several elements and isotopic ratios, in particular an important sink for seawater sulfate, Ca and Mg, and an important source of Li and B.

Description: Uncertainty over the identity and age of Toba tephras across peninsular India persists, with radiometric age dates contradicting earlier compositional data, which have been used to identify this important Stratigraphie marker as the Youngest Toba Tuff (YTT). To address this issue, new single glass shard analyses have been performed for samples from Morgaon and Bori (north-western India), which have recently been dated at c. 800 ka. These, and indeed all Toba tephra samples thus far analysed from India, show the presence of four populations of glass shards (defined by their Ba/Y ratio), which uniquely identifies them as products of the c. 75-ka Youngest Toba eruption. Confirmation that the YTT fingerprint is characteristic comes from new analyses of Oldest Toba Tuff (OTT) glass shards from five sites in the Indian Ocean. These are compositionally identical to Layer D from the ODP site 758 Sediment core (c. 800 ka), and belong to a single, low-Ba population, clearly different from YTT. These analyses show that there is essentially no reworked OTT material in the YTT eruption, and indicate unequivocally that all known Toba tephra occurrences in India belong to the c. 75-ka Youngest Toba eruption.

Description: A very close coupling exists between changes in atmospheric O2 and CO2 concentrations, owing to the chemistry of photosynthesis, respiration, and combustion. The coupling is not perfect, however, because CO2 variations are partially buffered by reactions involving the inorganic carbon system in seawater, which has no effect on O2. Measurements over the past two decades document variations in O2 on a range of space and time scales, including a long-term decrease driven mostly by fossil fuel burning and seasonal cycles driven by exchanges with the land biosphere and the oceans. In this chapter, these and other features seen in the measurements are described, also discussing variations in the tracer ‘atmospheric potential oxygen,’ which is a linear combination of O2 and CO2 designed to be insensitive to exchanges from the land biosphere and thereby sensitive mostly to oceanic processes. Challenges associated with measuring variations in O2 are addressed, and various applications of the observations are discussed, including quantifying the magnitude of the global land and ocean carbon sinks and testing ocean biogeochemical models. An updated budget for global carbon sinks based on O2 measurements from the Scripps O2 program is presented for the decades of the 1990s and 2000s.

Description: Marine laminated sediments in dysoxic areas of the ocean floor are an excellent archive for high-resolution climate reconstructions. While the existence of discontinuities produced by natural events, such as underwater landslides (slumps), strong bottom currents, and/or bioturbation is usually acknowledged for long records, the extent of their influence on high-resolution sequences is usually not considered. In the present work we show strong evidence for multiple stratigraphic discontinuities in different gravity and box-cores retrieved off Pisco (Peru) covering the last 600 years. Chronostratigraphies are largely based on cross-correlation of distinct sedimentary structures (determined by X-ray image analysis) and validated using 210Pb, 241Am, and 14C profiles, as well as proxy records. The cross-correlation of distinct stratigraphic layers allows for chronostratigraphic tie points and clearly shows that some sedimentary sequences are continuous across scales of tens of kilometers, indicating that regional processes often determine laminae formation. Some differences in laminae thickness were found among cores, which could be explained by different sedimentation rates, spatially variable deposition of diatom blooms, changes in silica dissolution and partial deposition/erosion caused by bottom currents. Using multiple stratigraphic tie points provides clear evidence for laminated sequences present in some cores to be missing in other cores. Moreover, instantaneous depositions from upslope were identified in all the cores disrupting the continuity of the sediment records. These discontinuities (instantaneous deposits and missing sequences) may be due to slumps, possibly triggered by earthquakes and/or erosion by strong bottom currents. In spite of the missing sequences in some cores, a continuous composite record of the last six centuries was reconstructed from spliced sequences of the different cores, which provides a well-constrained temporal framework to develop further high-resolution proxies in this region. The present work shows that paleoreconstructions developed from single cores, particularly in areas with strong seismic activity and/or strong bottom currents, are subject to both temporal gaps and instantaneous depositions from upslope, both of which could be misinterpreted as abrupt climate changes or anomalous climate events. We stress the need for multiple cores to determine the stratigraphic continuity and chronologies for high-resolution records.

Description: Forazoline A, a novel antifungal polyketide with in vivo efficacy against Candida albicans, was discovered using LCMS-based metabolomics to investigate marine-invertebrate-associated bacteria. Forazoline A had a highly unusual and unprecedented skeleton. Acquisition of 13C–13C gCOSY and 13C–15N HMQC NMR data provided the direct carbon–carbon and carbon–nitrogen connectivity, respectively. This approach represents the first example of determining direct 13C–15N connectivity for a natural product. Using yeast chemical genomics, we propose that forazoline A operated through a new mechanism of action with a phenotypic outcome of disrupting membrane integrity.

Description: Kelp forests represent a major habitat type in coastal waters worldwide and their structure and distribution is predicted to change due to global warming. Despite their ecological and economical importance, there is still a lack of reliable spatial information on their abundance and distribution. In recent years, various hydroacoustic mapping techniques for sublittoral environments evolved. However, in turbid coastal waters, such as off the island of Helgoland (Germany, North Sea), the kelp vegetation is present in shallow water depths normally excluded from hydroacoustic surveys. In this study, single beam survey data consisting of the two seafloor parameters roughness and hardness were obtained with RoxAnn from water depth between 2 and 18 m. Our primary aim was to reliably detect the kelp forest habitat with different densities and distinguish it from other vegetated zones. Five habitat classes were identified using underwater-video and were applied for classification of acoustic signatures. Subsequently, spatial prediction maps were produced via two classification approaches: Linear discriminant analysis (LDA) and manual classification routine (MC). LDA was able to distinguish dense kelp forest from other habitats (i.e. mixed seaweed vegetation, sand, and barren bedrock), but no variances in kelp density. In contrast, MC also provided information on medium dense kelp distribution which is characterized by intermediate roughness and hardness values evoked by reduced kelp abundances. The prediction maps reach accordance levels of 62% (LDA) and 68% (MC). The presence of vegetation (kelp and mixed seaweed vegetation) was determined with higher prediction abilities of 75% (LDA) and 76% (MC). Since the different habitat classes reveal acoustic signatures that strongly overlap, the manual classification method was more appropriate for separating different kelp forest densities and low-lying vegetation. It became evident that the occurrence of kelp in this area is not simply linked to water depth. Moreover, this study shows that the two seafloor parameters collected with RoxAnn are suitable indicators for the discrimination of different densely vegetated seafloor habitats in shallow environments.

Description: Eutrophication, coupled with loss of herbivory due to habitat degradation and overharvesting, has increased the frequency and severity of macroalgal blooms worldwide. Macroalgal blooms interfere with human activities in coastal areas, and sometimes necessitate costly algal removal programmes. They also have many detrimental effects on marine and estuarine ecosystems, including induction of hypoxia, release of toxic hydrogen sulphide into the sediments and atmosphere, and the loss of ecologically and economically important species. However, macroalgal blooms can also increase habitat complexity, provide organisms with food and shelter, and reduce other problems associated with eutrophication. These contrasting effects make their overall ecological impacts unclear. We conducted a systematic review and meta-analysis to estimate the overall effects of macroalgal blooms on several key measures of ecosystem structure and functioning in marine ecosystems. We also evaluated some of the ecological and methodological factors that might explain the highly variable effects observed in different studies. Averaged across all studies, macroalgal blooms had negative effects on the abundance and species richness of marine organisms, but blooms by different algal taxa had different consequences, ranging from strong negative to strong positive effects. Blooms' effects on species richness also depended on the habitat where they occurred, with the strongest negative effects seen in sandy or muddy subtidal habitats and in the rocky intertidal. Invertebrate communities also appeared to be particularly sensitive to blooms, suffering reductions in their abundance, species richness, and diversity. The total net primary productivity, gross primary productivity, and respiration of benthic ecosystems were higher during macroalgal blooms, but blooms had negative effects on the productivity and respiration of other organisms. These results suggest that, in addition to their direct social and economic costs, macroalgal blooms have ecological effects that may alter their capacity to deliver important ecosystem services.